PEARSON Fundamentals of Organic Chemistry Volume 1

VOLUME I
FUNDAMENTALS OF
ORGANIC
CHEMISTRY
for the JEE (Main and Advanced)
ANANYA GANGULY
Fundamentals of
Organic Chemistry
for the J E E
(Main and Advanced)
Volume I
Ananya Ganguly
00 Prelims Volume I.indd 1 4/7/2015 1:07:09 PM

To my son Ayushman
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Contents
Preface vii
Acknowledgments viii
Chapter 1 IUPAC NOMENCLATURE 1.1–1.82

Drawing Organic Molecules 1.2
Classification of Carbon and Hydrogen of Organic Compound 1.8
Nomenclature of Organic Compounds 1.10
Rules for Nomenclature (Alkanes) 1.15
Rules for Naming Compounds Containing Double and Triple Bonds 1.20
Nomenclature of Compounds Containing Functional Groups 1.22
Nomenclature of Compounds with More than One Similar Functional Groups 1.34
Writing the Structure of the Compound Whose Name is Given 1.49
The Names of Aromatic Compounds Elementary Idea 1.55
Aromatic Compounds with More than One Group Attached to the Benzene Ring 1.58
Nomenclature of Substituted Benzene Compounds—A Detailed Approach 1.59
ARYL Groups 1.60
Solved Conceptual Examples 1.68
Conceptual Assignments 1.72
Solutions 1.81
Chapter 2 GENERAL ORGANIC CHEMISTRY 2.1–2.278

Electronic Structure 2.1
Formal Charge 2.4
Octet Rule 2.6
Bonding in Methane and Ethane 2.8
Bonding in Ethene 2.11
Bonding in Ethyne (Acetylene) 2.13
Bonding in Benzene 2.15
Bonding in Carbonyl Compounds 2.18
Electronegativity 2.20
VSEPR Theory 2.23
Representation of a Chemical Reaction 2.27
Applications of inductive Effect 2.37
Resonance 2.40
Hyperconjugation 2.46
Aromaticity 2.51
Resonance Energy 2.56
Rearrangement in Carbocations 2.78

iv Contents
Carbanions 2.90
Free Radicals 2.100
Carbenes 2.107
Arynes 2.111
Nitrenes 2.113
Concept of Acids and Bases 2.116
Ortho Effect 2.131
Bases 2.140
Basicity 2.141
Isomerism 2.149
Tautomerism 2.158
Optical Isomerism 2.171
Conformations of Alkanes: Rotation About Carbon-Carbon Single Bonds 2.194
Cycloalkanes: Ring Strain 2.198
Conformations of Cyclohexane 2.200
Conformations of Monosubstituted Cyclohexanes 2.203
15 Nitrogen and Phosphours Chirality Centres 2.204
Conformations of Disubstituted Cyclohexanes 2.205
Conformations of 1,3-Disubstituted Cyclohexanes 2.206
Conformations of 1,2-Disubstituted Cyclohexanes 2.207
Conformations of Fused Rings 2.208
Stereochemistry of Reactions: Regioselective, Stereoselective, and Stereospecific Reactions 2.209
Solutions 2.254
Chapter 3 HYDROCARBON3.1–3.180
Saturated Hydrocarbons - Alkanes 3.1
Chemical Properties of Alkanes 3.18
Unsaturated Hydrocarbons Alkene 3.31
Nomenclature (See chapter ‘nomenclature’ for detail) 3.32
Diels - Alder Reaction 3.84
Alkyne 3.92
Solutions 3.157
Chapter 4 ELECTROPHILIC AROMATIC SUBSTITUTION 4.1–4.118
Aromaticity 4.1
Electrophilic Aromatic Substitution Reactions on Benzene 4.1
Nitration of Benzene 4.7
Friedel-Crafts Reaction 4.8
Halogenation 4.19
Sulphonation 4.20
Protonation 4.21
Chloromethylation 4.23
Reactivity and Orientation in Electrophilic Aromatic Substitution 4.30
Theory of Substituent Effects on Electrophilic Aromatic Substitution 4.40
Classification of Substituents 4.41
Reactions of Alkyl Benzenes 4.43
Birch Reduction 4.47
Aryl Halides 4.67
Nucleophilic Aromatic Substituents 4.71

Contents v
Reactions with Benzyne as the intermediate by Elimination-Addition Mechanism 4.77

Ipso Substitution 4.82
Solutions 4.108
Chapter 5 ANALYSIS OF ORGANIC COMPOUNDS 5.1–5.65

Purification of organic Compounds 5.1
Qualitative Analysis 5.15
Quantitative Elemental Analysis 5.23
Solutions 5.51

This page is intentionally left blank
Preface
I am indeed very delighted to present the book Fundamentals of Organic Chemistry for the JEE (Main and Advanced)
Volume I to the readers with elaborated concepts along with more solved and unsolved problems.
In all competitive examinations, there are several vital areas that a candidate needs to master—organic chemistry being
one of them. There are various books in the market on this topic having different approaches; however this book provides
simple, shortcut methods and time-saving tactics which are helpful during the examination to the students. It will also help
you to gain confidence through the right approach to a particular questions rather than attempting number of questions.
This book would be extremely useful for the students who enroll for examinations like JEE (Main and Advanced) and for
other engineering entrance examinations.
In order to bridge the gap between theory and practical, each concept is explained in detail, in an easy-to-understand
manner supported with numerous worked-out examples and practical. These will stimulate thought and facilitate advanced
learning.
One of the important factors that contribute to the success of a book is the way it has been developed. This book reflects
my experience and understanding of the requirements of the students. The methods and approaches discussed in this book
are tried and tested modes of instruction in the class.
Fundamentals of Organic Chemistry, Volume I cover topics like, IUPAC Nomenclature, General Organic Chemistry,
Hydrocarbon, Electrophilic Aromatic Substitution, and Analysis of Organic Compounds. Volume II covers, Alkyl Halides
and Aryl Halides, Alcohol, Phenol and Ether, Aldehyde and Ketone, Carboxylic Acids and Derivatives, Nitrogen Containing
Compounds, Carbohydrates, Amino Acids and Polymers.
I am sure that readers will appreciate this book and will find this book very useful to prepare for various examinations.
Your comments and suggestions would be very useful in improving the subsequent editions of this book.
Although we have taken utmost care to prepare the manuscript and checking subsequent proofs, there may be a
possibility of some errors creeping inside the book. We will welcome suggestions for further improvement of the book.
Please mail us your suggestions on: chemistrycoach1@gmail.com.
Ananya Ganguly

Acknowledgments
Fundamentals of Organic Chemistry, Volume I is the result of encouragement that I received from my students, who
insisted that, my knowledge and experience should benefit a wider audience.
I would like to thank my friends who have, over the years, been my support and strength. Writing this book has been a
long but fulfilling journey and I am fortunate to be assisted by a talented team of editors.
I am indebted to my family for keeping me motivated during all stages of the project. I always feel a divine power sup-
porting my efforts when my family is around. They actually made me work harder on the project.
I extend my sincere thanks to Pearson editorial team for their constant encouragement and support during the publica-
tion of this book.

IUPAC Nomenclature
1
Introduction
Carbon is the fourth most abundant chemical element in the universe by mass after hydrogen, helium, and oxygen. Carbon
is abundant in the Sun, stars, comets, and in the atmospheres of most planets.
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, com-
position, reactions, and preparation (by synthesis or by other means) of carbon-based compounds, hydrocarbons, and their
derivatives. These compounds may contain any number of other elements, including hydrogen, nitrogen, oxygen, the
halogens as well as phosphorus, silicon and sulphur.
An organic compound is any member of a large class of gaseous, liquid, or solid chemical compounds whose mol-
ecules contain carbon. For historical reasons discussed below, a few types of carbon-containing compounds such as car-
bides, carbonates, simpleoxides of carbon, and cyanides, as well as the allotropes of carbon such as diamond and graphite,
are considered inorganic. The distinction between “organic” and “inorganic” carbon compounds, while ‛useful in organiz-
ing the vast subject of chemistry... is somewhat arbitrary’.
Organic chemistry is the science concerned with all aspects of organic compounds. Organic synthesis is the methodol-
ogy of their preparation.
Vitalism
The word ‛organic’ is historical, dating back to the 1st century. For many centuries, Western alchemists believed in vital-
ism. This is the theory that certain compounds could be synthesized only from their classical elements — earth, water,
air, and fire — by action of a ‛life-force’ (vis vitalis) possessed only by organisms. Vitalism taught that these ‛organic’
compounds were fundamentally different from the ‛inorganic’ compounds that could be obtained from the elements by
chemical manipulation.
Vitalism survived for a while even after the rise of modern atomic theory and the replacement of the Aristotelian ele-
ments by those we know today. It first came under question in 1824, when Friedrich Wöhler synthesized oxalic acid, a
compound known to occur only in living organisms, from cyanogen. A more decisive experiment was Wöhler’s 1828
synthesis of urea from the inorganic salts potassium cyanate and ammonium sulfate. Urea had long been considered to be
an ‛organic’ compound, as it was known to occur only in the urine of living organisms. Wöhler’s experiments were fol-
lowed by many others, where increasingly complex ‛organic’ substances were produced from ‛inorganic’ ones without the
involvement of any living organism.
Modern Classification
Even after vitalism had been disproved, the distinction between ‛organic’ and ‛inorganic’ compounds has been retained
through the present. The modern meaning of ‛organic compound’ is any one of them that contains a significant amount of
carbon - even though many of the ‛organic compounds’ known today have no connection whatsoever with any substance
found in living organisms.
1.2 IUPAC Nomenclature
There is no ‛official’ definition of an organic compound. Some textbooks define an organic compound as one contain-
ing one or more C-H bonds; others include C-C bonds in the definition. Others state that if a molecule contains carbon―it
is organic.
Even the broader definition of ‛carbon-containing molecules’ requires the exclusion of carbon-containing alloys (in-
cluding steel), a relatively small number of carbon-containing compounds such as metal carbonates and carbonyls, simple
oxides of carbon and cyanides, as well as the allotropes of carbon and simple carbon halides and sulfides, which are usually
considered to be inorganic.
The ‛C-H’ definition excludes compounds that are historically and practically considered to be organic. Neither urea
nor oxalic acid is organic by this definition, yet they were two key compounds in the vitalism debate. The IUPAC Blue
Book on organic nomenclature specifically mentions urea and oxalic acid. Other compounds lacking C-H bonds that are
also traditionally considered to be organic include benzenehexol, mesoxalic acid, and carbon tetrachloride. Mellitic acid,
which contains no C-H bonds, is considered to be a possible organic substance in Martian soil. All do, however, contain
C-C bonds.
The ‛C-H bond only’ rule also leads to somewhat arbitrary divisions in sets of carbon-fluorine compounds, as, for ex-
ample, Teflon is considered by this rule ‛inorganic’ but Tefzel organic. Likewise, many Halons are considered inorganic,
whereas the rest are considered organic. For these and other reasons, most sources consider C-H compounds to be only a
subset of ‛organic’ compounds.
In summary, most carbon-containing compounds are organic, and most compounds with a C-H bond are organic. Not
all organic compounds necessarily contain C-H bonds (e.g., urea).
DRAWING ORGANIC MOLECULES

This page explains the various ways that organic molecules can be represented on paper or on screen - including molecular
formulae and various forms of structural formulae.
Molecular Formulae
A molecular formula simply counts the numbers of each sort of atom present in the molecule, but tells you nothing about
the way they are joined together.
For example, the molecular formula of butane is C4H10, and the molecular formula of ethanol is C2H6O.
Molecular formulae are very rarely used in organic chemistry, because they don't give any useful information about
the bonding in the molecule. About the only place where you might come across them is in equations for the combustion
of simple hydrocarbons, for example:
C5H12 + 8O2 5CO2 + 6H2O
In cases like this, the bonding in the organic molecule isn't important.
Structural Formulae
A structural formula shows how the various atoms are bonded. There are various ways of drawing this and you will need
to be familiar with all of them.
Displayed Formulae
A displayed formula shows all the bonds in a molecule as individual lines. You need to remember that each line represents
a pair of shared electrons.
For example, this is a model of methane together with its displayed formula:
+
+ & +
+
IUPAC Nomenclature 1.3
Notice that the way methane is drawn bears no resemblance to the actual shape of the molecule. Methane is not flat with
90° bond angles. This mismatch between what you draw and what the molecule actually looks like can lead to problems
if you aren't careful.
For example, consider a simple molecule with the molecular formula CH2Cl2. You might think that there were two dif-
ferent ways of arranging these atoms if you drew a displayed formula.
+ +
&O & &O + & &O
+ &O
The chlorines could be opposite each other or at right angles to each other. But these two structures are actually exactly
the same. Look at how they appear as models.
catch hold of the top

hydrogen and rotate the
molecule a bit
One structure is, in reality, a simple rotation of the other one.

Consider a slightly more complicated molecule, C2H5Cl. The displayed formula could be written as either of these:
+ + + &O
+ & & &O + & & +
+ + + +
But, again these are exactly the same. Look at the models.
ULJKWKDQGHQGRI
WKHPROHFXOH
URWDWHGDERXWWKH
&&ERQG
The commonest way to draw structural formulae

For anything other than the most simple molecules, drawing a fully displayed formula is a bit of a bother - especially all
the carbon-hydrogen bonds. You can simplify the formula by writing, for example, CH3 or CH2 instead of showing all
these bonds.
So for example, ethanoic acid would be shown in a fully displayed form and a simplified form as:
+
2 2
+ & & &+ &
2 + 2+
+
You could even condense it further to CH3COOH, and would probably do this if you had to write a simple chemical
equation involving ethanoic acid. You do, however, lose something by condensing the acid group in this way because you
can not immediately see how the bonding works.
You still have to be careful in drawing structures in this way. Remember from above that both these structures represent
the same molecule:
+ + + &O
+ & & &O + & & +
+ + + +
All of the next three structures represent butane.

CH3 — CH2 — CH2 — CH3 &+ &+ &+ &+
&+ &+ &+
&+
All of these are just versions of four carbon atoms joined up in a line. The only difference is that there has been some
rotation about some of the carbon-carbon bonds. You can see this in a couple of models.
molecule has been twisted
about this C-C bond
Not one of the structural formulae accurately represents the shape of butane. The convention is that we draw it with all
the carbon atoms in a straight line–as in the first of the above structures.
This is even more important when you start to have branched chains of carbon atoms. The following structures again
represent the same molecule–2-methylbutane.
&+
&+ &+ &+ &+ &+ &+ &+

&+
&+
&+ &+ &+ &+
&+
The two structures on the left are fairly obviously the same–all we have done is flip the molecule over. The other one
is not so obvious until you look at the structure in detail. There are four carbons joined up in a row, with a CH3 group at-
tached to the next-to-end one. That is exactly the same as the other two structures. If you had a model, the only difference
between these three diagrams would be that you would have rotated some of the bonds and turned the model around a bit.
To overcome this possible confusion, the convention is that you always look for the longest possible chain of carbon
atoms, and then draw it horizontally. Anything else is simply hung off that chain.
It does not matter in the least whether you draw any side groups pointing up or down. All of the following represent
exactly the same molecule.
%U
&+ &+ &+ &+ &+ 2+ %U &+
2+ &+ &+ &+ &+ &+ &+

2+ %U %U &+
&+ &+ &+ &+ &+ &+ &+ &+ &+ &+
&+ 2+

If you made a model of one of them, you could turn it into any other one simply by rotating one or more of the carbon-
carbon bonds.
How to draw structural formulae in 3-dimensions
There are occasions when it is important to be able to show the precise 3-D arrangement in parts of some molecules. To do
this, the bonds are shown using conventional symbols:
bond in plane of paper
bond going back into

paper away from you
bond coming out of paper towards you
For example, you might want to show the 3-D arrangement of the groups around the carbon, which has the -OH group
in butan-2-ol.
Butan-2-ol has the structural formula:
&+ &+ &+ &+
2+
Using the conventional bond notation, you could draw it as, for example:
&+&+ &+&+
& RU &
+ &+ + &+
2+ 2+
The only difference between these is a slight rotation of the bond between the two carbon atoms in the centre. This is
shown in the two models below. Look carefully at them–particularly at what has happened to the lone hydrogen atom. In the
left-hand model, it is tucked behind the carbon atom. In the right-hand model, it is in the same plane. The change is very slight.
It doesn't matter in the least which of the two arrangements you draw. You could easily invent other ones as well.
Choose one of them and get into the habit of drawing 3-dimensional structures that way.
Notice that no attempt was made to show the whole molecule in 3-dimensions in the structural formula diagrams. The
CH2CH3 group was left in a simple form. Keep diagrams simple–trying to show too much detail makes the whole thing
amazingly difficult to understand.
Skeletal Formulae
In a skeletal formula, all the hydrogen atoms are removed from carbon chains, leaving just a carbon skeleton with func-
tional groups attached to it.
For example, we have just been talking about butan-2-ol. The normal structural formula and the skeletal formula look
like this:
&+&+&+&+
2+ 2+
In a skeletal diagram of this sort,
 there is a carbon atom at each junction between bonds in a chain and at the end of each bond (unless there is something
else there already, like the -OH group in the example);
 there are enough hydrogen atoms attached to each carbon to make the total number of bonds on that carbon up to 4.
Diagrams of this sort take practice to interpret correctly, and may well not be acceptable to your examiners
(see below).
There are, however, some very common cases where they are frequently used. These cases involve rings of carbon
atoms, which are surprisingly awkward to draw tidily in a normal structural formula.
Cyclohexane, C6H12, is a ring of carbon atoms, each with two hydrogens attached. This is what it looks like in both a
structural formula and a skeletal formula.
&+
&+ &+
&+ &+
&+
F\FORKH[DQH
And this is cyclohexene, which is similar but contains a double bond:
&+
&+ &+
&+ &+
&+
F\FORKH[DQH
But the commonest of all is the benzene ring, C6H6, which has a special symbol of its own.
benzene ring
Bond-Line Formulae
We will use a very simplified formula called a bond-line formula to represent structural formulae. The bond-line repre-
sentation is the quickest of all to write because it shows only the carbon skeleton. The number of hydrogen atoms necessary
to fulfill the carbon atoms’ valences are assumed to be present, but we do not write them in. Other atoms (e.g., O, Cl, N)
are written in and hydrogens attached to those atoms are also written. Each intersection of two or more lines and the end
of a line represent a carbon atom unless some other atom is written in.
&+ &+
&+&+&O&+&+ &+ &+
&O &O
&+ &+
&+&+ &+ &+&+ &+ &+
&+
&+ &+
&+ 1&+&+ 1 &+ 1
&+ %RQGOLQH
IRUPXODH
Bond-line formulae are often used for cyclic compounds:
&+ + & &+

DQG
+ & &+
+ & &+
Muliple bonds are also indicated in bond-line formulae. For example:

&+ &+ &+
& &+ &+ &+&+2+

2+
&+
Problem
1. Outline the carbon skeleton of the following condensed structural formulae and then write each as a bond-line
formula.
(a) (CH3)2CHCH2CH3 (e) CH3CH2CH(OH)CH2CH3
(b) (CH3)2CHCH2CH2OH (f) CH2=C(CH2CH3)2O
2
(c) (CH3)2C=CHCH2CH3 (g) &+&&+&+&+&+
(d) CH3CH2CH2CH2CH3 (h) CH3CHC1CH2CH(CH3)2
CLASSIFICATION OF CARBON AND HYDROGEN OF ORGANIC COMPOUND

(a) Classification ‘A’–Degree of Carbon Atom and Hydrogen Atom
The degree is assigned on the basis of connectivity of carbon atoms with other carbon atoms in the chain. According to
this classification, we have four types of carbon atoms.
These are:
1. Primary carbon: (1°) A carbon atom linked to one carbon atom
2. Secondary carbon: (2°) A carbon atom linked with two carbon atoms
3. Tertiary carbon: (3°) A carbon attached to three carbon atoms
4. Quaternary carbon: (4°) A carbon attached to four carbon atoms
The hydrogens in a molecule are also referred to as primary, secondary, and tertiary. Primary hydrogens are attached
to primary carbons, secondary hydrogens are attached to secondary carbons, and tertiary hydrogens are attached to
tertiary carbons. There is no Quaternary Hydrogen atom.

+ + &+ &+
+ & & & & &+
+ + + &+

SULPDU\K\GURJHQ WHUWLDU\K\GURJHQ VHFRQGDU\K\GURJHQ &+
&+&+&+&+2+ &+&+&+2+ &+&+&+2+ &+&2+
&+ &+ &+
SULPDU\K\GURJHQ WHUWLDU\K\GURJHQ VHFRQGDU\K\GURJHQ
EXW\ODOFRKRO LVREXW\ODOFRKRO VHFEXW\ODOFRKRO WHUWEXW\ODOFRKRO

RU RU
VEXW\ODOFRKRO WEXW\ODOFRKRO
Illustration
1. (a) Provide a structural formula for CH3CH2C(CH3)2CH2CH(CH3)2, and define and identify all the primary (1°),
secondary (2°), tertiary (3°), and quaternary (4°) C’s. (b) Identify all the 1°, 2°, and 3° H’s. (e) Give number of H
atoms bonded to a 1°, 2°, 3°, and 4° carbon atom in an alkane. (d) Give the number of C atoms bonded to a 1°,
2°, 3°, and 4° carbon atom in an alkane.
Ans. (a) In the condensed formula all atoms or groups written after a C are bonded to it.
+ + +
+ + +
+ + &D + &D +
D E
+ &D &E &G &E &F &D + F G
+ + &D + + +
+ + +
1 °C is bonded to only one other C, a 2 °C to two other C’s, a 3 °C to three other C’s, and a 4° to four other
C’s. (The C of CH4 is super F.)
(b) 1 °H’s are those attached to 1 °C’s, 2 °H’s to 2 °C’s, and 3 °H’s to 3 °C’s. Other atoms or groups bonded to
C, like halogen, are similarly identified. (A 4 °H cannot exist because all four bonds of a 4 °C are bonded to
other C’s.)
(c) 3, 2, 1, and 0.
(d) 1, 2, 3, and 4.
(b) Classification ‘B’–With Respect to the Functional Group

In this method, the relative positions of different carbon atoms in a molecule are designated by small letters of Greek
alphabets with respect to the functional group it contains. The carbon atom directly attached to the functional group is
designated as a-C, the carbon atom next to it is indicated as b-C atom and the next to b-C is g-C atom and so on. Each of
the hydrogen’s is given the smaller a, b, g, d designation as the carbon atom to which it is attached.
For example,
&+ &+ &+ &+ &+2
G J E D )XQFWLRQDO
JURXS
(c) Alkyl Groups

An alkyl substituent (or an alkyl group) is an alkane from which a single hydrogen has been removed. Alkyl substituents
are named by replacing the ‛ane’ ending of the alkane with ‛yl.’ The letter ‛R’ is used to indicate any alkyl group.
&+ &+ &+ &+&+&+ &+&+ &+&+
DPHWK\OJURXS DQHWK\OJURXS DSURS\OJURXS DEXW\OJURXS
5
DQ\DON\OJURXS
Iso alkyl group: An alkyl group in which the second last carbon in the chain is branched to one –CH3 group.
For Example,
5HPRYDORI+
+& &+ &+
IURPFDUERQ
QSURS\OJURXS
+ & &+ &+
+& &+ &+

IURPFDUERQ
,VRRUVHFSURS\OJURXS
5HPRYDORI+
&+ &+ &+
IURP
FDUERQ &+
&+ &+ &+ ,VREXW\OJURXS
&+ 5HPRYDO PHWK\OSURS\O
RI+
&+
IURP
FDUERQ &+ & &+
7HUWLDU\EXW\OJURXS
>ccGLPHWK\OHWK\O@
&+ &+
VHFRQGDU\EXW\O>ccGLPHWK\O
&+ &+ HWK\O@
Neoalkyl Group
The alkyl group in which second last carbon of the chain is branched to two CH3 groups.
For Example
&+
&+ & &+ QHRSHQW\ORUGLPHWK\O
SURS\O
&+
&+ &+ VHFRQGDU\SHQW\ORU

PHWK\OEXW\O
&+ &+ &+
(d) Unsaturated Alkyl Group

CH2 = CH – Vinyl or ethenyl
CH2 = CH – CH2 – Alkyl or prop-2-enyl
CH3 – CH = CH – x prop-1-enyl
CH3 – CH = CH – CH2 – Crotyl

C6H5 – CH = CH – CH2 – Cinnamyl
C6H5 – Phenyl
C6H5CH2– Benzyl
+ & Tolyl
NOMENCLATURE OF ORGANIC COMPOUNDS

(A) Common or Trivial Nomenclature
In the early days, an organic compound was named as per its origin or its characteristic properties. These names are called
common names or trivial names. Take an example of formic acid (HCOOH). It originates from ants and the Latin name of
ant is formicium and also it behaves like an acid. Thus the name formic acid is given. More examples,
 Wood alcohol from wood

 Cocaine front Peruvian cocoa leaves
 Butyric acid from rancid butter
 Buckminsterfullerene is a common name given to the newly discovered C60 cluster (a form of carbon) noting its struc-
tural similarity to the geodesic domes popularized by the famous architect R. Buckminster Fuller.
Common names are useful, and in many cases indispensable, particularly when the alternative systematic names are
lengthy and complicated. Common names of some organic compounds are given in Table 1.1.
Table 1.1 Some Common Names of Compounds
Compound Common name

CH4 Methane
H3CCH2CH2CH3 n-Butane
(H3C)2CHCH3 Isobutane
(H3C)4C Neopentane
H3CCH2CH2OH n-Propyl alcohol
HCHO Formaldehyde
(H3C)2CO Acetone
CHCl3 Chloroform
CH3COOH Acetic acid
C6H6 Benzene
C6H5OH Phenol
C6H5NH2 Aniline
C6H5COCH3 Acetophenone
CH3OCH3 Dimethyl ether
(B) IUPAC (International Union of Pure and Applied Chemistry) Nomenclature

The IUPAC nomenclature of organic chemistry is a systematic method of naming organic chemical compounds as rec-
ommended by the International Union of Pure and Applied Chemistry (IUPAC). Ideally, every possible organic compound
should have a name from which an unambiguous structural formula can be drawn. There is also an IUPAC nomenclature
of inorganic chemistry.
For ordinary communication, to spare a tedious description, the official IUPAC naming recommendations are not
always followed in practice except when it is necessary to give a concise definition to a compound, or when the IUPAC
name is simpler (e.g. ethanol against ethyl alcohol). Otherwise the common or trivial name may be used, often derived
from the source of the compound. We will observe while naming the organic compounds that in some cases, trivial names
or common names have been retained by IUPAC.
Nomenclature of Organic Compounds

The term nomenclature means the system of naming. The systematic nomenclature of organic compounds is known as
IUPAC (International Union of Pure and Applied Chemistry) system, which is briefly discussed below.
According to IUPAC system, the name of an organic compound, in general, consists of the following parts:
(i) Word root
(ii) Primary suffix
(iii) Secondary suffix
(iv) Prefix(es)
(i) Word root: The word root represents the number of carbon atoms in the parent chain. The general word root for different
aliphatic compounds is ALK. The word root for different lengths of carbon chains are given below in Table 1.2.
Table 1.2 Some Prefixes
Number of carbons Prefix

1 Meth
2 Eth
3 Prop
4 But
5 Pent
6 Hex
7 Hept
8 Oct
9 Non
10 Dec
11 Undec
12 Dodec
13 Tridec
14 Tetradec
15 Pentadec
20 Eicos
30 Triacont
40 Tetracont
50 Pentacont
(ii) Primary Suffix: Primary suffix is used to represent saturation or unsaturation in the carbon chain. While writing the
name, primary suffix is added to the word root. Some of the primary suffixes are given below in Table 1.3.
Table 1.3 Some Primary Suffixes
Nature of Carbon Chain Primary Suffix

Saturated Carbon Chain ane
Unsaturated Carbon Chains
One C = C bond ene
Two C = C bonds adiene
Three C = C bonds atriene
One C = C bond yne
Two C = C bonds adiyne
It may be noted that an extra ‘a’ is added to the word root if the primary suffix to be added begins with a constant
(other than a, e, i, o, u.)
For example, for two double bonds, suffix is diene and if it is to be added to word root ‘but’ (for 4C atoms, it
becomes butadiene)
(iii) Secondary Suffix: Secondary suffix is used to indicate the functional group in the organic compounds. The terminal
‘e’ of the primary suffix is dropped if it is followed by a suffix beginning with ‘a’, ‘i’, ‘o’, ‘u’ or ‘y’. But it is retained
if secondary suffix begins with a consonant.
Secondary suffixes for various functional groups are given in Table 1.4.
Table 1.4 Some Organic families and Secondary Suffixes
Class of Organic General Functional Group Suffix IUPAC name of the Family
Compound Formula
(Word + pri. + sec.
root suffix suffix )
Alcohols R–OH –OH -ol Alkanol
Thioalcohols R–SH –SH -thiol Alkanethiol
Amines R–NH2 –NH2 -amine Alkanamine
Aldehydes R–CHO –CHO -al Alkanal
Ketones R–COR > CO -one Alkanone
Carboxylic acids R–COOH –COOH -oic Alkanoic Acid
Amines R–COOH2 –CONH2 -amide Alkanamide
Acid chlorides R–COCl –COCI -oyl chloride Alkanoyl Chloride
Esters R–COOR –COOR -oate Alkyl Alkanoate
Nitriles R–C ≡ N –C ≡ N -nitrile Alkane Nitrile
It may be noted that while adding the secondary suffix to the primary suffix, the terminal ‘e’ of the primary suffix
(i.e. ane, ene or yne) is dropped if the complete secondary suffix (the suffix plus multiplying affix, if any, such as di
tri tetra) begins with a vowel (a, e, i, o, u). However, the terminal ‘–e’ is retained if the secondary suffix begins with
a consonant.
For example,
–CH3 – CH2 – CH2 – CH2 – OH Word root but

Primary suffix ane
Sec. suffix –ol
So, its name is But + ane + ol = Butanol or Butan – 1– ol.

[Here, ‘e’ of ane is dropped because sec. suffix –‘ol’ begins with a vowel.]
(iv) Prefix: Prefix is a part of the name which appears before the word root.
Primary prefix: Indicates that whether the compound is cyclic or acyclic etc., primary prefix cyclo is used
immediately before the word root.
Primary prefix Word root Primary Suffix Secondary Suffix IUPAC name
Cyclo hex ane – Cyclohexane
Secondary Prefix
Prefixes that are used to represent the names of alkyl groups (branched chains) or some functional groups, which are
regarded as substituents, are secondary prefix.
(a) Alkyl groups are formed by the removal of H atom from the alkanes. These are represented by the general
formula CnH2n+1 or R-. Some alkyl groups along with their prefixes are given in Table 1.5.
Table 1.5 Some Alkyl Groups along with their Prefixes
Alkane Alkyl Group Abbreviation Prefix

CH4 CH3– Me- Methyl
C2H6 CH3CH2–– Et- Ethyl
C3H8 CH3CH2CH2– n-Pr- n-Propyl
C3H8 CH3– CH– Iso-Pro Isopropyl
|
CH3

Some unsaturated groups are given below :
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(b) Some functional groups are always indicated by the prefixes instead of secondary suffixes. These functional groups
along with their prefixes are listed in Table 1.6.
Table 1.6 Functional groups which are always represented by prefixes
Functional Group Prefix Family IUPAC Name

— NO2 Nitro R— NO2 Nitroalkane
— OR' alkoxy R— OR' Alkoxyalkane
— Cl Chloro R— Cl Chloroalkane
— Br Bromo R— Br Bromoalkane
—I lodo R— I Iodoalkane
—F Fluoro R— F Fluoroalkane
— NO Nitroso R— NO Nitrosoalkane
Table 1.7 Some Characteristic Groups with their Prefixes
Characteristic group Prefix

— CIO Chlorosyl-
— CIO2 Chloryl-
— CIO3 Perchloryl-
— IO Iodosyl-
— IO2 Iodyl-(replaces iodoxy-)
— I(OH)2 Dihydroxy-l3- iodanyl-(replaces dihydroxyiodo-)
— IX2 Dihydroxy-l3- iodanyl-(replaces dihaloiodo-)
= N2 Diazo-
— N3 Azido-
— SR (R)-sulfanyl- (and similarly, (R)-selanyl- and (R)-tellanyl-)
— SH3 l4-Sulf Anyl-
(c) In polyfunctional compounds, i.e., compounds with more than one functional group, one of the functional groups is
treated as the principal functional group and is indicated by the secondary suffix, whereas the other functional groups are
treated as substituents and are indicated by prefixes. The prefixes for various functional groups are given in Table 1.8.
Table 1.8 Prefixes for functional groups in polyfunctional compounds
Functional Group Prefix Functional Group Prefix

—OH Hydroxy — COOH Carboxy
— CN Cyano — COOR Carbalkoxy
— NC Isocyano — COCl Chloroformyl
— CHO Formyl or Aldo — CONH2 Carbamoyl
— SH Mercapto — NH2 Amino
— SR Alkylthio >CO Keto or Oxo
Arrangement of Prefixes, Word root and Suffixes: The prefixes, word root and suffixes are arranged as follows while
writing the name.
Prefix(es) + Word root + p. suffix + sec. suffix
RULES FOR NOMENCLATURE (ALKANES)

(A) Saturated Hydrocarbons (Alkanes)
Case-1. Unbranched alkane
Count the number of C-atoms and write the name depending on the number of C-atoms as mentioned in table 1.2, i.e. for
1 carbon–methane, for 2 carbons–ethane etc.
Case-2. Branched alkane
Rule 1. Longest chain rule
Select the longest continuous chain of carbon atoms in the molecule. The selected chain, containing the maximum number
of carbon atoms, is regarded as the parent or root chain . It gives the name of the parent hydrocarbon. Carbon atoms which
are not included in the parent chain are identified as substituents.
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6XEVWLWXHQWV
 For example, in the following compound, the parent chain consists of nine carbon atoms (structure I) and not eight
(structure II). So, the compound is named as derivative of nonane.
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Rule 2. Lowest Number or Lowest Sum Rule

The selected parent chain is numbered using Arabic numerals and the position of the alkyl group is indicated by the number
of the carbon atom to which the alkyl group is attached. The numbering is done in such a way that the substituted carbon
atoms have the lowest possible numbers.
For example, if X represents a substituent, then the correct numbering of the carbon chain is as given in structure A.
The numbering of the carbon chain as given in structure B is wrong because it gives higher number to the carbon atom
carrying the substituent.
; ;

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$ &RUUHFW % :URQJ
The number that indicates the position of the substituent or side chain is called locant. When series of the locants con-
taining the same number of terms are compared term by term, that series is lowest which contains the lowest number on
the occasion of first difference. Some examples are given below to illustrate the above idea:
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7ULPHWK\OKH[DQHDQGQRW &+ &+ &+

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The names of alkyl groups attached as a branch are then prefixed to the name of the parent alkane, and the posi-
tion of the substituents is indicated by the appropriate numbers. If different alkyl groups are present, they are listed in
alphabetical order.
For example,

&+ &+ &+ &+ &+ &+ &+
&+ &+ &+
(WK\OPHWK\OKHSWDQH
 It must be remembered that numbers are separated from the groups by hyphens, and there is no break between sub-
stituent and alkane names, i.e., between methyl and pentane, or ethyl and hexane.
Rule 3. Use of Prefixes Di, Tri, etc.

If the compound contains more than one similar alkyl groups, their positions are indicated separately and an appropriate
numerical prefix, di, tri, etc., is attached to the name of the substituents. The positions of the substitutents are separated by
commas. For example,
&+&+
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&+ &+

&
&+
&+

&+
&+
&+
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'LPHWK\OSHQWDQH 'LHWK\OSHQWDQH
Table 1.9 Basic numerical terms (multiplying affixes)
Number Numerical term Number Numerical term

1 mono- 90 nonaconta-
2 di- 100 hecta-
3 tri- 200 dicta-
4 tetra- 300 tricta-
5 penta- 400 tetracta-
6 hexa- 500 pentacta-
7 hepta- 600 hexacta-
8 octa- 700 heptacta-
9 nona- 800 octacta-
10 deca- 900 nonacta-
11 undeca- 1000 kilia-
12 dodeca- 2000 dilia-
20 icosa- 3000 trilia-
30 triaconta- 4000 tetralia-
40 tetraconta- 5000 pentalia-
50 pentaconta- 6000 hexalia-
60 hexaconta- 7000 heptalia-
70 heptaconta- 8000 octalia-
80 octaconta- 9000 nonalia-
Rule 4. Alphabetical Arrangement of Prefixes

If there are different alkyl substituents present in a compound, their names are written in the alphabetical order. However,
the numerical prefixes such as di, tri, etc. are not considered for the alphabetical order. For example,
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&+ &+

&+
&+
&+ &+

&+
&
&+
&+
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Rule 5. Naming different alkyl substituents at the equivalent positions

If two different alkyl groups are located at the equivalent positions, then numering of the chain is done in such a way that the
alkyl group which comes first in alphabetic order gets the lower position. For example, if ethyl and methyl groups are present
at equivalent positions, then carbon bearing ethyl group should get the lower number as illustrated in the following example.
&+ &+

&+ &+

&+
&+ &+

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(WK\OPHWK\OKH[DQH
Rule 6. Naming the Complex Alkyl Substituents

If the alkyl substituent is further branched, it is named as substituted alkyl group. In the complex substituent, the number-
ing of the carbon atoms is also done. The carbon atom attached to the parent chain is always numbered as 1. The prefix/
name of such a substituents is enclosed in brackets as illustrated in the following examples.
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The numerical prefixes ‘bis-’, ‘tris-’, ‘tetrakis-’, ‘pentakis-’ etc. are used to indicate a multiplicity of substituted sub-
stituents. The name of the substituted substituent is enclosed in parentheses. For example,
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Some Important Notes

1. For the alphabetical order of the various substituents, the name of the complex substituent is considered to begin with
the first letter of the complete name. We know that in case of simple substituents the multiplying prefixes are not
considered , however, they are regarded to be the part of the name for the complex substituent.
For example,
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2. It may be noted that dimethyl propyl (a complex substitution) is alphabetized under ‛d’ and not under ‛m’. Therefore,
it is cited before ethyl (e).
3. When the names of two or more complex substituents are composed of identical words, priority is given to the sub
substituent with lower locant at the first cited point of difference within the complex substituent.
For example,
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The substituent (1-methylbutyl) is written first because it has lower locant that the substituent (2-methylbutyl).
4. When there are more than one same complex substituents, it is indicated by the multiplying prefix bis (for two), tris
(for three), tetra kis (for four), etc.
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5. The prefixes iso- and neo- are considered to be part of alkyl group. The prefixes sec- and tert- are not considered to be
part of fundamental name. The use of ‘iso’ and related common prefixes for naming alkyl group is also allowed by
the IUPAC nomenclature as long as these are not further substituted.
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RULES FOR NAMING COMPOUNDS CONTAINING DOUBLE AND TRIPLE BONDS

1. Select the longest continuous chain of carbon atoms as the parent chain. If some carbon-carbon multiple bond is
present, the parent chain must contain the carbon atoms involved in it. The number of carbon atoms in the parent
chain determines the word root. The carbon atoms which are not included in the parent chain are considered alkyl
substituents and they determine the prefixes.
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&RUUHFWFKDLQ :URQJFKDLQ
If two equally long chains are possible, the chain with maximum number of side chains is selected as parent chain.
Note: It may be noted that the selected chain containing double or triple bonded carbon atoms (must include both the
carbon atoms of the double bond or triple bond) may or may not be the longest chain in the structure. For example, in the
above structure, the longest chain containing double bonded carbon atoms is of five carbon atoms and not of six.
Suffixes Denoting Multiple Bonds
The presence of one or more double or triple bonds in an otherwise saturated parent hydride (except for parent hydrides
with Hantzsch-Widman names) is denoted by changing the ‛-ane’ ending of the name of a saturated parent hydride to one
of the following:
Table 1.10
One Two Three etc.

Double bond -ene -adiene -atriene etc.
Triple bond -yne -adiyne -atriyne etc.
1. The presence of both double and triple bonds is similarly denoted by endings such as ‛-enyne’, ‛-adienyne’, ‛-enediyne’,
etc. Numbers as low as possible are given to double and triple bonds as a set, even though this may at times give ‛-yne’
a lower number than ‛-ene’. If a choice remains, preference for low locants is given to the double bonds. Only the
lower locant for a multiple bond is cited except when the numerical difference between the two locants is greater than
one, in which case the higher-numbered locant is cited in parentheses.
2. While writing the name of the alkene or alkyne, the suffix ‘ane’ of the corresponding alkane is replaced by ‘ene’ or
‘yne’ respectively.
3. The numbering must begin with the one end of the parent chain, but this is done in such a way that carbon atom
carrying the multiple bonds gets the lowest number. The position of the multiple bond is then indicated by using the
number of the first C-atom of the multiple bond.
Note: It may be noted that we give the lowest number to the carbon atom having double or triple bond and not to any
side chain (as in alkanes).

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4. All the rules for naming side chains or substituents are then followed (same as in alkanes).
5. If the multiple bond occurs two or more times in the chain, then it is named as diene or diyne, triene or triyne etc. The
positions or multiple bonds are also prefixed with numbers.
Some examples are given below:

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5. If the parent chain contains both the double and triple bonds, the following points should be followed:
If double bond and triple bond get the same locant from two sides of the parent carbon chain, double bond gets the
priority in the numbering but the name ends with triple bond. Example is given below.

+& & &+ & Ł &+
3HQWDHQ\QH
 The terminal ‘e’ in the name of alkene is dropped if it is followed by the suffix beginning with a,e, i, o, u. For example,
terminal ‘e’ of the ene is dropped in the following cases:
en – yne adien – yne

However, terminal ‛e’ is not dropped in case of ‛ene – diyne’ because it comes before diyne.

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3HQWDHQ\QH +H[DGLHQ\QH
3UHIHUHQFHRIORFDQWIRUHQH

+&Ł& &+ &+ &+
3HQWHQ\QH
Examples

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+&
+3 3 3+

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&+

+ & +& &+

+H[DGLHQH 3HQW\QH
&+
+& +& &+

+H[D 3HQWHQ\QH
GLHQ\QH

1+ 1
+ 1 1
1+

3HQWDD]HQH
13 1 2
12 3
11 14 4
10 8 5
9
Bicyclo[6.5.1]
tetradec-1(13)-ene
NOMENCLATURE OF COMPOUNDS CONTAINING FUNCTIONAL GROUPS

The rules for naming an organic compound are exactly the same as discussed already for compounds containing multiple
bonds. In this case, the preference for the lowest number is given to the carbon atom containing a functional group. The
rules are summarised below:
1. Select the longest continuous chain containing the carbon atom having a functional group. This is illustrated below:
)XQFWLRQDO*URXS
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&+ &+ & &+ &+ &+ &+ &+ & &+ &+ &+
&+ &+
&RUUHFW :URQJ
2. The numbering of atoms in the parent chain is done is such a way that carbon atom bearing the functional group gets
the lowest number.
3. All the rules for naming side chains or substituents are then followed as discussed in case of alkanes.
Let us apply these rules to write the names of some compounds.

&+ &+ 2

&+ & 2+ &+ & &+2+ &+ &+ &+ & &+ &+

&+ &+ &+
0HWK\OSURSDQRO 'LPHWK\OSURSDQRO 0HWK\ORQH
It may be noted that the functional group should get the lowest number even if it violates the lowest locant
rule.
&+

&+ & &+ &+ &+ &+ &+ &+ &+ &+&+2

&+&+ 2+ &+
0HWK\OKHSWDQDO
&+&+

(WK\OGLPHWK\OKHSWDQRO
It may be noted that if functional groups such as –CHO, –COOH, –CONH2, –COOR, –CN etc. are present in the
molecule, the numbering of the parent chain in such a case must start from the carbon atom of the functional group.
However, this number is normally not indicated in the IUPAC name of the compound.
&+

&+ &+ & &+ &+ &+&+ &+ &+

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4. Rules for Naming Compounds having functional groups, multiple bonds and side chains substituents:
If the organic compound contains a functional group, multiple bond, side chain or the substituent, the following order
of preference must be followed:
Functional group > Double bond > Triple bond > Side chain
For example,
&+

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%XWHQHGLRLFDFLG RU
0HWK\OKH[HQDO
%XWHQHGLRLFDFLG
Some of the functional groups are treated as side chains, e.g., halogen, nitro nitroso, ether.
5. Rules for Naming Organic Compounds containing two or more Functional groups
When an organic compound contains two or more functional groups, one group is regarded as the principal functional
group. The other group is treated as the secondary functional group and may be treated as substituent. The following
decreasing-order of preference is used for selecting the principal functional group:
COOH, SO3H, COOR (R = alkyl group), COCl, CONH2, CN > H C = O, > C = O, OH, NH2, > C = C <, C ≡
For example, if an organic group contains –COOH and – OH groups, then – COOH group is regarded as the principal
group and –OH group is the substituent and is called hydroxyl.
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2+

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+\GUR[\SHQWDQRLFDFLG IXQFWLRQJURXS
When an organic compound contains two or more different functional groups, the principal group forms the suffix of
the name while the other functional groups are considered as substituents and indicated as prefixes.
Table 1.11 Different functional Groups and Corresponding Suffixes and Prefixes
Class Functional Group General Formula Prefix (p) or Secondary Suffix (s) General IUPAC Name
(1) (2) (3) (4) (5)

Alcohols –OH R–OH –Ol (s) Alkanol
Ethers –O–R R–O–R Alkoxy (p) Alkoxy alkane
Ketones & 5 & 5 –one (s) Alkanone
2 2
Primary amines –NH2 R–NH2 Amino-(p) Amino alkane
Halides –X R–1 Halo-(p) Halo alkane
X = F, Cl Br, I
2
Nitro 1 12 R–1 Halo (p) Halo alkane
Compounds
2
Aldehydes –C–H(–CHO) R–CHO –al (s) Alkanal
±„„„
Carboxylic –C–OH R–COOH –oic acid (s) Alkanoic acid
acids ±„„„
±„„„ ±„„„
Amides –amide (s) Alkan amide
–C–NH2 R–C–NH2
±„„„ ±„„„
Acyl halides –C–X R–C–X –oyl halide Alkanoyl halide
X Cl, Br
±„„„ ±„„„
Esters –C–OR' R–C–O–R' Alkyl (p) oate (s) Alkyl alkanoate
±„„„ ±„„„ ±„„„ ±„„„
Acid anthydride –C–O–C– ±±±± –oic anhydride (s) Alkanoic anthyride
Cyanides –CN R–CN –nitrile Alkane nitrile
Table 1.12
Class Formula Prefix Suffix

Alcoholates, Phenolates —O– oxido- -olate
Amidines —C(=NH)–NH2 carbamimidoyl- -carboximidamide
—(C)(=NH)—NH2 --- -imidamide
Carboxylates —COO– carboxylato- -carboxylate
Class Formula Prefix Suffix

—(C)OO –
--- -oate
Hydroperoxides —O—OH hydroperoxy- ---
Imines =NH imino- -imine
=NR (R)-imino- ---
Peroxides —O—OR (R)-peroxy- ---
Salts (of carboxylic acids) —COO–M+ --- (cation) ...carboxylate
—(C)OO–M+ --- (cation) ...oate
Sulfides —SR (R)-sulfanyl- ---
Sulfonates —SO2—O– sulfonato- -sulfonate
Sulfonic acid —SO2—OH sulfo- -sulfonic acid
Thiolates —S– sulfido- -thiolate
Thiols —SH Sulfanyl- -thiol
Let us now apply various rules to write the names of some organic compounds.
Alcohols

2+
2+ 2+ +2

HWKDQRO SURSDQRO HWKDQHGLRO
HWK\ODOFRKRO SURS\ODOFRKRO Q HWK\OHQHJO\FRO
Alcohols (R-OH) take the suffix ‛-ol’ with an infix numerical bonding position: CH3CH2CH2OH is propan-1-ol. The suf-
fixes -diol, -triol, -tetraol etc. are used for multiple -OH groups: Ethylene glycol CH2OHCH2OH is ethane-1, 2-diol.
2+
2+

2
K\GUR[\SURSDQRLFDFLG
If higher precedence functional groups are present (see order of precedence, below), the prefix ‛hydroxy’ is used with
the bonding position: CH3CHOHCOOH is 2-hydroxypropanoic acid.
Halogens (Alkyl Halides)

)
&O )
&O
)
&O &O +
+ %U
WULFKORURPHWKDQH EURPRFKORUR
FKORURIRUP WULIOXRURHWKDQH
KDORWKDQH
Halogen functional groups are prefixed with the bonding position and take the form fluoro-, chloro-, bromo-, iodo- etc.
depending on the halogen. Multiple groups are dichloro-, trichloro- etc., and dissimilar groups are ordered alphabetically
as before. For example, CHCl3 (chloroform) is trichloromethane. The anesthetic Halothane (CF3CHBrCl) is 2-bromo-
2-chloro-1,1,1-trifluoroethane.
Ketones
2 2

2
SURSDQRQH R[RKH[DQDO
DFHWRQH
In general, ketones (R-CO-R) take the suffix ‛-one’ (pronounced own, not won) with an infix position number:
CH3CH2CH2COCH3 is pentan-2-one. If a higher precedence suffix is in use, the prefix ‛oxo-’ is used: CH3CH2CH2
COCH2CHO is 3-oxohexanal.
Process: It is a non terminal group. Count the C- in the main chain at minimum locant in simple ketones. Otherwise,
follow the seniority table.
For example,
&+ 2
&+&+ & & &+

&+ (WK\OPHWK\OSHQWDQRQH
&+

&2&+ &2
$FHWRSKHQRQH %HQ]RSKHQRQH
The above names are retained. So derivatives of these compounds will get the base names of the above compounds.
2

& &+

&+ &+ GLPHWK\ODFHWRSKHQRQH

Aldehydes
2
2 2+
2
+ +
PHWKDQDO 2
IRUPDOGHK\GH R[RSURSDQRLFDFLG F\FORKH[DQHFDUEDOGHK\GH
Aldehydes (R-CHO) take the suffix ‛-al’. If other functional groups are present, the chain is numbered such that the alde-
hyde carbon is in the ‛1’ position, unless functional groups of higher precedence are present.
If a prefix form is required, ‛oxo-’ is used (as for ketones), with the position number indicating the end of a chain: CHO-
CH2COOH is 3-oxopropanoic acid. If the carbon in the carbonyl group cannot be included in the attached chain (for in-
stance, in the case of cyclic aldehydes), the prefix ‛formyl-’ or the suffix ‛-carbaldehyde’ is used: C6H11CHO is cyclohex-
anecarbaldehyde. If a aldehyde is attached to a benzene and is the main functional group, the suffix becomes benzaldehyde.
Process
This is also a terminal group, rule 1 is followed as above. At the end we use ‘al’
For the cyclic compounds we use carboxaldehyde. For example,

&+ & 2 &+ &+ 2 &+ 2

+ &+ 2 &\FORKH[DQH
(WKDQDO 3URSDQHGLDO FDUER[DOGHK\GH
& 2 .HWRQH
Carboxylic Acids
2+
2
HWKDQRLFDFLG
DFHWLFDFLG
In general, carboxylic acids are named with the suffix -‛oic acid’ (etymologically a back-formation from benzoic acid). As
for aldehydes, they take the ‛1’ position on the parent chain, but do not have their position number indicated. For example,
CH3CH2CH2CH2COOH (valeric acid) is named pentanoic acid. For common carboxylic acids, some traditional names such
as acetic acid are in such widespread use, they are considered retained IUPAC names, although ‛systematic’ names such as
ethanoic acid are also acceptable. For carboxylic acids attached to a benzene ring such as Ph-COOH, these are named as
benzoic acid or its derivatives.
If there are multiple carboxyl groups on the same parent chain, the suffix ‛-carboxylic acid’ can be used (as -dicarboxylic
acid, -tricarboxylic acid etc.). In these cases, the carbon in the carboxyl group does not count as part of the main alkane
chain. The same is true for the prefix form, ‛carboxyl-’. Citric acid is one example; it is named 2-hydroxypropane-
1,2,3-tricarboxylic acid, rather than 3-carboxy, 3-hydroxypentanedioic acid.
Process
1. Count the C of— CO2 H and put it in the longest chain (this is a 3 terminal group).
2. Find the base name, i.e., rest name and add ‘oic acid’ at last and follow seniority. For example,

&+&22+ &+&+&22+
(WKDQRLFDFLG 3URSDQRLFDFLG

&22+
&+ &22+ &22+

3URSDQHGLRLFDFLG &\FORSURSDQHFDUER[\OLFDFLG
With cyclic compounds, C of CO2 H is not counted in the main chain; therefore, use carboxylic acid.
Ethers
2

2 2

PHWKR[\PHWKDQH PHWKR[\HWKDQH PHWKR[\SURSDQH
GLPHWK\OHWKHU HWK\OPHWK\OHWKHU LVRSURS\OPHWK\OHWKHU
Ethers (R-O-R) consist of an oxygen atom between two attached carbon chains. The shorter of the two chains becomes the
first part of the name with the -‛ane’ suffix changed to -‛oxy’, and the longer alkane chain becomes the suffix of the name
of the ether. Thus, CH3OCH3 is methoxymethane, and CH3OCH2CH3 is methoxyethane (not ethoxymethane). If the oxygen
is not attached to the end of the main alkane chain, then the whole shorter alkyl-plus-ether group is treated as a side-chain
and prefixed with its bonding position on the main chain. Thus, CH3OCH(CH3)2 is 2-methoxypropane.
Esters
Main Article
2 2 2
2 2 2
PHWK\OPHWKDQRDWH PHWK\OHWKDQRDWH HWK\OPHWKDQRDWH
IRUPDWH DFHWDWH HWK\OIRUPDWH
Esters (R–CO–O–R') are named as alkyl derivatives of carboxylic acids. The alkyl (R’) group is named first. The
R–CO–O part is then named as a separate word based on the carboxylic acid name, with the ending changed from ‛-oic acid’
to ‛-oate’. For example, CH3CH2CH2CH2COOCH3 is methyl pentanoate, and (CH3)2CHCH2CH2COOCH2CH3 is ethyl 4-
methylpentanoate. For esters such as ethyl acetate (CH3COOCH2CH3), ethyl formate (HCOOCH2CH3) or dimethyl phthal-
ate that are based on common acids, IUPAC recommends use of these established names, called retained names. The
‛-oate’ changes to ‛-ate’. Some simple examples, named both ways, are shown in the figure above.
2

2
EXW\OSURSDQRDWH
If the alkyl group is not attached at the end of the chain, the bond position to the ester group is infixed before ‛-yl’:
CH3CH2CH(CH3)OOCCH2CH3 may be called but-2-yl propanoate or but-2-yl propionate.
Amines and Amides

1+

1+
1+
PHWKDQDPLQH SURSDQDPLQH SURSDQDPLQH
PHWK\ODPLQH QSURS\ODPLQH LVRSURS\ODPLQH
1+ 1
1PHWK\OHWKDQDPLQH 1HWK\O1PHWK\OSURSDQDPLQH
Amines (R-NH2) are named for the attached alkane chain with the suffix ‛-amine’ (e.g., CH3NH2 Methyl amine). If nec-
essary, the bonding position is infixed: CH3CH2CH2NH2–propan-1-amine, CH3CHNH2CH3–propan-2-amine. The prefix
form is ‛amino-’.
For secondary amines (of the form R-NH-R), the longest carbon chain attached to the nitrogen atom becomes the prima-
ry name of the amine; the other chain is prefixed as an alkyl group with location prefix given as an italic N: CH3NHCH2CH3
is N-methylethanamine. Tertiary amines (R-NR-R) are treated similarly: CH3CH2N(CH3)CH2CH2CH3 is N-ethyl-N-
methylpropanamine. Again, the substituent groups are ordered alphabetically.
1+ 1
2 2
HWKDQDPLGH 11GLPHWK\OPHWKDQDPLGH
DFHWDPLGH
Amides (R-CO-NH2) take the suffix ‛-amide’, or ‛-carboxamide’ if the carbon in the amide group cannot be included
in the main chain . The prefix form is both ‛carbamoyl-’ and ‛amido-’.
Secondary and tertiary amides are treated similarly to the case of amines: alkane chains bonded to the nitrogen atoms
are treated as substituents with the location prefix N: HCON(CH3)2 is N, N-dimethylmethanamide.
2 2
±&2; DFLGKDOLGH ±&21+ DPLGH & 2 DQK\GULGH & 25 HVWHU
& 2
±&Ł1 QLWULOHVRUF\DQLGH ±1& LVRF\DQLGH
Process
We will take one example from each to understand the writing technique.
For example,
2
&+ & &O

5RRWQDPHHWKDQ
Suffix or name of the functional group : oyl chloride.

Therefore, ethanoylchloride is the IUPAC name.
2
&+&+ & 1+

5RRWQDPH3URSDQ
6XIIL[RUQDPHRIWKHIXQFWLRQDOJURXSDPLGH
2
Therefore, the name is propanamide. Similarly for CONH2, it is cycloprapanecarboxamide. For &+ & 2 ,
&+ & 2
ethanoic anhydride is the IUPAC name. As we can think of the formation of this compound as follows:
2
2 2
&+ &
&+ & 2 + +2 & &+ ¨ &+ &
2
(WKDQRLFDFLG (WKDQRLFDFLG 2
For mixed anhydride, e.g., CH3 — — O — —H, ethanoic methanoic anhydride is the IUPAC name
2 2
In case of &+ & 2&+, write the alkyl group (R) of & first. Give space then write the parent acid’s root
methyl ethanoate
2 5
name and add ‘oate’ finally.
2
For + & 2 &+, IUPAC name is methyl methonate.
2
& 2&+
3UHIL[0HWK\O Suffix: Carboxylate
Root name: cyclohexane, therefore the name is PHWK\OF\FORKH[DQFDUER[\ODWH
VSDFH
&Ł1
&+±&Ł1 &\FORKH[DQHFDUERQLWULOH
(WKDQHQLWULOH
5RRWQDPH 6XIIL[
5RRWQDPH6XIIL[ 1RVSDFH
&+ 1 &
0HWK\O FDUE\ODPLQH
5RRWQDPH 6XIIL[
ZLWKµ\O¶
&+&+ &22+
±2+ DOFRKRO ±6+ WKLRO
2+

&+&+ 2+ +\GUR[\ SURSDQRLF DFLG

Root name : Ethane 3UHIL[ 5RRWQDPH 6XIIL[
Suffix : ol
Therefore Ethanol
is the IUPAC name
CH3CH2 – SH
Root Name : ethane
Suffix : thiol
Therefore, ethane thiol is the IUPAC name of the above compound.

&+&+ &22+
6+
0HUFDSWRSURSDQRLFDFLG
3UHIL[ 5RRWQDPH 6XIIL[

±1+ DPLQH

&+&+ 1+
5RRWQDPH(WKDQ
6XIIL[ DPLQH
Therefore IUPAC name is ethanamine.

&+&+&+ 1 &+&+
&+
N-Ethyl-N-methylpropanamine. Here, we count number of carbon atoms along the chain having maximum C as the
root name (i.e., alkanamine part comes from the alkane with longest chain).
&+1+
1+
&\FOREXWDQDPLQH &\FORSURS\OHWKDQDPLQH
Aromatic amines have common names and are used as their base names while writing the names of their derivatives.
1+ 1+
&+
DQLOLQH RPSWROXLGLQH
IUPAC has retained the common names for aromatic amine like aniline etc. The other groups Cl, Br, I, NO2 etc. are
used as prefixes and seniority depends on alphabetical seniority of their names.
For Example,
&+ 2 &+&+
0HWKR[\HWKDQH
1RVSDFH
Likewise, considering the smaller alkyl group in the alkoxy part and larger alkyl group as alkane, the name of the fol-
lowing compound is
&+

&+ 2 &+
&+
0HWKR[\LVRSURSDQH
RU
0HWKR[\SURSDQH
2
&+ &+
&O %U &+ &+ &+

%URPR&KORURHWKDQH &O
DOSKDEHWLFDOVHQLRULW\ FKORURHSR[\SURSDQH
Many derivatives of principal characteristic groups or functional parent compounds may be named by name modifiers
which consist of one or more separate words placed after the name of the parent structure. This method is most useful in
an indexing environment.
Illustrations
2. Give IUPAC name of the following compound:

&+ &+ &+ &+ &+ &+
&+2+ &+&+
Ans. 1. The longest chain containing functional group is of six carbon atoms. Therefore, the word root is ‛hex’.
&+ &+ &+ &+ &+ &+

&+2+ &+&+
2. There is no multiple bond in it. Hence, the primary suffix is ‛ane’.

3. The functional group is –OH. Hence, secondary suffix is –ol.
4. The chain is numbered as shown. The functional group –OH is on carbon 1. Moreover, there is a methyl group
on carbon 4 and ethyl group on carbon 2.
5. The IUPAC name is, therefore, 2-Ethyl-4-methylhexan-1-ol.
3. Give the IUPAC name of the following compound:
&+ &+ &+ &+ &+ &+ &+2

&+

&+ &+ &+ &+ &+ &+ &+2
&+
Ans. 1. The longest chain containing functional group is of seven carbon atoms. Therefore, word root is Hept.
2. As C = C double bond is present in the molecule. Thus, the primary suffix is ‛ene’.
3. The secondary suffix is ‛al’ because of presence of –CHO group.
4. The chain is numbered as shown as that carbon atom of –CHO group gets number 1. The methyl group is
present on carbon 5 while position of double bond is 3.
5. Thus, IUPAC name is Methylhept-3-en-1-al.
## Practice Exercise
1. Write the secondary suffixes for the following functional groups:
(i) –CN (ii) –COCl (iii) –CO–
(iv) –CHO (v) –COOH (vi) –NH2
2. Give IUPAC names of the following:

2 &+ &+
(i) 2 & &+ &+ (ii) & &+&+
2+
(iii) &+&+&+&21+ (iv) &+ &+ &+ 1+
&+ &+ &+
3. Give IUPAC names of the following compounds:

(i) &+ &+ &+ &22&+ (ii) &+ &+ &+ &+2
&+ &+ &+
&+ &+
(iii) &+ &+ &2 &+ &+ (iv) &+ & &+ & &+
&+ &+ &O %U
(v) (CH3CH2)3COH (vi) CH3–C = C–CO–CH2CH3
SOLUTIONS
1. (i) –nitrile (ii) –oyl chloride (iii) –one
(iv) –al (v) –oic acid (vi) –amine
2. (i) Phethyl 2-methylpropanoate (ii) 2-Phethylbutan-2-ol

(iii) 2-Methylbutanamide (iv) 2,3-Dimethylpropan-1-amine
3. (i) Ethyl 2-methylbutanoate (ii) 2,3-Dimethylbutanal

(iii) 2,4-Dimethylpentan-3-one (iv) 3-Bromo-5-chloro-3,5-dimethyl-heptane
(v) 3-Ethylpentan-3-ol (vi) Hex-4-yn-3-one
Some More Solved Examples
O
4CH
3 – 3CH2 – 2CH – 1C – OCH3 Methyl 2-ethylbutanoate
C2H5
O
4CH
3 – 3CH = 2CH – 1C – OH But 2-en-1-oic acid
OCH3
4CH – 3CH = 2C – 1CH3 2-Methoxybut-2-ene
3
CH3 O
3CH
2 = 2C –– 1C – OC2H5 Ethyl 2-methylprop-2-enoate
CH3 CH3
4CH
3 – 3CH – 2CH – 1CH2NH2 2, 3-Dimethylbutan-l-amine
O
1CH – 2C – 3CH – 4CH – 5CH3 3-Ethyl-4-methylpentan-2-one
3
C2H5 CH3
O
4CH
3 – 3CH – 2CH
2 – 1C – Br 3-Methylbutanoyl bromide
CH3
3CH – 2CH – 1CH2 – OH 2-Phenylpropan-1-ol
3
C6H5
&+

&+ & &+ &+ &+ &+ 4-lodo-2,2,3-trimethylthexane
&+&+
&+

&+ &+

&+
&+
& &+ 4-Chloro-2,3-dimethylhexan-2-ol
&O &+ 2+
2
&+

&+ &
&+ 3-methylbutane-2-one
&+
&+ &2 Ethanoic propanoic anhydride

2
&+ &+ &2
NOMENCLATURE OF COMPOUNDS WITH MORE THAN ONE

SIMILAR FUNCTIONAL GROUPS
If the organic molecule contains more than one similar functional groups, then in addition to various rules, the numerical
prefixes di (for 2), tri (for 3), etc. are added before the secondary suffix, which indicates the functional group. While adding
such words, the vowel ‛e’ of the primary suffix is retained. For example,
4CH – 3CH – 2CH –1CH2
3
OH OH OH
Here, word root is ‛but’, primary suffix is ‛ane’ and secondary siffix is ‛ol’. The –OH groups are positioned at carbon
number 1,2 and 3. Thus, the name is
Butane-1,2,3-triol
Some more examples of the compounds containing more than one similar functional groups are given below.
4CH –3CH––2CH–1CH –OH 2-Ethylbutane-1,3-diol

3 2
OH C2H5
4CH –3C––2C–1CH
3 3
Butane-2,3-dione
O O
4CH = 3CH––2CH = 1CH2 Buta-1, 3-diene
2
4CH – 3CH – 2CH
2 2 2
Pentane-1, 5-dioic acid
5COOH 1COOH
4CH – 3CH
2 = 2CH – 1CHO Pent-2-ene-1,5-dial
5CHO
2CH – 1CN Butane-1,4-dinitrile

2
3CH – 4CN
2
1CH – 2CH
2 – 3CH2 – 4CH2 2-Methylbutane-1,4-diamine
NH2 CH3 NH2
CH2Cl
3
CH2 – CH – 1CH2
2
1,3-Dicholoro-2-(chloromethyl) propane
Cl Cl
CH3
1CH – 2CH
3 – 3CH – 4CH – 5C – 6CH3 3,5,5 – Trimethylhexane-2,4-diol
OH CH3 OH CH3
1 2 3 4
HOOC–CH = CH–COOH But-2-en-1, 4-dioic acid
Note: If an unbranched chain is linked directly to more than two carboxyl groups, these groups are named by substitutive
use of suffix ‛tricarboxylic acid’ etc. The principal chain selected should be linked directly to maximum possible number
of carboxyl groups.
For example,
COOH
1 2 3 4
HOOC–CH2 – CH – CH2– CH2 –COOH
Butane-1, 2, 4-tricarboxylic acid
COOH COOH
1 2 3 4 5
HOOC – CH2 – CH – CH2 – CH2 – CH2 – COOH
Pentane-1,2,3,4,5-tetracarboxylic acid
The carboxyl groups which are not directly linked to the principal chain are expressed by ‛carboxyalkyl’ prefixes.
COOH COOH
6 5 4 3 2 1
CH3 – CH – CH2– CH – CH – CH2 –COOH
CH2COOH
3-(Carboxymethyl) hexane-1,2,5-tricarboxylic acid
Similarly, the subjective prefixes for aldehydes, cyanides, acylchlorides and amides are carbaldehyde, carbonitrilie,
chlorocarbonyl and carboxamide respectively.
Naming the compounds with Two or More Different Functional Groups

If a molecule contains more than one dissimilar functional groups, the parent chain must contain maximum possible num-
ber of functional groups. The numbering of the parent chain is done in such a way so that the functional group of higher
priority gets the lower number. The order of priority of various groups for the sake of numbering is
Carboxylic acids > acid anhydrides > esters > acidchlorides > amides > nitriles, isocyanides > aldehydes > ketones >
alcohols > amines > alkenes, alkynes > halo, nitro, alkoxy, alkyl (always substituent).
As pointed out earlier, that the functional group which gets priority is treated as principal functional group and is
indicated by the secondary suffix. On the other hand, the other functional groups in the compound are considered as
substituents and are indicated by suitable prefixes. The prefixes for such functional groups have been given in Table 1.13.
Table 1.13: Prefixes for functional Groups in Polyfunctional Compounds
Functional Group Prefix

–OH Hydroxy
–CN Cyano
–NC Isocyano
–CHO Formyl or Oxo
–SH Mercapto
–SR Alkylthio
–COOH Carboxy
–COOR Carbalkoxy
–COCl Chloroformyl
–CONH2 Carbamoyl
–NH2 Amino
=NH Imino
>CO Keto or Oxo
Let us write the IUPAC name of the following poly-functional compound.

CH3
4CH – 3C –– 2C – 1CH3
3
OH O
Here, the word root is ‛but’, and primary suffix is ‛ane’. There are two functional groups, but CO group gets prefer-
ence over –OH group. Thus, secondary suffix is ‛one’. The prefixes are, methyl and hydroxyl. Thus, the name is
3-hydroxy-3-methylbutan-2-one
It may be noted that if two groups of same preference appear at identical positions from the either end of the chain, then
the group whose prefix comes first in alphabetic order gets the number. For example,
Br – 1CH2 – 2CH2 – 3CH2– 4CH2 –5CH2 –I
Here, ‛bromo’ group gets preference over ‛iodo’ group. Thus, the name of the compound is
I-Bromo-5-iodopentane
Some Important 1993 Recommendations of IUPAC Nomenclature of Organic Compounds

1. Locants (numbers and/or letters) are placed immediately before the part of the name to which they relate. For example,
CH3CH2CH = CH2 should be named as but-1-ene
CH3CH2 CH2OH should be named as propan-1-ol
Similarly, a few more examples are given below:

OH
1
CH3
3 2 1
2 CH3 CH3 – C – CH2OH
4 3 2 1
3 CH3 – CH = C – CH2OH CH3
Cyclopent-2-en-1-ol 2-Methylbut-2-en-1-ol 2,2-Dimethylpropan-1-ol
2. The locant I is often omitted when there is no ambiguity.
For example, CH3CH2CH2COOH CH3CH2CHO

Butanoic acid Propanal
&+&+
CH3CH2CH2CN &O 2+
Butane nitrile &KORURHWKDQRO
In all the above examples, locant I for the functional group is omitted because the position of the functional group is
unambiguous. However, in the following cases, the position of the functional group must be mentioned.
CH3CH2CH2OH CH3CH2CH2NH2
Propan-l-ol Propan-l-amine
Here, we cannot write simply propanol (or propanamine) because there are two propanols: propan-l-ol and propan-
2-ol.
3. Arrangement of Prefixes
(i) Simple prefixes such as methyl, ethyl, chloro, nitro, hydroxyl etc. are arranged alphabetically. The prefixes di, tri
etc. are, however, not considered for comparison.
For example,

&+&+&+&+&+&+&+&+
&+ &+
(WK\OPHWK\ORFWDQH

&+&+
&O %U
%URPRFKORURFWKDQH
(ii) The name of a prefix for a substituted substituent is considered to begin with the first letter of its complete name.
For example,
&O
&+ &+ &+

&+ &+ &+ &+ &+ &+ &+ &+
&+
4-(2-Chloropropyl)-3-methyloctane
For the substituted substituent 2-chloropropyl, ‘C’ is taken as the first letter.
(iii) When two or more prefixes consists of identical roman letters, priority for citation is given to the group which
contains the lowest locant at the first point of difference.
For example,
&O &+ &+

&+ &+&O
1.(1-Chloroethyl)-4-(2-chloroethyl) cyclohexane
Here, 1-chloroethyl gets priority over 2-chlorethyl.

Some more examples of the poly functional compounds are given below.
Illustrations
14. &+ & &+

&+2+
2&+ &O &+

4. &+ &+

&+2 Ans. 4-Chloro-3-methyl-but-2-en-1-ol
2
Ans. 2- Methoxypropanal
15. &+ &+ &

&+ &+
&+
%U &21+

5. &+ & &22&+ Ans. 2-(Bromomethyl)-3-oxopentanamide
Ans. Methyl 2-methylprop-2-enoate
16. (CH3)3C. CH2CH2Cl
6. CH3 – CH= CH– COOH
4 3 2 1
Ans. 1-Chloro-3, 3-dimethylbutane
Ans. But-2-en-l-oic acid

17. &+ &+ &+ &+ &+2
2+
&+ 2+ 2+

7. &+ &+ &22+
Ans. 2-3-Dihydroxy-4-methylpentanal
Ans. 2-Hydroxpropanoic acid
18. &+ &2 &+ &+ &+&O
8. HO–2CH–1COOH
| &+
HO–3CH–4COOH
Ans. 5-Chloro-3-methylpentan-2-one
Ans. 2,3-Dihydroxbutane-1,4-dioic acid
2+ 2

9. &+ &+ & &22+ 19. &+ & &+ & &+

&+ 2 +
Ans. 3-Methyl-2-oxobutanoic acid
Ans. 4-Hydroxypentan-2-one
10. NC–3CH2–2CH2–1COOH
20. &+ &+ &+ &+ &+
Ans. 3-Cyanopropanoic acid &O %U 2+

&+&22+ Ans. 3-Bromo-4-chlorpentan-2-ol
2+
11. &
&22+ %U &O

&+&22+ 21. &+ &+ &

&+ &+ &O
Ans. 2-Hydroxpropane-1,2,3-tricarboxylic acid 2+
2
Ans. 3-Bromo-4,5-dichloropentan-3-ol

12. &+ & &+ &+ &

22. &+ &+ &+ 2 &+
&22&+ 2+
2+
Ans. 4-Carbethoxypent-3-enoic acid Ans. 1-Ethoxypropan-2-ol
1 2 3 4 5
13. &+ &+ & & 1+ 23. CH3 – CO – CH – CH2 – CH2Cl
&+ 2 2 %U C2H5
Ans. 2-oxo-3methyl-(N-bromo) butanamide Ans. 5-Chloro-3-ethylpentan-2-one
4. Write the correct order of priority of the following groups:
2 2
(i) & 1 & 2+ (ii) &+2 & &O 62+
2 2
(iii) & 25 & 1+ &+2
5. Write the IUPAC names of the following compounds:

(i) HOH2C –CH = CH – CH2OH (ii) +& & &+ &+2+
&+
(iii) +& & &+ &+&+&+2 (iv) CH3COCOOH
&O 2
(v) &+ &+&+2 (vi) &+ &+& &+ 2&+
2+ &O &+ &+
(vii) &+ &&O (viii) C6H5–CH = CH – COOH
2
(ix) &+ &+ & &+ 2&+&+ (x) &+ &+ &+
2&+ &+ 2+ 2+ 2+
&2+
2&+ 2 &+
(xi) (xii) 2 & &+ &+
(xiii) [(CH3)2CH]3COH (xiv) (CH3)3COH

&+
(xv) &+ &+ &+ & &+&O (xvi) CH3CH2CH(CHO)CH2COOH
%U %U
12
(xvii) +1 12
6. Write correct IUPAC names of the following polyfunctional compounds :

OH OH
| |
(i) CH2 = CH–CH2Cl (ii) CH3CH CHCH2OH
&+
(iii) &+ & 2&+ &+2 (iv) &+ &+ &22+
&+
&+ &+&+2
&+2 2 2
(v) &+ & &+&+ (vi) &+ & & 2&+&+
&+2+
2 2 2 2
(vii) &+ & & &+2&+
(viii) + & & 2+
CN
2 |
(ix) &+&+ 1 & + (x) CH3CH2CHCH2CN
&O
7. Write IUPAC names of the following compounds:
(i) CH3OCH2CH2CH2OC2H5 (ii) HOCH2CHCHO
NH2
O
(iii) CH3–C–N–CH2CH3 (iv) HC≡C–CH=CH–CH3
H
OH
(v) CH3–C–COOH
H
SOLUTIONS
O
||
4. (i) –C ≡ N> –C– > –OH (ii) –SO3H > –COCl > –CHO
(iii) –COOR > –CONH2 > –CHO
5. (i) But-2-ene-1, 4-diol (ii) 3-Methyl-but-3-en-l-ol
(iii) 2-Chlorohex-5-yn-l-al (iv) 2-Ketopropanoic acid
(v) 2-Chloro-3-hydroxypropanal (vi) 2-Methoxy-4-methylpentan-3-one
(vii) 1,1,1-Trichloro-2,2-diphenylethane (viii) 3-Phenylprop-2-en-l-oic acid
(ix) 2-Ethoxy-4-methoxypentan-3-one (x) Propane 1,2,3-triol
(xi) 2-Methoxybenezoic acid (xii) Phenyl 2-methylpropanoate
(xiii) 2,4-Dimethyl-3-(1-nethylethyl) pentan-3-ol (xiv) 2-Methylpropan-2-ol
(xv) 2,3-Dibromo-1-chloro-2-methylpentane (xvi) 3-Formylpentanoic acid
(xvii) 2,4-Dinitro benezamine
6. (i) 3-chloroprop-1-ene (ii) butane-1,2,3-triol
(iii) 2-Methoxy-2,3-dimethylbutanal (iv) 3-Formyl-2-methylproanoic acid
(v) 2-Ethyl-3-hydroxy-2-methyl propanal (vi) Ethyl-(2-oxo) propanoate
(vii) 1-Methoxy-2-3,-butanedione (viii) Formylmethanoic acid
(ix) N-Chloro-N-ethyl methanamide (x) 2-Ethyl-butane-1,4-dinitrile
7. (i) 1-Ethoxy-3-methoxypropane (ii) 2-Amino-3-hydroxypropanal
(iii) N-Ethyl ethanamide (iv) Pent-3-en-1-yne
(v) 2-Hydroxypropanoic acid
Cyclic hydrocarbons
These compounds contain carbon chain skeletons which are closed to form rings. The saturated hydrocarbons with ring of
carbon atoms in the molecule are called cycloalkanes. These have the general formula CnH2n.
The cyclic compound is named by prefixing cyclo the name of the corresponding straight chain alkane. For example,
+ & &+
+& &+
RU RU
&+ +& &+
&+&\FORSURSDQH &+&\FOREXWDQH
If side chains are present, then the rules given in the previous section are applied. For example,
&+ &+
0HWK\OF\FORKH[DQH (WK\OF\FORSHQWDQH
When more than one side chains are present, the numbering is done beginning with one side chain so that the next side
chain gets the lower possible number. For example,
&+ &+ &+ &+ 0RUHEUDQFKHG

&DUERQJHWV

ORZHUQXPEHUV

&+ &+&+&+ &+&+
'LPHWK\OF\FOREXWDQH 0HWK\SURS\OF\FORKH[DQH (WK\O
1RW0HWK\OSURS\OF\FORDONDQH GLPHWK\OF\FORKH[DQH
QRW(WK\OGLPHWK\OF\FORKH[DQH
When a single ring system is attached to a single chain with a greater number of carbon atoms or when more than one
ring system is attached to a single chain, then it is named cycloalkylalkanes. For example,
CH2 CH2
1 2 3 4
CH2 – CH2 – CH2 – CH3 CH2
1-Cyclopropyl butane 1, 3-Dicyclohexyl propane
CH3
CH2 – CH2 – CH2

1,3-Bis (2-methylcyclopropyl) propane
CH3
CH2 – CH2 – CH2 – CH2 – CH3

1-Cyclobutylpentane Cyclohexyl cyclohexane
In case of substituted cycloalkenes, the double bond is given the lowest possible number and numbering is done in such
a way that the substituents get the lowest number.
CH3
CH3
3
3 CH3
2
2
1 1
3-Methylcyclohex-1-ene 2, 3-Dimethylcyclopent-1-ene
If some substituent of functional group is present, it is indicated by some appropriate prefix or suffix, and its
position is indicated by numbering the carbon atoms of the ring. The numbering is done in such a way so as assign
least possible number to the functional group or substituent in accordance with the rules already discussed. Some
examples are:
OH NO2
1 3
2 2
3 1
CH3 CH3
3-Methylcyclohexanol 1-Methyl-3-nitroclohexene
CH3
CH 3
3
2 CH3
1 C2 H5
2,3-Dimethylcyclopentene 1-Ethyl-2-methylcyclobutene
O 3 1
CH3 –CH–CH = CH2
1
2
3
OH
3-hydroxcyclohexanone 3-Cyclopenty but-1-ene
Names of Bridged Bicyclic Hydrocarbons

Saturated bicyclic systems having two or more atoms in common are named by prefixing ‘bicyclo’ to the name of the cy-
clic parent hydrocarbon system containing the same total number of carbon atoms in the skeleton. The number of carbon
atoms in each of the three bridges, connecting the two tertiary carbon atoms is indicated in parentheses, in descending
order and Arabic numerals are used to indicate the number of carbon atoms and the numbers are separated by full stops.
The bicyclic system is numbered starting with one of the tertiary bridging carbon and proceeding through longest
bridge to the second bridging carbon continuing back to the first bridging carbon through the second longest chain. Num-
bering is completed by numbering the shortest bridge beginning with the atom next to the bridging carbon. Some illustra-
tions are given below.
5 10 2 1
1 3 6
9 2
1 4 7
8 4 5 3
2 3 7 6 5 4
Bicyclo [2.1.0] pentane Bicyclo [4.4.0] decane Bicyclo [2.2.1] heptane
7
2 1
1 7 2
1
6 3 7 8
2 9 3
4 4 6
3 5 6 4
5 5
Bicyclo [2.2.1] hept-2-ene Bicyclo [3.2.0] heptane Bicyclo [3.2.2] Nonane
Names of Spiro Bicyclic Hydrocarbons

Spiro bicyclic hydrocarbons contain two rings consisting of carbon atoms only and the two rings are linked by a common
carbon. These compounds are named by placing prefix ‘spiro’ before the name of the acyclic parent hydrocarbon with
same number of skeletal carbon atoms. The numbers of skeletal atoms linked to the spiro atom are indicated by Arabic
numbers, separated by a fullstops. The numbers are written in ascending order and enclosed in square brackets.
Numbering of a spiro bicyclic hydrocarbon starts with a ring carbon next to the spiro atom and proceeds first through
the smaller ring and then through the spiro atom and around the second ring. Some examples are given on the next page.
8 9 7 9 10 1 2 CH3
4 6 1 5
7 2 3
8 3
5 2
6 5 3 4 7 6 4
Spiro [3, 5] nonane Spiro [2, 4] heptane 2-Methylspiro [4, 5] deca-1, 6-diene
Naming of Unbranched Assemblies Consisting of Two or More Identical Ring Systems

Such systems are named by placing an appropriate numerical prefix bi-ter-, quarter- etc. for 2, 3, 4 etc. before the name of
the parent hydride corresponding to the repetitive unit.
2 1 1′ 2′ 4′′ 3′′
3 4 4′ 3′ 1′′ 2′′
1, 1′-Bicyclorpropane 1, 1′ : 3′, 1′′-Tercyclobutane
3 1 1′ 2′ 1′′ 2′′
4 3′ 3′′
Biphenyl 1, 1’ : 2’, 1’’-Tercyclopropane
It may be mentioned here that in case of assemblies consisting of benzene ring the word phenyl is used.
Some Solved Examples of Bicyclic Compounds
O
CH2CH 3
1 1 3
6 2 6
7 7 4
5 3 5
4 6, 6-Dimethylbricyclo [3. 1.1]
1-Ethylibicycol [2.2.1] heptane hept-3-en-2-one
HO 1
2 2
6 3
7 1
7
3 5
4 6 5 4

1-Methylbicyclo [2. 2.1] hept-5-en-2-ol 3,3-Dimethylbicyclohept-6-ene
7 Cl
5 1
4 1 4
6 2
5 6
3 2 7 8 3
Bicyclo [2.2.1] heptane 5-chlorospiro [3.4] oct-5-ene
9 10 1
1
2
5 4 2
8
3
7 6 4 3
Spiro [4.5] deca-1, 6-diene 2, 2, 4, 4-Tetramethyl bicyclo
[1.1.0] butane
Naming Compounds with Bond Line Formulae

In this representation of organic molecules, carbon and hydrogen atoms are not shown and the lines representing carbon-
carbon bonds are drawn in zig-zag manner. A single line (–) represents a single bond, two parallel lines (=) represent a
double bond and three parallel lines (≡) represent a triple bond. The only atoms specifically written are those that are nei-
ther carbon nor hydrogen bound to carbon. The intersection of lines represents carbon atoms carrying appropriate number
of hydrogen atoms. For example, buta-1, 3-diene (CH2=CH–CH=CH2) can be represented as follows:
2 4
1 3
Illustrations 2 OH
3
1
Give IUPAC name of the following: 27.
2 4 4
5
24. 1 3 5 Ans. pent-1-en-3-ol
Ans. 4-Methylpente-1,3-diene
2 4 1
6
2
25. 1 3 5
28.
3 5
Ans. Hexa-1,3,5-triene
2 4
3 1 Ans. 6-Ethyl-1-methylcyclohexa-1,
26. 3-diene
4
5
Ans. 3-Ethyl-4-methylpenta-1, 3-diene
4 2
2 OH 3
1 31. 5
1
3 CHO
29.
4
O Ans. 3-Methylpent-4-enal
5
4 2
6 5 3 1
7 Me Me
32.
Ans. 2, 6-Dimethylhepta-2, 5-dienoic Me Me
6 8 10
acid
7 9
Br
Ans. 5,6-Diethyl dic-4-ene
2 4
3 3
30. 1 5 2 4
33.
O 1
Ans. 2-Bromopentan-3-one
Ans. 2-Ethenyl-3-methylcyclohexa-1, 3-diene
8. Give systematic names of the following:
COOH
Et
(i) (ii)
CH3
OH OH
CHO
(iii) (iv)
CH3
H3C Cl
O
(v) (vi)
Br
(vii) CH –CH–CHO (viii) CH3–CH–CH–CH 3
3
OH
9. Give IUPAC names of the following structures:
(i) (ii)
COOH Cl
(iii) (iv) OH
Cl OH
10. Write the correct IUPAC names of the following bond line formulae:
O
O
(i) (ii) H CO
3
Cl
Me
(iii) (iv)
O OMe
Me
Me
H OH
(v) HO H (vi) Me Me
Me Me
Me
Et
OH Me
(vii) (viii) Me
H H Me COOH
O
Me
(ix) (x) N
O
(xi) ( xii) CHO

Me Me
(xiii) (xiv)
O
H H O
SOLUTIONS
8. (i) 1- Ethylcyclohexene (ii) 5-Methylcyclohex-2-ene carboxeylic acid
(ii) Cyclohex-3-en-l-ol (iv) 2-Hydroxycyclopentanecarbaldhyde
(v) 2,3-Dimethcyclohexnanone (vi) 1-Bromo-2-chlorocyclobutene
(vii) 2-Cyclobutylpropanal (viii) 3-Cyclopropylbutan-2-ol.
9. (i) 4-Ethyl-3-propylhept-1-ene (ii) 4-(1,2-Dimethylbutyl) hepta-1, 3,5-triene
(iii) 3-Chloro-2-(1-propenyl)-2,4-hexadienoic acid
3-Chloro-4-cyclopropyl cyclobutane 1,2-diol
(iv) 3-chloro-4-cyclopropyl-1,2-cyclobuan-1,2-diol.
10. (i) 2-Methylpropanoyl chloride (ii) Methyl propanoate
(iii) Methyl 2-ethylbutanoate (iv) 5-Ethyl-4, 6-dimethyloct-1-ene
(v) Butane-2,3-diol (vi) 5,6-Diethyl-3-methyldec-4-ene
(vii) 3-Methyl cyclopentan-1-ol (viii) 7-Ethyl-6-methylundec-6-cnoic acid
(ix) Ethyl propanoate (x) N-Ethyl-N-methyl propan-1-amine
(xi) Hex-3-yne (xii) 3-Ethyl-4-methylpentanal
(xiii) 2,3-Dimethyloxirane (xiv) Tetrahydrofuran
Some More Solved Examples

6
CH3 – 5CH2 – 4CH – 3CH2 – 2CH – Cl 2,4-Dichlorohexane
Cl 1
Cl
7CH 6CH 5CH 4CH
3 2 = 3CH2CH21CHO 6-Methylhept-3-enal
CH3
5CH –4C
3 – 3CH–2C–1CH3 3-Methylpentane-2, 4-dione
O CH3 O
6CH –5CH– 4CH –3CH –2CH–Br 2-Bromo-5-methylhexanoic acid

3 2 2
1COOH
CH3
CH3
1CH –2CH – 3C–OH
3 2 3-Methylpentan-3-ol
4CH
2
5CH
3
O O
H–C–C–H Ethanedial
O O
HO–C–C–OH Ethanedioic acid
1
CH2=2CH–3CH2–4C≡5CH Pent-1-en-4-yne
5
CH3–4CH=3CH–2C≡1CH1 pent-3-en-1-yne
5CH –4CH–3CH –2C–1CH
3 2 3
4-Hydroxypentan-2-one
OH O
NH2
4CH –3CH– 2CH–1COOH
3 2-Amino-3-methylbutanoic acid
CH3
OH
6
CH3– CH3– C{ C– CH–1CHO
5 4 3 2
2-Hydroxy-5-methylhex-3-ynal
CH3
8CH –7CH–6CH
3 = 5CH–4C – 3CH= 2CH–1CH3 7-Methylocta-2,5-dien-4-one
CH3 O
CH3
5
CH3–4CH–3CH2–2CH–1COOH 4-Formyl-2-methylpentanoic acid
CHO
O
COOH
2-Ketocycloexanecarboxylic acid
CONH2
CH3
2-Methylcyclopentanecarboxamide
O
CH3
5,6-Dimethylcyclohex-2-en-l-one
CH3
–2CH–1CCl3 l,l,l-Trichloro-2,2-diphenylethane
Here, the ring, –represents C6H5–, i.e., phenyl group. For details, see nomenclature of atomic compounds. In case
the phenyl group is further substituted, the carbon atoms of the ring are separately numbered starting from the carbon atom
of the ring directly attached to the parent chain in such a way that substituent on ring gets lowest possible position. This
has been illustrated in the following examples:
3CH –2CH–1COOH
3
1
2
2-(4-Chlorophenyl) propanoic acid
3
4
Cl
Br O
3CH –2C–1C–OEt
3
1
2
Ethyl-2-bromo-2(-3-nitrophenyl) propanoate
3
NO2
If the compound contains more than one similar complex radicals/substituents, then the numerical prefixes such as di,
tri, tetra, etc. are replaced by bis, tris, tetrakis, etc. respectively.
The following examples illustrate this point:
Cl 2 3
Cl–1C –2CH–1 4
–Cl 1,1,1-Trichloro-2,2-bis (4-chloropheneyl) ethane
1
Cl 2
3
4
Cl
CH2Cl
Cl–1CH2 – C–3CH2Cl
2
1,3-Dichloro-2,2-bis (chloromethyl) propane
CH2Cl
WRITING THE STRUCTURE OF THE COMPOUND WHOSE NAME IS GIVEN

For writing the structure of the compound from the given IUPAC name the following steps are followed:
1. Write the straight chain of carbon atoms with respect to the word root.
2. Number the carbon chain from either of the ends.
3. Fill in the multiple bond (if any) and attach the substituents or functional groups at the appropriate positions.
4. Attach suitable number of hydrogen atoms to each carbon so as to satisfy its tetracovalency.
For example, let us derive the structure of the compound having IUPAC name 4-chloro-3-methyl-pentan-2-ol by fol-
lowing various steps.
1. The word root ‘pent’ indicates a chain of five carbon atoms.
C–C–C–C–C
2. The primary suffix ‘ane’ indicates, it is saturated compound and secondary prefix ‛ol’ indicates, the presence of –OH
group at carbon 2.
1
C–2C–3C–4C–5C
3. In addition, there is a –Cl group at carbon 4 and CH3– at carbon 3.

CH3
1C–2C–3C–4C–5C
OH Cl
4. Filling in the appropriate number of hydrogens, we get
CH3
H3C–HC–CH–CH–CH 3
OH Cl
Illustrations
34. Derive the structure of

(i) 2,2-Dimethylpentan-1-ol (ii) 4-Hydroxypentan-2-one
(iii) 4-Methylcyclohex-2-en-1-one (iv) 2-Amino-3-methylbutanoic acid.
Ans. (i) The word root ‘pent’ indicates the presence of 5 carbon atoms chain. The secondary suffix ‘ol’ indicates the
presence of –OH group at carbon number 1. there are two methyl groups at position number 2.
Thus, the structure of the compound is
CH3
CH3–CH2–CH2 –C–CH2OH
CH3
(ii) The word root ‘pent’ indicates the presence of 5 carbon atoms chain.
The secondary suffix ‘one’ indicates presence of carbonyl or keto group at position number 2. Prefix hydroxy
indicates the presence of –OH group at carbon number 4.
OH O
CH3–CH–CH 2–C–CH3
(iii) The word root ‘hex’ and prefix ‘cyclo’ indicates the presence of a ring of six carbon atoms.
The primary suffix ‘en’ indicates the presence of a double bond (at position number 2) and secondary suffix ‘one’
indicates the presence of keto group (at position number 1).
There is a methyl group at carbon number 4.
O
1
2
3
4
CH3
(iv) The word root ‘but’ indicates a chain of four carbon atoms.
The secondary suffix ‘oic acid’ indicates it is a carboxylic acid (–COOH).
Prefixes ‘amino’ and ‘methyl’ indicate the presence of –NH2 group and –CH3 group at the indicated positions
respectively. Thus, structure of the compound is
CH3 NH2
4 1
CH3– CH– 2CH–COOH
3
Common or Trivial Names

Although IUPAC system nomenclature has taken prime position, certain common names are so familiar that they are so
frequently used by chemists. The common names of important of various families are given below.
1. ALKANES (PARAFFINS)
The first three members of this family have the same common as well as IUPAC name. The higher members can exist as
a number of isomers. The various isomers of butanes and pentanes are distinguished by use of prefixes n- (for normal),
CH3
‛iso-’ and ‛neo-’. Prefix n- is used for straight chain alkanes, ‛iso-’ is used for the molecules containing CH –
CH3
(isopropyl) group and ‛neo-’ is used for molecules containing (CH3)3 C – group at the one end of the chain. Some
examples are given below.
Molecular Formula Common Name

CH 3 CH 2 CH 2 CH 3 n-Butane
CH3
CH – CH3 iso-Butane
CH3
CH 3 CH 2 CH 2 CH 2 CH 3 n-Pentane
CH3
CHCH2CH3 iso-Pentane
CH3
CH3
CH3 – C – CH3 neo-Pentane
CH3
CH3
CH3 – CHCH2CH2CH3 iso-Hexane
CH3
CH3 – C – CH2CH3 neo-hexane
CH3
2. ALKENES (OLEFINS)
CH2 = CH2 Ethylene
CH3–CH = CH2 Propylene
CH3–CH = CH–CH3 b-Butylene
CH3
CH = CH3 Iso-Butylene
CH3
CH2 = C = CH2 Allene
3. ALKYNES (ACETYLENS)
HC ≡ CH Acetylene
CH3C ≡ CH Methylacetylene (Allylene)
CH3CH2C ≡ CH Ethylacetylene
CH3C ≡ CCH3 Dimethylacetylene (crotonylene)
4. ALCOHOLS
CH3OH Methyl alcohol
CH3CH2OH Ethyl alcohol
CH3CH2CH2OH n- Propyl alcohol
CH3CH2CH2CH2OH n-Butyl alcohol
CH3
CH–CH2–OH3 Iso-Butyl alcohol
CH3
CH2 = CH–OH Vinyl alcohol
CH2 = CH–CH2–OH Allyl alcohol
CH ≡ C–CH2–OH Propargyl alcohol
5. ALKYL HALIDES
Molecular formula Common Name

CH3Cl Methyl chloride
CH3CH2Cl Ethyl chloride
CH2 = CH–Cl Vinyl chloride
CH2 = CH–CH2–Br Allyl bromide
6. PRIMARY AMINES

CH3NH2 Methylamine
CH3CH2NH2 Ethylamine
CH2 CH2CH2NH2 n-Propylamine
7. ISOCYANIDES

CH3NC Methyl isocyanide
CH3CH2NC Ethyl isocyanide
8. CARBOXYLIC ACIDS
HCOOH Formic acid
CH3COOH Acetic acid
CH3 CH2COOH Propionic acid
CH3CH2CH2COOH n-Butyric acid
CH3CH2CH2CH2COOH n-Valeric acid
CH3
CH–COOH Iso-Butyric acid
CH3
CH2 = CH–COOH Acrylic acid
9. ALDEHYDES
HCHO Formaldehyde
CH3CHO Acetaldehyde
CH3 CH2CHO Propionaldehyde
CH3CH2CH2CHO n-Butyraldehyde
CH3CH2CH2CH2CHO n-Valeraldehyde
CH3
CH–CHO Iso-Butyraldehyde
CH3
CH2 = CH–CHO Acrolein

CH3CH = CH–CHO Crotonaldehyde
10. ACID CHLORIDES

HCOCl Formyl chloride
CH3COCl Acetyl chloride
CH3 CH2COCl Propionyl chloride
11. AMIDES
HCONH2 Formamide
CH3CONH2 Acetamide
HCON(CH3)2 N, N-Dimethyl Formamide (DMF)
CH3CON(CH3)2 N, N-Dimethyl acetamide
CH2 = CH – CONHCH3 N-Methylacrylamide
12. EASTERS
O
Methyl formate
H–C–OCH3
O
Methyl acetate
CH3–C–OCH3
O
Methyl propionate
CH3–CH2–C–OCH3
O
Ethyl valerate
CH3–CH2CH2CH2–C–OC2H5
13. ACID ANHYDRIDES

(CH3CO)2O Acetic anhydride
(CH3CH2CO)2O Propionic anhydride
14. CYANIDES
CH3CN Acetonitrile
CH3CH2CN Propiononitrile
CH3 CH2CH2CN Butyronitrile
15. ETHERS
CH3–O–CH3 Dimethylether
CH3–O–CH2CH3 Ethylmethylether
CH3 CH2–O–CH2CH3 Diethylether
CH3 CH3
CH–O–CH Di-isopropylether
CH3 CH3
CH2=CH–O–CH2–CH=CH2 Allylvinylether
16. KETONES
CH3COCH3 Dimethyl ketone or Acetone
CH3COCH2CH3 Ethylmethylketone
CH3 CO–CH=CH2 Methylvinylketone
17. SECONDARY AMINES

CH3–NH–CH3 Dimethylamine
CH3
CH3–CH 2–NH–CH Ethyl isopropylamine
CH3
18. TERTIARY AMINES

CH 3–N–CH3 Trimethyl amine
CH3
C 2H5–N–CH3 Diethyl methyl amine
C2H5
The Names of Aromatic Compounds Elementary Idea

We will consider an aromatic compound, which contains a benzene ring. It assumes that you are reasonably confident
about naming compounds containing chains of carbon atoms (aliphatic compounds).
Naming aromatic compounds isn't quite so straightforward as naming chain compounds. Often, more than one name is
acceptable, and it's not uncommon to find the old names still in use as well.
Background
The benzene ring
All aromatic compounds are based on benzene, C6H6, which has a ring of six carbon atoms and has the following symbol:
Each corner of the hexagon has a carbon atom with a hydrogen attached.
The phenyl group
Remember that you get a methyl group, CH3, by removing a hydrogen from methane, CH4.
You get a phenyl group, C6H5, by removing a hydrogen from a benzene ring, C6H6. Like a methyl or an ethyl group, a
phenyl group is always attached to something else.
Aromatic compounds with only one Group Attached to the Benzene Ring
Cases where the name is based on benzene
chlorobenzene
This is a simple example of a halogen attached to the benzene ring. The name is self-obvious.
Cl
The simplified formula for this is C6H5Cl. You could therefore (although you never do) call it phenyl chloride. When-
ever you draw a benzene ring with one other thing attached to it, you are in fact drawing a phenyl group. In order to attach
something else, you have to remove one of the existing hydrogen atoms, and so automatically make a phenyl group.
nitrobenzene
The nitro group, NO2, is attached to a benzene ring.
NO2
The simplified formula for this is C6H5NO2.
methylbenzene
Another obvious name - the benzene ring has a methyl group attached. Other alkyl side-chains would be named similarly
- for example, ethylbenzene. The old name for methylbenzene is toluene, and you may still hear that.
CH3
The simplified formula for this is C6H5CH3.
(chloromethyl) benzene
A variant on this which you may need to know about is where one of the hydrogens on the CH3 group is replaced by a
chlorine atom. Notice the brackets around the (chloromethyl) in the name. This is so that you are sure that the chlorine is
part of the methyl group and is not somewhere else on the ring.
CH2Cl
If more than one of the hydrogens had been replaced by chlorine, the names would be (dichloromethyl) benzene or
(trichloromethyl) benzene. Again, notice the importance of the brackets in showing that the chlorines are part of the side
group and are not directly attached to the ring.
benzoic acid (benzenecarboxylic acid)

Benzoic acid is the older name, but is still in common use. It is a lot easier to say and write than the modern alternative.
Whatever you call it, it has a carboxylic acid group, -COOH, attached to the benzene ring.
COOH
cases where the name is based on phenyl

Remember that the phenyl group is a benzene ring minus a hydrogen atom –C6H5. If you draw a benzene ring with one
group attached, you have drawn a phenyl group.
phenylamine
Phenylamine is a primary amine and contains the -NH2 group attached to a benzene ring.
NH2
The old name of phenylamine is aniline, and you could also reasonably call it aminobenzene. Phenylamine is what it is
most commonly for UK-based exam purposes.
phenylethene
This is an ethene molecule with a phenyl group attached. Ethene is a two carbon chain with a carbon-carbon double bond.
Phenylethene is therefore:
CH=CH2
The old name for phenylethene is styrene—the monomer from which polystyrene is made.
phenylethanone
This is a slightly awkward name - take it to pieces. It consists of a two carbon chain with no carbon-carbon double bond.
The ‛one’ ending shows that it is a ketone, and so has a C=O group somewhere in the middle. Attached to the carbon chain
is a phenyl group. Putting that together gives:
O
C CH3
phenyl ethanoate
This is an ester based on ethanoic acid. The hydrogen atom in the -COOH group has been replaced by a phenyl group.
O
CH3 C
O
phenol
Phenol has an -OH group attached to a benzene ring and so has a formula C6H5OH.
OH
AROMATIC COMPOUNDS WITH MORE THAN ONE GROUP ATTACHED TO

THE BENZENE RING
Numbering the Ring
Any group already attached to the ring is given the number 1 position. Where you draw it on the ring (at the top or in any
other position) does not matter—that is just a question of rotating the molecule a bit. It is much easier, though, to get in the
habit of drawing your main group at the top.
The other ring positions are then numbered from 2 to 6. You can number them either clockwise or anti-clockwise. As
with chain compounds, you number the ring so that the name you end up with has the smallest possible numbers in it.
Examples will make this clear.
Some simple examples
Substituting chlorine atoms on the ring
Look at these compounds:
CH3 CH3 CH3
Cl
Cl
Cl
2-chloromethylbenzene 3-chloromethylbenzene 4-chloromethylbenzene
All of these are based on methylbenzene and so the methyl group is given the number 1 position on the ring.
Why is it 2-chloromethylbenzene rather than 6-chloromethylbenzene? The ring is numbered clockwise in this case
because that produces a 2- in the name rather than a 6-. 2 is smaller than 6.
2-hydroxybenzoic acid
This might also be called 2-hydroxybenzenecarboxylic acid. There is a -COOH group attached to the ring and, because the
name is based on benzoic acid, that group is assigned the number 1 position. Next door to it in the 2 position is a hydroxy
group, –OH.
COOH
OH
benzene-1,4-dicarboxylic acid
The ‛di’ shows that there are two carboxylic acid groups, -COOH, one of them in the 1 position and the other opposite it
in the 4 position.
COOH
COOH
2,4,6-trichlorophenol
This is based on phenol - with an -OH group attached in the number 1 position on the ring. There are 3 chlorine atoms
substituted onto the ring in the 2, 4 and 6 positions.
OH
Cl Cl
Cl
methyl 3-nitrobenzoate
This is a name you might come across as a part of a practical exercise in nitrating benzene rings. It is included partly for
that reason, and partly because it is a relatively complicated name to finish with.
The structure of the name shows that it is an ester. You can tell that from the ‛oate’ ending, and the methyl group float-
ing separately from the rest of the name at the beginning.
The ester is based on the acid, 3-nitrobenzoic acid. So start with that.
There will be a benzene ring with a -COOH group in the number 1 position and a nitro group, NO2, in the 3 position.
The -COOH group is modified to make an ester by replacing the hydrogen of the -COOH group by a methyl group.
Methyl 3-nitrobenzoate is therefore:
COOCH3
NO2
NOMENCLATURE OF SUBSTITUTED BENZENE COMPOUNDS—A DETAILED APPROACH

Aromatic compounds are those which contain one or more benzene rings in them. An aromatic compound has two main
parts:
(i) Nucleus
(ii) Side Chain
(i) Nucleus: The benzene ring represented by regular hexagonal of six carbon atoms with three double bonds in the
alternate positions is referred to as nucleus. The ring may be represented by any of the following ways:
H
C
HC CH
HC CH
C
H
(i) (ii) (iii) (iv)
(ii) Side Chain: The alkyl or any other aliphatic group containing at least one carbon atom attached to the nucleus is
called side chain. These are formed by replacing one or more hydrogen atoms in the ring by alkyl radicals i.e., R(R
may be –CH3, –C2H5, –C3H7 etc.)
R Side chain
Ring of nucleus
If one atom of hydrogen of benzene molecule is replaced by another atom or group of atoms, the derivative formed is
called monovalent substituted derivative. It can exist only in one form because all the six hydrogens of benzene repre-
sent equivalent positions. For example, C6H5X, where X is a monovalent group.
When two hydrogen atoms of benzene are replaced by two monovalent atoms or group of atoms, the resulting product
can have three different forms. These forms are distinguished by giving the numbers. The position occupied by one of the
substituent is given as 1 and the other position is numbered in a clockwise director
(i) Ortho (or 1,2-): The compound is said to be ‛ortho’ (or 1, 2-) if the two substituents are on the adjacent carbon
atoms.
(ii) Mete (or 1,3-): The compound is said to be ‛meta’ or (1, 3-) if the two substituents are on alternate carbon atoms.
(iii) Para (or 1,4-): The compound is said to be ‛para’ (or 1, 4-) if the two substituents are on diagonally situated carbon
atoms.
Ortho, meta and para are generally represented as o-, m- and p- respectively as shown below:
X X X
1 X 1 1
2 2 2
3 3
X
X
(1, 2-) Ortho (1, 3-) Meta (1, 4-) Para
ARYL GROUPS
The radicals obtained by removal of one or more hydrogen atoms of the aromatic hydrocarbon molecules are known as
aryl radicals or aryl groups.
For example,
CH2 CH C
Phenyl
(From nucleus) Benzyl Benzal Benzo
From Side
Common or Trivial Names

Although IUPAC system nomenclature has taken prime position, certain common names are so familiar that they are very
frequently used by chemists. The common names of important of various families are given below.
Nomenclature of Aromatic Compounds

The term aromatic is derived from Greek work aroma which means pleasant smelling compounds. But in present form,
the aromatic compounds are cyclic compounds which contain one or more benzene type rings. Benzene is the simplest
hydrocarbon of aromatic series which has a planar cyclic ring of six carbon atoms having three double bonds in alternate
positions as shown below.
CH 1
HC CH 6 2
OR
5 3
HC CH
CH 4
The carbon atoms of benzene are numbered from 1 to 6 as shown above. The benzene ring is called the nucleus and
alkyl groups attached to the ring are called side chains.
CH3
Side chain
Nucleus
Benzene forms only one mono substituted derivative. However, it can form three disubstituted derivatives; namely 1,2;
1,3 and 1,4 derivatives. These are respectively called ortho (or o-), meta (or m-) and para (or p-) derivatives.
‛Tri’ and ‛poly’ substituted derivatives are named by numbering the chain in such a way that the parent group gets the
lowest number and the lowest locant rule is obeyed.
Nomenclature of Different Aromatic Families

The families of aromatic compounds are similar to those of aliphatic compounds. The names of some important members
of each family are given below. Some of the common names, which are universally accepted, are also given in brackets.
1. Hydrocarbons (Arenes)
(a) Hydrocarbons containing condensed rings
Benezene Naphathalene Anthracene Phenanthrene
(b) Hydrocarbons containing one ring only
CH3 C2H5 CH=CH2 CH3
CH3
Methylbenzene Ethylbenzene Phenylethene 1,2-Dimethyl benezene

(Toluene) (0-Xylene) (Styrene)
CH3 CH3 CH3 CH3 CH CH3

CH3
CH3
H3C
CH3 CH3
1 3,-Dimethyl 1,3,5-Trimethyl 1,2,3-Trimethyl Isopropyl

benezene benezene benezene benezene
(m-Xylene) (Mesitylene)
2. Aromatic or aryl radicals
CH2 CH C
Phhenyl radical Benezyl (monovalent) Benzal (divalent) Benzo (trivalent)
CH3 CH3 CH3

H3C CH3
CH3
0-Tolyl m-Tolyl p-Tolyl Mesityl
3. Halogen derivatives
Cl CH3 Cl
Cl
Cl
Chlorobenezene 3-Chlorotoluene 1,4-Dichlorobenezene
Cl Cl
CH2–Cl CH C Cl
Cl Cl
Chloro phenyl Dichloro phenyl Trichloro phenyl

Methane methane methane
(Benzyl chloride) (Benzyl chloride) (Benzyl trichloride)
4. Phenols
OH CH3 CH2 OH
OH
Hydroxy benezene 3-Hydroxy toluene Pheneylmethanol
(Phenol) (m-Cresol) (Benzyl alcohol)
Here, benzyl alcohol is not a phenol but an aromatic alcohol.

5. Amino derivatives
NH2 CH3
H H
NH2 N
N CH3
Aminobenezene 2-Methyl aniline N-Methyl aniline N-Phenylaniline

(Aniline) (2-amino toluene)
6. Ketones
COCH3
O O
C C CH2CH3
Methyl Phenyl ketone Diphenyl ketone Propiophenone

Or Or
Acetophenone Benezophenone
7. Aldehydes
CHO CHO
OH
Benezaldehyde 2-Hydroxy benzadehyde
8. Carboxylic acids
COOH
COOH COOH
COOH
COOH COOH COOH

Benezoic acid 1,2-Benezene 1,3-Benezene 1,4-Benezene
Terephathalic acid dicarboxylic acid dicarboxylic acid dicarboxylic acid
(Phthalic cid) (Isophthalic acid) (Terephathalic acid)
9. Acid derivatives
O
O O
O=C–Cl O=C–NH 2 C–O–CH3
C N –C–O–C–
Benzoyl chloride benezamide Methyl benzoate Benzonitrile Benzoic anhydride

(Phenyl cyanide)
10. Sulphonic acids

SO2OH CH3 SO3H SO3H
Benezene
sulphonic acid SO2OH NH2 COOH
p-Toluene sulphonic 4, Aminobenezene sulphonic 4-Sulphobenzoic
Acids (PTS) acid (Sulphanilic acid) acid
11. Nitro derivatives

CH3 OH
NO2
O2N NO2 O N NO2
2
NO2
NO2 NO2
1,2-Dinitro benzene 2,4,6-Trinitro toluene 2,4,6-Trinitro phenol
(T.N.T.) (Picric acid)
12. Diazonium salts

+ – + –
N2Cl N2HSO4
Benzene diazonium Benezene diazonium

Chloride hydrogen sulphate
13. Grignard reagents

Mgl
MgBr
CH3
Phenyl magnesium p-Tolyl
Bromide magnesium
iodide
14. Isocyanides
NC CH3
NC
Phenyl isocyanide 2-Methyl phenyl

isocyanide
Some common as well as IUPAC names or benzene derivatives

CH3 OH CHO COCH3 OCH3 CH2OH
Toluene Phenol Benzaldehyde Acetophenone Anisole Benzyl alcohol
O
CO2H CONH2 NH2 CH2CO2H CH2 CH2 OH
CH3
Benzoic acid Benzamide Aniline Phenyl acetic Styrene o-Cresol

acid oxide
OH OH OH NH2 OH OH
OH CH3 CO2H CHO
OH
OH
Catechol Resorcinol Hydroquinone o-Toluidine Salicylic acid Salicylaldehyde
CH3 CO2H CO2H CO2H OH

CO2H CO2H
CO2H HO OH
CO2H
o-Toluic acid Phthalic acid Isopthalic acid Terephthalic acid Phloroglucinol
Example: Give IUPAC names of the following organic molecules:

OCH3
CH3
(i) H CO OH (ii)
3
C2H5
NO2
OMe NH2
OEt
(iii) (iv)
Cl
COOH CH3
Solution:
(i) 5-Methoxy-2-nitrophenol (ii) 4-Ethyl-2-methylanisole
(iii) 2-Chloro-4-methoxybenzoic acid (iv) 2-Ethoxy-4-methylaniline
Problems
For practice and Revision
Give IUPAC names of the following:
O
CH2COOH C OH
(i) (ii)
OH
CH3
CH2Cl
CH CH CH3
(iii) (iv)
Cl CHO
O CH
CH2 C CH3 CH OH CH OCH3
(v) (vi)
CH3
C2 H 5
(vii) C6H5–C–CH–CH3 (viii) Br CH2 CH2 Br
OH
O OC2H5
CH2CHO
C
Br
(ix) (x)
Br
Names of some Hyterocyclic Compounds

Heterocyclic compounds are the cyclic compounds which contain atoms of some other element than carbon in addition
to the atoms of carbon. Some important heterocyclic compounds along with their names are given below. The hetero-
atom in a heterocyclic compound is given the lowest possible number consistent with an orderly progression around the
ring system.
4
4 3 4 3 5 3 4 3
5 2 5 2 6 2 5 2
O N N1 S1
H
Furan Pyrrole Pyridine Thiophene
5 4 5 4
4 3 6 3 6 3
5 2 7 2 7 N2
N1 8 N1 8 1
H
Pyrrolidine Quinoline Isoquinoline
4 3 3 2 4 3 3 2
5 5 2
2
O1 N1 S1
Br O1
H
Tetrahydrofuran Aziridine 2-Bromothiophene Oxirane
(Ethylene oxide)
Hydro prefixes
If the name of the parent hydride implies the presence of the maximum number of noncumulative double bonds, other
states of hydrogenation can usually be indicated by the use of the prefix ‛hydro-’ together with an appropriate numerical
prefix signifying the addition of hydrogen atoms. This operation is regarded as the reduction of double bonds; thus, hy-
drogen atoms can only be added in pairs (by the use of ‛dihydro-’, ‛tetrahydro-’, etc.). ‛Indicated hydrogen’ is included
if required by the parent hydride.
Examples of R-3.1.2
9
8 1
2
8 1 1 2
N 7
7 2 8 3
3
7 4
6 3 6 4
5
5 4 6 5
1, 4-Dihydron aphthalene 2,3,4,5-Tetrahydroazocine 6,7-Dihydro-5H-benzo[7]annulene
SOLVED CONCEPTUAL EXAMPLES
GIVE IUPAC NAMES OF THE FOLLOWING COMPOUNDS CH2

CH2 – CH3
CH2 C
1. (CH 3 )2 C = CH 2 12.
Ans. 2-Methylpropene CH 2 CH
2. (CH 3 )2 CH − CH 2 − CH 2 Cl
CH2
Ans. 1-Chloro-3-methylbutane
Ans. 1-Ethylcyclohexene
3. (CH 3 )3 COH
OH
Ans. 2-Methylpropan-2-ol
CH
4. HOH 2 C − CH = CH − CH 2 OH
13. H2C CH2
Ans. But-2-en-1, 4-diol
HC CH2
5. (CH 3 )2 CHCH 2 CH(CH 3 )2
Ans. 2, 4-Dimethylpentane CH
Ans. Cyclohex-3-en-1-ol
6. H 2 C = C − CH 2 − CH 2 − OH
| CH3
CH 3 14. H3C O
Ans. 3-Methyl-but—3-en-1-ol
7. HC ≡ C − CH 2 − CH 2 − CH − CHO Ans. 2, 3-Dimethylcyclohexanone

|
Cl 15. CH3 – CH – CHO
Ans. 2-Chlorohex-5-yn-1-al
8. CH2CHO Ans. 2-Cyclobutylpropanal

C2H5
Ans. Phenylethanol
16. C6H5 – C – CH – CH3
9. CH3 – CH – CH – COOH
OH
CH3 CH3
Ans. 2, 3-Dimethylbutanoic acid Ans. 3, 3-Diphenylpentan-2-ol
10. CH3 – CH – CH2Cl

17. (CH 3 )2 C(CCl 3 )2
CH3
Ans. 1, 1, 1, 3, 3, 3-Hexachloro-2-, 2-dimethylpropane
Ans. 1-Chloro-2-methylpropane
Me
CH3
18. Me Me
11. CH – C – CH Me Me
3 3
CHO Me is methyl group

Ans. 2, 2-Dimethylpropanal Ans. 5, 6-Diethyl-3-methyldec-4-ene
Me O CH3
6
Me 5
7 Me 30. CH3CH2 – C – N – CH3
19.
2
4 Ans. N, N-Dimethylpropanamide
Me 3
COOH
1
E is ethyl group
31. CH 3 − CH − CO − CI
|
Ans. 4, 5, 7-Trimethyl non-4-enoic acid CH 3
20. ClCH 2 CH 2 COCl Ans. 2-Methylpropanoyl chloride
Ans. 3-Chloropropanoyl chloride 32. OH
21. (CH 3 )2 CHCOOC 2 H 5
Ans. Pent-4-yn-1-ol
Ans. Ethyl-2-methylpropanoate
Cl
22. C6H5 – C(CH3)2
33. OH
OH
Br
Ans. 2-Phenyl-propan-2-ol Ans. 2-Bromo-3-chlorohept-5-en-l-ol
23. CH3 – CH – CO – CH – CH3 Cl OH
CH3 CH3
34. Br
Ans. 2, 4-Dimethyl-pentan-3-one
NO2 Br
24. CH3 – C – CH2 – C – CH3 Ans. 4-Bromo-3-chloro-5-cyclopropylcyclohexanol
C2H5 C2H5 35. OH
Ans. 3-Bromo-3, 5-dimethyl-5-nitroheptane
Cl
F Cl
Br
25. CH3 – C – CH2 – C – CH3 Ans. 3-Bromo-2-chloro-5-methylidenecyclohexanol
C2H5 C2H5 HO
Ans. 3-Chloro-5-fluoro-3, 5-dimethylheptane

36. Br
Cl
26. CH3 – CH – CH2 – COOC2H5
CH3 Ans. 2-Bromo-5-chlorocyclopenta-2, 4-dien-1-ol
Ans. Ethyl-3-methylbutanoate OH
37.
CH3
27. CH – CH – C – CH – CH Cl
3 2 2
OH
Br Br
Ans. 2, 3-Dibromo-1-chloro-3-methylpentane Ans. Dodec-10-en-4-yne-3, 8-diol
Cl
28. (C 2 H 5 )2 CH − CHO
Ans. 2-Ethylbutanal 38.
CH2CH3 OH
29. CH2 = CH = CH – C = CH2
Cl Ans. 3-Chloro-5-(1-methylethenyl)cyclopenta 1,
Ans. 2-Chloro-3-ethyl-penta-1, 4-diene 3-dien-l-ol
39. O
47.
Ans. Buta-l,3-diyne
Br NH Br
40.
Ans. N, 3-Dibromobutanamide
Br
Ans. Dec-2-en-5-yne O
Br
48.
OH Cl NH
Cl
Cl
Ans. 4-Bromo-N-(3-bromo-2-chloropropyl)-3-
41. chloropentanamide
Br Br
Ans. 3,5-Dibromo-2-chloro-4-ethenylcyclohexanol 49. O
O
42.
O Ans. 3,4-Dicyclopropyloct-7-yn-2-one
O
NH Cl O
Ans. Cyclopropylmethyl cyclobutanecarboxylate Br
50. Cl OH
O
43.
O Ans. 7-(1-Bromoethyl)-3,4-dichloro-6-(formylamino)
non-8-enoic acid
O
Ans. Cyclobutylmethyl cyclopropanecarboxylate O

O
44.
O 51.
Ans. Ethyl 3-phenylpropanoate

Ans. Prop-2-en-1-yl 3-ethylpent-4-enoate
45. O
52.
Ans. Octylbenzene
O OH
Ans. 3-Methylidenehept-1-en-6-yn-4-one
O
53.
46. Cl
O
O Cl
Cl
Ans. 9-Ethyl-3-methylundecane-2,5,10-trione Ans. 3-(Trichloromethyl)benzoic acid
O OH CO2H
Cl
60.
54.
NO2C
Ans. 6-Chloro-5-cyano-4-nitrocyclohex-2-ene
Ans. 4-EthenyIbenzoic acid carboxylic acid
O O
HO
N O
61.
Br
55. OH
Br Cl O
Cl Ans. 10-Chloro-9-cyano-4-(methoxycarbonyl)-10-
oxodecanoic acid
Ans. 2,5-Dibromo-4-chlorophenol
WRITE THE STRUCTURAL FORMULAE
O
1. But-3-en-1-ol
56. O Ans. HOH 2 C − CH 2 − HC = CH 2
2. 2-Aminoethanol
OH
Ans. 4-Acetyloct-6-enoic acid Ans. H 2 N − CH 2 − CH 2 OH
3. 2-Chloro-3-methylbutane
O Ans. H C − CH − CH − CH
3 3
O | |
57. CH 3 Cl
OH 4. Octa-3, 5-diene
O
Ans. H 3 C − H 2 C − HC = CH − HC = CH − CH2 − CH 3
Ans. 3-FormyI-4-methyl-5-oxopentanoic acid
5. 4-Ethyl-5-methyl-hex-2-ene
CH 3
O Cl |
Ans. H 3 C − HC = CH − CH − CH − CH 3
|
58.
C2 H5
Cl Br
Ans. 1-(3-Bromo-5-chlorophenyl)-2-chloroethanone ARE THE FOLLOWING NAMES CORRECT IN IUPAC
SYSTEM ? IF NOT WRITE THE CORRECT NAMES
CO2H
OH 1. Pent-3-yne
Ans. No, it should be Pent-2-yne
59. O2N 2. 4, 4, 3-Trimethyl-hex-1-yne
CN Ans. No, it should be 3, 4, 4-Trimethylhex-1-yne
3. Hexa-1, 6-diene
Ans. 4-Cyano-2-hydroxy-5-nitrocyclohexane
carboxylic acid Ans. No, it should be Hexa-1, 5-diene
CONCEPTUAL ASSIGNMENTS
STEP—I CHECK YOUR CONCEPT 6. The IUPAC name of the compound

H
1. The correct IUPAC name of the compound CH3CH2N is
CH = O
CH3
| (a) aldoethanamine
CH3 CHCHCH3 is (b) N-Formyl aminoethane
| (c) ethyl formylamine
C 2H5
(d) N-Ethyl methanamide
(a) 2-ethyl-3-methyl butane
O
(b) 2-Isopropyl butane ||
(c) 3, 4-Dimethyl pentane 7. The IUPAC name of CH3 CH 2 OCH2 C − H is
(d) 2, 3-Dimethyl pentane (a) formyl methyl ethyl ether
2. The IUPAC name for the compound (b) ethyl aldomethyl ether
CH3 CH = CH − CHCH 3 is (c) 2-Ethoxy formate
| (d) 2-Ethoxy ethanal
C ≡ CH O
(a) 4-Ethyl-2-pentane 8. The correct IUPAC name of is
(b) 1-Ethyl-3-methyl-2-butane
O
(c) 3-Methylhex-4-en-1-yne
(d) 4-Methyl-2-hexen-5-yne (a) Ethanedial (b) 2-Ketopropanal
(c) Butane-2,-3dione (d) Ethanedione
3. The correct IUPAC name of the compound
is 9. The IUPAC name of
O CH3 − CH − CH 2 CH(OH) − CH 3 is
|
(a) Pent-4-en-2-one CH CH
2 3
(b) 3-Buten-1-al
(c) 3-Acetyl propene-1 (a) 2-Ethylpentan-4-ol
(d) Formyl Propene (b) 4-Ethylpentan-2-ol
(c) 4-Methylhexan-2-ol
(d) 4-Methylhexan-2-ol
OH
10. The principal functional group of following compound
CH3CH2C – CH2 is is
OH O
CH3 | ||
ClCH 2 CH CH 2 − C − CH2 NO2
(a) ter-pentanol cyclo propane
(a) nitro (b) alcohol
(b) 2-Cyclobutylbutan-2-ol
(c) alkyl halide (d) ketone
(c) 1-Cyclopropyl-2-methylbutan-2-ol
(d) 2-Cyclobutylbutan-2-ol 11. The correct IUPAC name of
5. The IUPAC name of the compound CH2 (OH) H CH2
CH(NH2)CO2H is
CH3CH2 – C – CH – CH 2 is
(a) 2-Amine-3-hydroxypropanoic acid
(b) 1-Hydroxy-2-aminopropan-3-oic acid CH2Cl
(c) 2-Amino-3-hydroxy propanoic acid (a) 1-Chloro-2-butyl cyclo propane
(d) 1-Amino-2-hydroxy propanoic acid (b) 1-Chloro-2-cyclopropyl butane
(c) 1-Chloromethyl-1-ethyl cyclo propane (a) – NH2 (b)– NO2

(d) 3-Chloromethyl-1, 2-methylene pentane (c) −CN (d) – C= O
|
O O
|| || 20. 3-Methyl-butan-1-ol is the IUPAC name of
12. The correct OUPAC name of CH3 − C − O − C − H is
(a) sec-pentyl alcohol
(a) acetyl methanoate (b) tert-pentyl alcohol
(b) formyl ethanoate (c) iso-pentyl alcohol
(c) ethoxy methanoate (d) neo-amyl alcohol
(d) ethanoic methanoic anhydride
STEP—II APPLY YOUR CONCEPT
13. The IUPAC name of the compound is

(a) Bicyclo [2.1.0] pentane 1. The compound is known by which of the
(b) 1, 2-cyclopropylcyclobutane
(c) cyclopentane (4, 3) annulene following names ?
(d) 1, 2-methylnecyclobutane (a) Bicyclo-[2.2.1] octane
CH = CH (b) Bicyclo- [2.2.2] octane
| | (c) Bicyclo-[1.2.1] octane
14. The name of CHO NH 2 is (d) Bicyclo-[1.1.1] octane
(a) 1-emino prop-2-enal 2. The correct structure of iso-octane is
(b) 3-amino prop-2-enal
(a) (CH 3 )3 CCH(CH 3 )CH 2 CH 3
(c) 1-amino-2-formylthene
(d) 3-emino-1-oxoprop-2-ene (b) (CH 3 )3 CHCH(CH 3 )CH(CH 3 )2
(c) (CH 3 )3 CCH 2 CH(CH 3 )2
15. The correct IUPAC name of the acrolein is
(d) CH 3 CH(CH 3 )CH 2 CH(CH 3 )2
(a) prop-2-enal (b) cyanomethane
(c) methanenitrile (d) cyanoethane 3. The IUPAC name of the compound
16. A student named a certain compound as 2, 3-diethyl Cl CH2CH3
butane. Its correct IUPAC name is C=C is
CH3 I
(a) 2, 3-dimethyl hexane
(b) 3, 4-Dimethyl hexane (a) trans-2-chloro-3-iodo-bent-2-ene
(c) 2-Ethyl-3-methyl pentane (b) cis-2-chloro-3-iodo-2-pentane
(d) 2-Ethyl-butane (c) trans-3-iodo-4-chloro-3-pentene
(d) cis-3-iodo-4-chloro-3-pentene
17. The IUPAC name of Cl3CCH2CHO is
4. The correct IUPAC name of the compound with
(a) chloral
molecular formula (CH3)3 C – CH3 is
(b) trichloropropanal
(a) Pentane
(c) 1, 1, 1-trichloropanal
(b) 1, 1, 1-trimethyl pentane
(d) 3, 3, 3-trichloropropanal
(c) 2, 2-dimethyl propane
18. When – COOC2H5 group is present as a substituent in (d) Neopentane
the chain it shall be named 5. The correct decreasing order of preference of
(a) ethoxy methanone functional groups during the IUPAC nomenclature of
(b) ethyl methanoate poly functional compounds is
(c) carbethoxy (a) — COOH, — SO3H — CONH2, — CHO
(d) ethyl carboxy (b) — SO3H, — COOH, — CONH2 — CHO
19. Which group is always taken as a substituent in the (c) — CHO, — COOH: — SO3H, — CONH3
nomenclature ? (d) — CONH2, — CHO, — SO3H, — COOH
6. The alkane which has only primary hydrogen atoms 13. The IUPAC name of the compound
is
(a) pentane
is
(b) isopentane
HO
(c) neopentane
(d) 2,2-dimethylbutane (a) 3,3-dimethyl-,l-hydroxy cyclohexane
(b) l,1-dimethyl-3-hydroxy cyclohexan
7. The IUPAC name of CH3CH(OH)CH2CH2COOH is
(c) 3,3-dimethyl-1-cyclohexanol
(a) 4-hydroxy pentanoic acid (d) l,l-dimethyl-3-cyclohexanol
(b) l-carboxybutan-3-ol
14. The compound having only primary hydrogen atoms is:
(c) l-carboxybutan-4-ol
(d) 4-carboxybutan-2-o1 (a) butane (b) iso-butene
(c) cyclohexane (d) 2,3-dimethylbutene
8. The name(s) of the following compound is
OH 15. The compound which contains all the four 1°, 2°, 3°
and 4° carbon atom is
CH2 C CH2 (a) 2,3-dimethylpentane
(b) 3-chloro-2,3-dimethylpentane
COOH COOH COOH (c) 2,3,4-trimethyIpentane
(a) 2-hydroxypropane-1,2,3-tricarboxy lie acid (d) 3,3-dimethylpentane
(b) 3-carboxy-3-hydroxy-l,5-pentanedioic acid
(c) citric acid Cl
16. The IUPAC name of is
(d) all of the above
O
9. The IUPAC name of the following compound is
(a) 2-ethy 1-3-methyl butanoyl chloride
CH2 CH CH2 (b) 2,3-dimethyl pentanoyl chloride
(c) 3,4-dimethyI pentanoyl chloride
CN CN CN
(d) l-chloro-l-oxo-2,3-dimethyl pentane
(a) 1,2,3-tricyano propane 17. The IUPAC name of the compound shown below is
(b) propane tricarbylamine
Cl
(c) Propane-1,2,3-tricarbonitrile
(d) 3-cyanopropane-l,5-dmitriIe
10. The structure of 4-methylpent-2-en-l-ol is
Br
(a) (CH3)2C = CHCH,CH2OH
(a) 2-bromo-6-chlorocyclohex-1 -ene
(b) (CH3)2CHCH = CHCH2OH
(b) 6-bromo-2-chlorocyclohexene
(c) CH3CH2CH = CHCH2OH
(c) 3-bromo-l-chlorocyclohexene
(d) CH3CHOHCH = C(CH3)2
(d) l-bromo-3-chlorocyclohexene
11. The correct name of CH3 CH2 CH2 is
18. The IUPAC name Cl CH2 CH C CH2OH is
C ≡ C CH
CH2CH3
(a) hex-3-yn-5-ene (b) hex-5-en-3-yne
(c) hex-3-yn-l-ene (d) hex-l-en-3-yne (a) l-chloro-2-ethyl-4-hydroxybut-2-ene
(b) 4-hydroxy-1 -chloro-2-ethylbut-2-ene
12. Which of the following compounds has isopropyl
(c) 4-chloro-2-ethylbut-2-en-1 –ol
group?
(d) 2-ethyl-4-chlorobut-2-en-l-ol
(a) 2,2,3,3-tetramethylpentane
(b) 2,2-dimethylpentane 19. The IUPAC name of CH3COCH(CH3 )2 is:
(c) 2,2,3-trimethylpentane (a) isopropyl methyl ketone
(d) 2-methylpentane (b) 2-methyl-3-butanone
(c) 4-methyl-isopropyl ketone which second carbon is substituted. Correct IUPAC

(d) 3-methyl-2-butanone name of compound (R) is
(a) 1-(1-Methylethyl)-2-(1-methylpropyl)
20. The IUPAC name of is cyclohexane
(b) 1-(2-Methylethyl)-2-(1-methYlpropyl)
(a) 3-ethyl-4,4-dimethylheptane cyclohexane
(b) l,l-diethyl-2,2-dimethylpentane (c) 1-(1-Methylethyl)-2-(2-methylpropyl)
(c) 4,4-dimethyl-5,5-diethylpentane cyclohexane
(d) 5,5-diethyl-4,4-dimethylpentane (d) 1-(-1-Methylethyl)-2-butylcyclohexane
Cl
STEP—III CHECK YOUR EXPERTISE
CH3
Confront the Conceptual Questions as Present JEE Pattern 5. IUAC name of Br C2H5 is
MCQS with only one correct answer (a) 4-Bromo-6-chloro-2-ethyl-1-methylcyclohex-
1. The IUPAC name of the following compound is 1-ene
(b) 5-Bromo-1-chloro-3-ethyl-2-methylcyclohex-
COOC2H5 2-ene
(c) 5-Bromo-3-chloro-1-ethyl-2-methylcyclohex-
COCl 1-ene
(a) 2-(Ethoxycarbonyl)benzalychloride (d) 1-Bromo-5-chloro-3-ethyl-4-methylcyclohex-
(b) Ethyl 2-(Chloroformy) benzoate 3-ene
(c) Ethyly 2-(chloromethanoyl) benzoate
(d) Ethyl 2-(Chorocarbonyl) benzene carboxylale 6. Correct IUPAC name of the following compound is:
Br
HO
2. The IUPAC name of the compound will be

(a) Tropyluim bromide
(b) 1-Bromocyclohepta-2, 4, 6-triene Br
(c) 3-Bromocyclohepta-1, 4, 6-triene
(a) 3-(Hepta-2,4,6-trienyl)-4 bromo cyclopenta-2, 4,
(d) 7-Bromocyclohepta-1, 3, 5-triene
-dien-1-ol
O (b) 7-(2-Bromo-4-hydroxy cyclopenta-1,4-dienyl)
Et hepta-1,3,5-triene
3. Correct IUPAC name of the compound O is (c) 7-(5-Bromo-3-hydroxycyclopenta-1,4-dienyl)
Me hepta-1,3,5-triene
O (d) 3-Bromo-4-(hepta-2,4,6-trienyl)cyclopenta-2,4-
dien-1-oll
(a) 2-Ethyl-3methylbut-2-ene-1, 4-dioic anhydride
(b) 3-Ethyle-2-methylbut-2-enedioic anhydride 7. Which of the following structure(s) is the correct
(c) 2-Ethyle-3-Methyl-1, 4-Diketobut-2-enoic structure of 3-etyly-5, 5-diisopropyl-7-methlnonane
anhydride
(d) 2-Ethyl-3-methylcyclopenatanoxy-1, 4-dione
(a)
4. A hydrocarbon (R) has six membered ring in which
there is no unsaturation. Two alkyl groups are
attached to the ring adjacent to each other. One group
has 3 carbon atoms with branching at 1st carbon atom (b)
of chain and another has 4 carbon atoms. The larger
alkyl group has main chain of three carbon atoms of
(a) bicyclo [2.2.0] octane

(b) bicyclo [0.2.2] hexane
(c) (c) bicyclo [2.1.1] hexane
(d) bicyclo [2.2.0] hexane
12. The IUPAC name of
CH3 O
(d) CH3 C C CH2 CH2OH is
(a) l-hydroxy-4-methylpentan-3-one
8. The correct IUPAC name of the following compound
(b) 2-methyl-5-hydroxypentan-3-one
is
(c) 4-methyl-3-oxopentan-l-ol
(d) hexan-l-ol-3-one
(a) 5,6-Diethyl-8-methyl dec-6-ene CHO
(b) 5,6-Diethyl-3-methyl dec-4-ene NO2
(c) 5,6-Diethyl-3-methyl dec-4-ene
(d) 2,4,5-Triethylnon-3-ene is
9. IUPAC name of compound OCH3
Cl (a) 2-formyl-5-methoxynitrobenzene
is (b) 4-formyi-3-nitroanisole
(c) 4-methoxy-2-nitrobenzaldehyde I
Br
(d) 4-methoxy-6-nitrobenzaldehyde
(a) 3-Bromo 7-chloro-7 ethyl-5-(1,1-dimethyethyl)- 14. The IUPAC name of tertiary butyl iodide is
5-(2-methylpropyl)-3-methylnonane (a) l-iodo-3-methyl propane
(b) 3-Bromo 7-chloro-5-(1,1-dimethyethyl)-7-ethyl- (b) 2-iodo-2-methyl propane
3methyl-5-(2-methylpropyl)nonane (c) 4-iodobutane
(c) 3-Bromo 7-chloro-7 ethyl-3-, methyl-5-(1,1- (d) 2-iodobutane
dimethyethyl)-5-(2-methylpropyl)nonane
(d) 3-Bromo-5-(1,1-dimethyethyl)-5-(2- 15. The correct structure of 4-bromo-3-methyl but-1-ene
methylpropyl)-7-chloro-7ethyl-5—3-methyl- is
nonane (a) BrCH = C(CH3)2
(b) H2C = C(CH3)CH2CH2Br
10. Correct IUPAC name of the compound
(c) H2C = CH — CH(CH3) —CH2Br
H3C CH2 O C O C CH2 CH3 is (d) CH3—C(CH3) = CHCH2Br
O O 16. The IUPAC name of the compound
(a) 4-(Ethyl methanolyonxy) phenylpropanoate
O
(b) Diethyl Benzene-1,4-dicarloxylate CH3
(c) 4-(1-Oxo-2-oxabutyl) phenylpropanoate C N
is
(d) 1-(1-Oxo-2-oxbutyl)-4-(1-oxopropoxy) benzene CH3
11. The IUPAC name of the following compound is: (a) cyclopropionamide
(b) N-methyl cyclopropanamide
(c) N, N-dimethyl cyclopropane carboxamide
(d) none of the above
17. The IUPAC name of the following compound 22. The IUPAC name of the compound
CH3
CH3 N C CH2 CH3 is is

CH3 C2H5 (a) 2,4,5,6-tetramethyI-7-ethyldeca-l,7-diene
(a) N, N′-dimethyl-1-ethyl-1-methyl propan-1-amine (b) 7-ethyl-2,4,5,6-tetramethyldeca-1,8-diene
(b) 1-Methyl-1-ethyl-N, N′-dimethyl propanamine (c) 4-ethyl-5,6,7,9-tetramethyldeca-2,9-diene
(c) 1-Ethyl-N, N′-dimethyl propan-1-amine (d) none of the above
(d) 1-Ethyl-1-methyl-N, N′-dimethyl propanamine 23. Which one of the following compounds has IUPAC
18. The IUPAC name of nomenclature?
Cl (a) CH3 CH2 CH2 COOC2H5
ethylbutanoate
CH3 C CH2 CH = CH CH3 is (b) CH3 CH CHCH3
H CH3 OH
(a) 5-chlorohex-2-ene 2-methylbutan-3-ol
(b) 2-chlorohex-5-ene (c) CH3CH C CH2CH3

(c) l-chloro-l-methylpent-3-ene CH3 O
(d) 5-chloro-5-methylpent-2-ene 2-methylpentan-3-one
(d) CH3 CH CH2CHO
19. The 1UPAC name of
CH2 C CH CH2 C NH2, is CH3
3-methylbutanal
CONH2 NH CONH2 O
24. CH3CH2CH2
(a) 2-iminobutan-l,3,4-tricarboxamide
(b) 3-imino-4-carbamoylhexan-l,6-diamide
CH3 CH2CH3
(c) 6-amino-2-imino-4-carbamylhexanamide
(d) none of the above The IUPAC name of the above compound will be
(a) 5-ethyl-1 -methyl-2-propylcyclohexane
20. The 1UPAC name of the compound (b) 1 -ethyl-3-methyl-4-propylcyclohexane
(c) 4-ethyl-2-methyl-l-propylcyclohexane
CH3 is
(d) l-propyl-3-ethyl-2-methylcyclohexane
CH3
(a) 3-(3-methylcyclopentyl) benzene
CH3
(b) 1-(3’-methyIcyclopenlyl) benzene 25.
(c) 2-(2-methylcyclopentyl) benzene CH3
(d) none of the above
What will be the IUPAC name of the above compound?
CH3 (a) 1,1,2-trimethylcyclopentane
CH3 (b) 1,2,2-trimethylcyclopentane
CH CH2 CH2 CH
21. CH3 (c) 1,1,5-trimethylcyclopentane
(d) None of the above
C2H5
26. Select the correct IUPAC name of the following
The IUPAC name of the above compound will be compound:
(a) l-ethyl-4-(5-methylhexyl) cyclohex-1-ene Cl
(b) l-ethyl-4(l,4-dimethylpentyl) cyclohex-1-ene
(c) 5-(1,4-dimethylpentyI)-2-ethylcyclohex-3-ene
(d) 4-( 1,4-dimethylpentyl)-1-ethylcyclohex-1 -ene C2H5 OH
(a) 2-ethyl, 1-chloro, cyclohexanol IUPAC name

(b) 4-chloro, 3-ethylcyclohexanol 1. cyclohexanoic acid
(c) 4-chloro, 5-ethylcyclohexanol 2. 1,2,4- benzene tricarboxylic acid
(d) 4-hydroxy, 2-ethyl-1-chlorocyciohexane 3. 4-methylcyclohexane- carboxylic acid
4. 4-bromobenzoic acid
27. Give the IUPAC name of the following compound: 31. Select the correct priority for citation as principal
S group:
CH3 C CH2 COOH O O O
(a) 3-Thiabutanoic acid (a) C OH > C > C H > OH > SH

(b) 3-Sulphobutanoic acid O O O
(c) 3-Thiobutanoic acid
(d) 3-Thioxobutanoic acid (b) C OH > C > C H > SH > OH
O O O
28. Select the correct IUPAC name of the following
compound: (c) C OH > C >H C > SH > OH
O O O
(d) C OH > C H> C > OH > SH
(a) 1,1-eye cyclobutyl heptane 32. What will be the prefix in the following compound?
(b) Bicyclo [6.3.0] nonane HOOC CH2
(c) Spiro [3.6] decane
(d) Spiro [6.3] decane HOOC CH2 CH CH2 CH2 COOH
(a) methylcarboxy (b) carboxymethyl
CH CH2 (c) carboxyethyl (d) elbylcarboxy
29. 33. The IUPAC name of
O
Give the correct IUPAC name of the above compound:
C CH3 is
(a) 2-viny 1-3,4,7,10-tetrahydronaphthalene
(b) 1 -vinyl-5,8,9,10-tetrahydronaphthalene (a) phenylethanone (b) methylphenylketone
(c) 9-Ethenylbicyclo [4.4.0] deca-l,4,9-triene (c) acetophenone (d) pbenylmethylketone
(d) 3-ethenyl bicyclo [4.4.0] deca-3,5,8-triene O
30. The IUPAC name of which of the following
compounds is not correct? 34. CH3 CH C CH OCH2 CH3
Compound
OCH3 CH3
COOH The IUPAC name of this compound is

(a)
(a) 2-ethoxy-4-inethoxy-pentan-3-one
COOH (b) 2-methoxy-4-ethoxy-pentan-3-one
(c) 2-ethoxy-3 -methoxy-pentan-3 -one
(b) HOOC COOH (d) none of the above
35. The IUPAC name of BrCH2CHCOCH2CH2CH3, is
(c) CH3 CONH2

COOH
(a) 2-bromomethyl-3-oxohexanamide
(b) l-bromo-2-amido-3-oxohexane
(d) Br COOH (c) 1 -bromo-2-amido-n-propylketone
(d) 3-bromo-2-propyl propanamide
36. Which name is incorrect? 3. CnH2n+2O (C) aldehydes, ketones

4. CnH2nO (D) alkynes, alkadienes
Codes:
(a) Bicyclo (2.2.1) hept-2-ene (a) 1-A, 2-B, 3-C, 4-D (b) 1-D, 2-C, 3-B, 4-A
(c) 1-B, 2-D, 3-A, 4-C (d) 1-C, 2-A, 3-D, 4-B
(b) Bicyclo (3.2.1) octane
2. Match the following:
O O
1. Dimethyl acetylene (A) Propanone
(c) Bicyclo (2.2.2) octane-2,6- 2. Methyl acetic acid (B) Trichloromethane
dione 3. Chloroform (C) Propanoic acid
4. Acetone (D) But-2-yne
Codes:
(d) Bicyclo (2.2.0) hexane
(a) 1-D, 2-C, 3-B, 4-A (b) l-A, 2-B, 3-C, 4-D
(c) 1-C, 2-D, 3-A, 4-B (d) 1-B, 2-A, 3-D, 4-C

[Hint: The IUPAC name of is bicyclo
(2.2.2) hexane] Codes:
(a) 1-A, 2-B, 3-C, 4-E, 5-D
37. Select the correct IUPAC names among the following:
(b) 1-B, 2-A, 3-E, 4-D, 5-C
Compound IUPAC name (c) 1-C, 2-E, 3-D, 4-B, 5-A
1. 2+& &+ &+ 3,7-dimethyloct- (d) I-D, 2-C, 3-B, 4-A, 5-E
2,6-dienal (e) 1-E, 2-D, 3-A, 4-C, 5-B
&+
4. Match the List I and List II and select the correct
answer from the given code:
2. Spiro (3,6) decane
List I List II
I A. 1. Fused bicycle
B. 2. Bridged bicyclic
3. 3-Ethyl-7-
iodobicyclo (2.2.1)
heptane
Et
C. 3. Spirocyclic
4. N N-ethyl-N-methyl
ethanamine Codes :
(a) (A-3),(B-l),(C-2) (b) (A-l), (B-2), (C-3)
(c) (A-3),(B-2),(C-1) (d) (A-2), (B-l), (C-3)
(a) 1, 2, 4 (b) 1, 3, 4
(c) 2, 3, 4 (d) 1, 2, 3 COMPREHENSION
In addition to the standard ring systems (such as cyclohex-
COLUMN MATCHING
ane), cyclic compounds can also be bicyclic, tricyclic etc. or
they can be spirocyclic, bicyclic or bridge head carbons. The
1. Match the List I and List II and select the correct
points of attachment of two rings are called bridge head atoms.
answer using the code given below the lists:
Some bicyclic compounds like camphor are commonly
List I List II found in plants. Others like norbornane can be synthesized
1. CnH2n (A) alcohols, ether in the laboratory. The formal names of bicyclic and related
2. CnH2n–2 (B) alkenes, cycloalkanes ring systems are based on:
(1) Total number of atoms in the molecule. H

(2) The number of atoms in each bridge connecting the 2. (A) : is called cyclohexanitrile.
bridge head atoms. These numbers are written in CN
square brackets in decreasing order. (R) : It is an aromatic compound
Spirocyclic compounds have two fused rings, but only 3. (A) : The locant (2.8.7) is preferred over the locant
one bridge head atom. Spirocyclic compounds are named (3.4.9).
like bicyclic compounds, but have the prefix spirocyclo. (R) : The lowest locant number at first difference is
Answer the following questions: preferred.
4. (A) : The IUPAC name of CH3—CH=CH—C=C—II
1. is pent-3-en-l-yne and not pent-2-en-4-yne.
(R) : The lowest locant rule for multiple bond is
preferred.
What is the IUPAC name of the above compound?
(a) cyclo [1.2.2] heptane 5. (A) : The correct IUPAC name for the compound
(b) bicyclo [1.2.2] heptane C6H5COOCH2CH2COOH is 3-benzoyloxy propanoic
acid.
(c) bicycle [2.2.1] heptane
(R) : It is named as derivative of cyclopentane
(d) cyclo [2.2.1] heptane
because the number of carbon atoms in the ring is
more than that in the side chain.
2. The number of atoms in each bridge are:
SUBJECTIVE QUESTIONS
(a) [3.1] (b) [3.1.0]
Write down the ‘IUPAC’ nomenclature of the following
(c) [1.3.0] (d) [2.1.0]
molecules.
3. Select the correct statements about the following
compounds:
1.
(a) It is a tricyclic compound. NO2 HOOC

5 6 2′ 3′
(b) It is bicycle compound.
(c) It is spiro compound. 2. 4
1 1′
4′
(d) Its IUPAC name is bicyclo [2.2.2] octane.
3 2 6′ 5′
ASSERTION REASONING COOH O2N
O
Following questions consist of an Assertion (A) and Reason 1′ 2′ 3′ 4′
(R). Use the following keys to select correct answer: CH2CH2COCH3
1
(a) If both assertion and reason are correct and reason is 3. 2
the correct explanation of the assertion.

(b) If both assertion and reason are correct but reason is 1
9 10 CH3
not correct explanation of the assertion.
5 2
(c) If assertion is correct but reason is incorrect. 4. 8
(d) If assertion is incorrect but reason is correct. 3
7 6 4
1. (A) : The IUPAC name of the compound 8 1
7
O is cyclohexylidene methanone 2
5.
6 4
(R) : CH2 = C = O is called ketone O 3
5
8 1
7
2 8
7
4 11.
3 6
3 5
5 4
6. 1
9 10 1
2 CN
6 2 CH3
12. 8
5
CH3
7 6 4 3
3 2 1 1
7. CH3 C COOC2H5
1′
13. 2 3 4
2′
1
3′ 6 2
NO2
14. 7
5 3
O
4
COOH
2 Cl
3 1 9 10 1 2
6
4 15. 8
5
8. OHC 5
7 6 4 3
9. CH2 CH CH2 2
1 3
CONH2 CONH2 CONH2 16. 6
7 4
5
O O
6 5 4 3 2 1 3′
2 2′′
10. H C CH2 CH2 CH CH2 C H 1
17. 1′ 2′ 1′′
CH2CHO 3 3′′
SOLUTIONS
ANSWER KEYS
STEP – I
1. (d) 2. (c) 3. (a) 4. (c) 5. (c) 6. (d) 7. (d) 8. (c) 9. (d) 10. (d)
11. (b) 12. (d) 13. (a) 14. (b) 15. (a) 16. (b) 17. (d) 18. (c) 19. (b) 20. (c)
STEP – II
1. (b) 2. (c) 3. (a) 4. (c) 5. (a) 6. (c) 7. (a) 8. (a, c) 9. (c) 10. (b)
11. (d) 12. (d) 13. (c) 14. (b) 15. (b) 16. (b) 17. (c) 18. (c) 19. (d) 20. (a)
STEP – III
MCQS WITH ONLY ONE CORRECT ANSWER

O 2

1 C OC2H5 (W
1. (d) 2. (d) 3. (a) 2

2 C Cl 0H
2
O (WK\OPHWK\OEXWHQHGLRLFDQK\GULGH
Ethyl 2-(Chlorocarbonyl) benzene carboxylate.
6
5 1
4. (c) 5. (c) 6. (d) 7. (b) 8. (c) 9. (b)
4 2
3
2 3
1
10. (b) CH3 CH2 O C O C CH2 CH3 11. (d) 12. (a) 13. (c) 14. (b) 15. (c)
4
O O
Ethyl 4-propanoyloxybenzenecarboxylate
16. (c) 17. (d) 18. (a) 19. (b) 20. (b)
21. (b) 22. (a) 23. (b) 24. (c) 25. (a) 26. (b) 27. (a) 28. (c) 29. (c) 30. (a)
31. (d) 32. (b) 33. (a) 34. (a) 35. (a) 36. (d) 37. (a)
COLUMN MATCHING
1. (c) 2. (a) 3. (b) 4. (a)
COMPREHENSION
1. (c) 2. (b) 3. (b, d)
ASSERTION REASONING
1. (b) 2. (c) 3. (a) 4. (a) 5. (a)
SUBJECTIVE QUESTIONS
1. 1, 1′, 3′, 1′-Tercyclobutane.
3 4
1′ 2′
2 1
1′′ 2′′
4′ 3′
4′′ 3′′
1, 1′, 3′, 1′′-Tercyclobutane
2. 6,6’-Dinitrophenyl-2, 2’-dicarboxylic acid 3. 2-(3’-Oxobutyl) cyclohexan-1-one

4. 2-Methyl spiro [4.5] deca-1,6 diene 5. 5-Oxa-spiro [3.4] octane
6. Bicyclo [2.2.2] oct-5-ene-2-nitrile 7. Ethyl-2-methyl-2-(3’-nitro phenyl) propanoate
8. 4-Formyl-2-oxocycIohexane carboxylic acid 9. Propane-1, 2, 3-tricarboxamide
10. 3-(Formyi methyl) hexane-1.6-dial 11. Bicyclo [3.2.1] octane
12. 2-Methyl spiro [4.5] deca-1, 6-diene 13. Bicyclo [1.1.0] butane
14. 7,7-DimethyI bicyclo [2.2.1] heptane 15. 2-Chlorospiro [4.5] decane
16. 2,6,6-Trimethylbicyclo [3.1.1] hept-2-ene 17. 1,1’, 2’, l”-Tercyclppropane.
General Organic
Chemistry
2
Introduction
Before reading this chapter, students are advised to go through the topic ‘chemical bonding’ from any standard text book
of Inorganic Chemistry.
ELECTRONIC STRUCTURE
A Simple View
In any introductory chemistry cours, you will have come across the electronic structures of hydrogen and carbon drawn as
H C
NOTE:
There are many places where you could still make use of this model of the atom. It is, however, a simplification and can be
misleading. It gives the impression that the electrons are circling the nucleus in orbits like planets around the sun. As you
will see in a moment, it is impossible to know exactly how they are actually moving.
The circles show energy levels representing increasing distances from the nucleus. You could straighten the circles out
and draw the electronic structure as a simple energy diagram.
more levels (not used in carbon)
e
n second level
e
r first level
g
y
carbon’s nucleus (not to scale)
Atomic Orbitals
Orbits and orbitals sound similar, but they have quite different meanings. It is essential that you understand the difference
between them.
2.2 General Organic Chemistry
The impossibility of drawing orbits for electrons

To plot a path for something you need to know where exactly the object is and be able to work out exactly where it is going
to be an instant later. You can not do this for electrons.
NOTE:
In order to plot a plane’s course, it is no use knowing its exact location in mid-Atlantic if you do not know its direction or
speed. Equally it is no use knowing that it is travelling at 500 mph due west if you have no idea whether it is near Iceland
or the Azores at that particular moment.
The Heisenberg Uncertainty Principle says (loosely) that you can not know with certainty both where an electron is
and where it is going next. That makes it impossible to plot an orbit for an electron around a nucleus. Is this a big problem?
No. If something is impossible, you have to accept it and find a way around it.
Hydrogen’s electron–the 1s orbital
NOTE:
In this diagram (and the orbital diagrams that follow), the nucleus is shown very much larger than it really
is. This is just for clarity. Suppose you had a single hydrogen atom and at a particular instant, you plotted
the position of the one electron. Soon afterwards, you do the same thing, and find that it is in a new position. a 1s orbital
You have no idea how it got from the first place to the second.
You keep on doing this over and over again, and gradually build up a sort of 3D map of the places that the electron is
likely to be found in.
In the case of hydrogen, the electron can be found anywhere within a spherical space surrounding the nucleus. The
diagram shows a cross-section through this spherical space.
95% of the time (or any other percentage you choose), the electron will be found within a fairly easily defined region of
space quite close to the nucleus. Such a region of space is called an orbital. You can think of an orbital as being the region
of space in which the electron lives. Note: If you wanted to be absolutely 100 per cent sure of where the electron is, you
would have to draw an orbital the size of the Universe.
What is the electron doing in the orbital? We do not know, we can not know, and so we just ignore the problem. All you
can say is that if an electron is in a particular orbital it will have a particular definable energy.
Each Orbital has a Name

The orbital occupied by the hydrogen electron is called a 1s orbital. The ‘1’ represents the fact that the orbital is in the
energy level closest to the nucleus. The ‘s’ tells you about the shape of the orbital. ‘s’ orbitals are spherically symmetric
around the nucleus–in each case, like a hollow ball made of rather chunky material with the nucleus at its centre.
The orbital on the left is a 2s orbital. This is similar to a 1s orbital except that the region where there is the greatest
chance of finding the electron is further from the nucleus–this is an orbital at the second energy level.
If you look carefully, you will notice that there is another region of slightly higher electron density (where the dots are
thicker) nearer the nucleus. (‘Electron density’ is another way of talking about how likely you are to find an electron at a
particular place.)
2s (and 3s, 4s, etc.) electrons spend some of their time closer to the nucleus than you might expect.
The effect of this is to slightly reduce the energy of electrons in ‘s’ orbitals. The nearer to the nucleus
the electrons get, the lower gets their energy.
3s, 4s (etc.) orbitals get progressively further from the nucleus.
p orbitals
Not all electrons inhabit s orbitals (in fact, very few electrons live in s orbitals). At the first energy
level, the only orbital available to electrons is the 1s orbital, but at the second level, as well as a 2s
a 2s orbital
orbital, there are also orbitals called 2p orbitals.
General Organic Chemistry 2.3
A p orbital is rather like two identical balloons tied together at the nucleus. The diagram on the right is a
cross-section through that 3-dimensional region of space. Once again, the orbital shows where there is a 95
per cent chance of finding a particular electron.
If you imagine a horizontal plane through the nucleus, with one lobe of the orbital above the plane and the
other beneath it, there is zero probability of finding the electron on that plane. So how does the electron get
from one lobe to the other if it can never pass through the plane of the nucleus?
Unlike an s orbital, a p orbital points in a particular direction–the one drawn points up and down the page.
At any one energy level, it is possible to have three absolutely equivalent p orbitals pointing mutually
a p orbital
at right angles to each other. These are arbitrarily given the symbols px, py and pz. This is simply for conve-
nience–what you might think of as the x, y or z direction changes constantly as the atom tumbles in space.
Py
PZ
PX
The p orbitals at the second energy level are called 2px, 2py and 2pz. There are similar orbitals at subsequent levels–3px,
3py, 3pz, 4px, 4py, 4pz and so on.
All levels except for the first level have p orbitals. At the higher levels the lobes get more elongated, with the most
likely place to find the electron more distant from the nucleus.
Fitting electrons into orbitals

Because for the moment we are only interested in the electronic structures of hydrogen and carbon, we do not need to
concern ourselves with what happens beyond the second energy level.
REMEMBER:
 At the first level, there is only one orbital—the 1s orbital.
 At the second level, there are four orbitals—the 2s, 2px, 2py and 2pz orbitals.
 Each orbital can hold either 1 or 2 electrons, but no more.
Electrons-in-boxes
Orbitals can be represented as boxes with the electrons in them shown as arrows. Often an up-arrow and a down-arrow are
used to show that the electrons are in some way different.
The need to have all electrons in an atom different comes out of quantum theory. If they live in different orbitals, that
is fine, but if they are both in the same orbital there has to be some subtle distinction between them. Quantum theory al-
locates them a property known as ‘spin’-which is what the arrows are intended to suggest.
A 1s orbital holding two electrons would be drawn as shown on the right, but it can be written even more
quickly as 1s2. This is read as ‘one s two’, not as ‘one s squared’.
You must not confuse the two numbers in this notation. 1s
energy level number of electrons

in orbital
1s2
type of orbital
The order of filling orbitals

Electrons fill low energy orbitals (closer to the nucleus) before they fill higher energy ones. Where there is a choice be-
tween orbitals of equal energy, they fill the orbitals singly as far as possible.
The diagram (not to scale) summarises the energies of the various orbitals in the first and second levels.
e
n 2p
e 2s
r
g
y
1s
Notice that the 2s orbital has a slightly lower energy than the 2p orbitals. That means that the 2s orbital will fill with
electrons before the 2p orbitals. All the 2p orbitals have exactly the same energy.
The Electronic Structure of Hydrogen

Hydrogen only has one electron and that will go into the orbital with the lowest energy–the 1s orbital. Hydrogen has an
electronic structure of 1s1. We have already described this orbital earlier.
The electronic structure of carbon
Carbon has six electrons. Two of them will be found in the 1s orbital, close to the nucleus. The next two will go into the 2s
orbital. The remaining ones will be in two separate 2p orbitals. This is because the p orbitals all have the same energy and
the electrons prefer to be on their own if that is the case.
e
n 2px 2py 2pz
e 2s
r
g
y
1s
People sometimes wonder why the electrons choose to go into the 2px and 2py orbitals rather than the 2pz. They do not.
All of the 2p orbitals are exactly equivalent, and the names we give them are entirely arbitrary. It just looks tidier if we
call the orbitals the electrons occupy the 2px and 2py. The electronic structure of carbon is normally written 1s22s22px12py1
FORMAL CHARGE
Formal charge represents actual charge on an atom in its non bonded or bonded state. If the number of its own valence elec-
trons in its nonbonded or bonded state is more than its number of valence electrons in the neutral isolated atomic state, it is
thought to be negatively charged and it will have negative formal charge. If it contains less than that number of electrons,
it will have a positive formal charge.
Let us consider the chlorine atom which contains seven valence electrons in the isolated neutral atomic state.
Cl (Z = 17) 1s22s22p63s23p5
7 valence electrons
(The total number of electrons in the shell with maximum quantum number is the number of valence electrons.)
Therefore, the Lewis formula of chlorine atom is as follows.
Cl The formal charge of chlorine atom under this condition is zero (o) or we can say it has no formal charge and it is
neutral atom.
Now consider the following chlorine atom.
Cl We see that chlorine atom contains 8 valence electrons which is one more than that of the neutral atom. Therefore
it will have one unit negative formal charge and the correct representation will be as follows.
-
Cl This is called chloride ion.
Similarly, the following chlorine atom has 6 valence electrons. It contains one less electron than that of the neutral
atom.
Cl
Therefore, it will have one unit positive formal charge and the correct representation will be as follows.
+
Cl
So far, we have discussed how to assign formal charge to any isolated atom.
We’ll now discuss the formal charge to any bonded atom. Let us take the same chorine atom in the bonded state.
Cl CH = CH2 Cl CH = CH2
(I) (II)
When chlorine makes one (I) pure covalent bond, it contributes one electron of its own. Therefore, one pure covalent
bond attached to it is equivalent to one valence electron of that atom. If one covalent bond attacked to chlorine is thought
to be equivalent to one electron of chlorine, structure (I) can be written as structure (II). Now, we can see that, the number
of valence electrons of chlorine is ‘7’ which is that of a neutral atom. Hence, chlorine does not have any formal charge in
that bonded state or we say its formal charge is zero.
Let us consider the following structures (III) and (IV).
Cl = C CH3 Cl = C CH3
H H
(III) (IV)
In structure (III), chlorine atom is bonded to two pure covalent bonds which are equivalent to two valence electrons of
chlorine. So, structure (III) can be written as structure (IV). In structure (IV), the number of valence electrons of chlorine
appears to be ‘8’ which is one unit more than that of the neutral atom. Therefore, chlorine atom has one unit of negative
formal charge and the correct representation will be as follows.
Cl = C CH3
H
Consider the following structures (V) and (VI).
Cl
Cl
H H H H
C C C C
H H H H
(V) (VI)
In structure (V), we can again convert the covalent bond attached to chlorine to one valence electron. Now we get
structure (VI) in which chlorine has 6 valence electrons which means it has one less electron than its normal neutral state.
So it gets one unit positive formal charge and the correct representation will be as follows.
+
Cl
H H
C C
H H
Now, we can also derive a formula to calculate the formal charge. The formula is given below.
 No. of valence   No. of pure   No. of nonbonded 

The formed ch arg e on an atom 
= electorns of isolated  −  covalentt bonds  −  electorns on 
in bonded or non bonded state      
 neutral atom   attached to it   that atom 
= (x) ( y) (z)
[Think yourself how we got to the above formula]
Let us apply this formula to the following structures

x = 7 Formal charge = x – y – z
-
Cl y=0 y=7–0–8 Cl
z = 8 = –1
x = 7 Formal charge = x – y – z
Cl— CH = CH2 y=1 y=7–1–6
z = 6 =0
x = 7 Formal charge = 7 – 2 – 6 = –1
Cl = CH – CH3 y = 2 Here, the correct structure is
z=6
CI = CH CH3

Cl x = 7 Formal charge = x – y – z = 7 – 2 – 4 = +1
y=2
H2C CH2 z=4
Here the correct structure is
+
Cl
H2C CH2
Remember that bonded atoms normally have the following limited values of formal charge : –1, 0, +1. (–2 or +2 are
not formed and thus are 2 unstable)
However, non bonded atoms can have other values.
For example, sulphur in its neutral isolated state, has six valence electrons. In bonded state it can have ‘–1’ state but not
the –2 state. In the isolated ionic state it can attain ‘–2’ state.
2
H S S
OCTET RULE
If any atom has eight valence electrons (s2p6 configuration), it is found to be very stable. Hund’s rule also supports this fact.
Inert gases have eight valence electrons (except He) in their nonbonded state. Therefore, they are already very stable
and they prefer to remain in that nonbonded state.
The atoms of other elements (specially the main group elements) tend to attain this inert gas configuration (eight va-
lence electrons) in their bonded state. This is known as ‘the octet rule’.
In NaCl, we can assume that the bonding between sodium and chlorine has significant ionic character and treat it as
pure ionic bond. Therefore, Na will remain as Na+ and Cl will remain Cl– forming Na+Cl–.
Na(z = 11) 1s22s22p63s1 or (Ne) 3s1
1s 2 2s 2 2p 6
Na+ or (Ne)
8ve −
Cl(Z = 17) (Ne) 3s23p5
3s 2 3p 6
Cl– (Ne) or (Ar)
8ve −
So, we can see that both Na+ and Cl– have achieved their complete octet in NaCl.
In NF3, we have bonds between nitrogen and fluorine atoms. These bonds have greater extent of covalent character and
the Lewis structure of NF3 can be shown.
N
F F
F
Nitrogen has five valence electrons in the nonbonded state. It uses three of these five electrons to form three bonds to
the three fluorine atoms. Remember each covalent bond contributes two electrons to each bonded atom because the bonded
electron pair is shared by both the bonded atoms. In bonded state, nitrogen has three bonded electrons pairs (3 × 2 = 6
electrons) and one lone pair (lp) (two electrons that nitrogen did not use in bonding). So the total number of electrons of
nitrogen in the bonded state is (6 + 2) = 8
Therefore, nitrogen has satisfied the octet rule.
Similarly, fluorine has seven valence electrons in the nonbond state. It uses one electron to form bond to nitrogen in
bonded state, it has three lone pairs and one bond pair—a total of eight valence electrons in the bonded state. So ‘octet
rule’ holds true.
Formal Charge vs Oxidation State

The concept of oxidation states constitutes a competing method to assess the distribution of electrons in molecules. If the
formal charges and oxidation states of the atoms in carbon dioxide are compared, the following values are arrived at:
O C O
Formal Charge 0 0 0
Oxidation State 2– 4+ 2–
The reason for the difference between these values is that formal charges and oxidation states represent fundamentally
different ways of looking at the distribution of electrons amongst the atoms in the molecule. With formal charge, the elec-
trons in each covalent bond are assumed to be split exactly evenly between the two atoms in the bond (hence the dividing
by two in the method described above). The formal charge view of the CO2 molecule is essentially shown below:
‘Split’electrons in
covalent bonds evenly
O= =C= =O
O C O
The covalent (sharing) aspect of the bonding is overemphasized in the use of formal charges, since in reality there is a
higher electron density around the oxygen atoms due to their higher electronegativity compared to the carbon atom. This
can be most effectively visualized in an electrostatic potential map.
With the oxidation state formalism, the electrons in the bonds are ‘awarded’ to the atom with the greater electronegativ-
ity. The oxidation state view of the CO2 molecule is shown below:
‘Award’ electrons in
bonds to oxygen
O C O
2– 4+ 2–
O C O
Oxidation states overemphasize the ionic nature of the bonding; most chemists agree that the difference in electronega-
tivity between carbon and oxygen is insufficient to regard the bonds as being ionic in nature.
In reality, the distribution of electrons in the molecule lies somewhere between these two extremes. The inadequacy of
the simple Lewis structure view of molecules led to the development of the more generally applicable and accurate valence
bond theory of Slater, Pauling, et al., and henceforth the molecular orbital theory developed by Mulliken and Hund.
BONDING IN METHANE AND ETHANE

Methane, CH4
The simple view of the bonding in methane
You will be famillar with drawing methane using dots and crosses diagrams, but it is worth looking at its structure a bit
more closely.
promotion
2px 2py 2pz

2s
H C H
2px 2py 2pz
2s
2px 2py 2pz H

2s
There is a serious mismatch between this structure and the modern electronic structure of carbon, 1s22s22px12py1. The
modern structure shows that there are only two unpaired electrons for hydrogens to share with, instead of the 4 which the
simple view requires.
You can see this more readily using the electrons-in-boxes notation. Only the 2-level electrons are shown. The 1s2
electrons are too deep inside the atom to be involved in bonding. The only electrons directly available for sharing are the
2p electrons. Why is then methane not CH2?
Promotion of an electron
When bonds are formed, energy is released and the system becomes more stable. If carbon forms four bonds rather than
two, twice as much energy is released and so the resulting molecule becomes even more stable.
There is only a small energy gap between the 2s and 2p orbitals, and so it pays the carbon to provide a small amount
of energy to promote an electron from the 2s to the empty 2p to give four unpaired electrons. The extra energy released
when the bonds form more than compensates for the initial input. The carbon atom is now said to be in an excited state.
NOTE:
People sometimes worry that the promoted electron is drawn as an up-arrow, whereas it started as a down-arrow. The
reason for this is actually fairly complicated–well beyond the level we are working at. Just get in the habit of writing it like
this because it makes the diagrams look tidy.
Now that we have got four unpaired electrons ready for bonding, another problem arises. In methane all the carbon-
hydrogen bonds are identical, but our electrons are in two different kinds of orbitals. You are not going to get four identical
bonds unless you start from four identical orbitals.
Hybridisation
The electrons rearrange themselves again in a process called hybridisation. This reorganises the electrons into four identical
hybrid orbitals called sp3 hybrids (because they are made from one s orbital and three p orbitals). You should read ‘sp3’ as
‘s p three’-not as ‘s p cubed’.
sp3 hybrid orbitals
sp3 hybrid orbitals look a bit like half a p orbital, and they arrange themselves in space so that they are as far apart as
possible. You can picture the nucleus as being at the centre of a tetrahedron (a triangularly based pyramid) with the orbitals
pointing to the corners. For clarity, the nucleus is drawn far larger than it really is.
What happens when the bonds are formed?

Remember that hydrogen’s electron is in a 1s orbital–a spherically symmetric region of space surrounding the nucleus
where there is some fixed chance (say 95 per cent) of finding the electron. When a covalent bond is formed, the atomic
orbitals (the orbitals in the individual atoms) merge to produce a new molecular orbital which contains the electron pair
which creates the bond.
hydrogen nucleus
embedded in new
molecular orbital
hydrogen
atoms
Four molecular orbitals are formed, looking rather like the original sp3 hybrids, but with a hydrogen nucleus embedded
in each lobe. Each orbital holds the 2 electrons that we have previously drawn as a dot and a cross.
The principles involved–promotion of electrons if necessary, then hybridisation, followed by the formation of
molecular orbitals–can be applied to any covalently-bound molecule.
The shape of methane
When sp3 orbitals are formed, they arrange themselves so that they are as far apart as possible. That is a tetrahedral ar-
rangement, with an angle of 109.5°.
Nothing changes in terms of the shape when the hydrogen atoms combine with the carbon, and so the methane mol-
ecule is also tetrahedral with 109.5° bond angles.
Ethane, C2H6
The formation of molecular orbitals in ethane
Ethane is not particularly important in its own right, but is included because it is a simple example of how a carbon-carbon
single bond is formed.
Each carbon atom in ethane promotes an electron and then forms sp3 hybrids exactly as we have described in methane.
So just before bonding, the atoms look like this:
+ +
+ & & +
+ +

The hydrogens bond with the two carbons to produce molecular orbitals just as they did with methane. The two car-
bon atoms bond by merging their remaining sp3 hybrid orbitals end-to-end to make a new molecular orbital. The bond
formed by this end-to-end overlap is called a sigma bond. The bonds between the carbons and hydrogens are also sigma
bonds.
hydrogen nucleus
embedded in new
molecular orbital
sigma (σ) bond
In any sigma bond, the most likely place to find the pair of electrons is on a line between the two nuclei.
The shape of ethane around each carbon atom
The shape is again determined by the way the sp3 orbitals are arranged around each carbon atom. That is a tetrahedral
arrangement, with an angle of 109.5°.
When the ethane molecule is put together, the arrangement around each carbon atom is again tetrahedral with
approximately 109.5° bond angles. Why only ‘approximately’? This time, each carbon atoms does not have four identical
things attached. There will be a small amount of distortion because of the attachment of three hydrogens and one carbon,
rather than four hydrogens.
Free rotation about the carbon-carbon single bond
The two ends of this molecule can spin quite freely about the sigma bond so that there are, in a sense, an infinite number
of possibilities for the shape of an ethane molecule. Some possible shapes are:
In each case, the left hand CH3 group has been kept in a constant position so that you can see the effect of spinning the
right hand one.
Other alkanes
All other alkanes will be bonded in the same way:
 The carbon atoms will each promote an electron and then hybridise to give sp3 hybrid orbitals.
 The carbon atoms will join each other by forming sigma bonds by the end-to-end overlap of their sp3 hybrid orbitals.
 Hydrogen atoms will join on wherever they are needed by overlapping their 1s1 orbitals with sp3 hybrid orbitals on the
carbon atoms.
BONDING IN ETHENE
Ethene, C2H4
The simple view of the bonding in ethene
At a simple level, you will have drawn ethene showing two bonds between the carbon atoms. Each line in this diagram
represents one pair of shared electrons.
H H
C C
H H
Ethene is actually much more interesting than this.

An orbital view of the bonding in ethene
Ethene is built from hydrogen atoms (1s1) and carbon atoms (1s22s22px12py1).
The carbon atom does not have enough unpaired electrons to form the required number of bonds, so it needs to promote
one of the 2s2 pair into the empty 2pz orbital. This is exactly the same as happens whenever carbon forms bonds–whatever
else it ends up joined to. So the first thing that happens is
Promotion of an electron
promotion
2px 2py 2pz 2px 2py 2pz

2s 2s
There is only a small energy gap between the 2s and 2p orbitals, and an electron is promoted from the 2s to the empty 2p to
give four unpaired electrons. The extra energy released when these electrons are used for bonding more than compensates
for the initial input.
The carbon atom is now said to be in an excited state.
Hybridisation
In the case of ethene, there is a difference from, say, methane or ethane, because each carbon is only joining to three other
atoms rather than four. When the carbon atoms hybridize their outer orbitals before forming bonds, this time they only
hybridize three of the orbitals rather than all four. They use the 2s electron and two of the 2p electrons, but leave the other
2p electron unchanged.
π bond
H H
C C
H H
2pz
2px 2py 2pz
2s
π bond
H H
C C
H H
hybrid orbital
The new orbitals formed are called sp2 hybrids, because they are made by an s orbital and two p orbitals reorganising
themselves. sp2 orbitals look rather like sp3 orbitals that you have already come across in the bonding in methane, except
that they are shorter and fatter. The three sp2 hybrid orbitals arrange themselves as far apart as possible, which is at 120°
to each other in a plane. The remaining p orbital is at right angles to them.
The two carbon atoms and four hydrogen atoms would look like this before they joined together:
The various atomic orbitals which are pointing towards each other now merge to give molecular orbitals, each contain-
ing a bonding pair of electrons. These are sigma bonds–just like those formed by end-to-end overlap of atomic orbitals in,
say, ethane.
The p orbitals on each carbon are not pointing towards each other, and so we will leave those for a moment. In the
diagram, the black dots represent the nuclei of the atoms.
Notice that the p orbitals are so close that they are overlapping sideways.
This sideways overlap also creates a molecular orbital, but of a different kind. In this one, the electrons are not held
on the line between the two nuclei, but above and below the plane of the molecule. A bond formed in this way is called
a pi bond.
For clarity, the sigma bonds are shown using lines–each line representing one pair of shared electrons. The various sorts
of lines show the directions the bonds point in. An ordinary line represents a bond in the plane of the paper, a broken line
is a bond going back away from you, and a wedge shows a bond coming out towards you.
NOTE:
The really interesting bond in ethene is the pi bond. In almost all cases where you will draw the structure of ethene, the
sigma bonds will be shown as lines.
Be clear about what a pi bond is. It is a region of space in which you can find the two electrons which make up the
bond. Those two electrons can live anywhere within that space. It would be quite misleading to think of one living in the
top and the other in the bottom.
Taking chemistry further
This is another example of the curious behaviour of electrons. How do the electrons get from one half of the pi bond to the
other if they are never found in between? It is an unanswerable question if you think of electrons as particles.
Even if your syllabus does not expect you to know how a pi bond is formed, it will expect you to know that it exists.
The pi bond dominates the chemistry of ethene. It is very vulnerable to attack–a very negative region of space above and
below the plane of the molecule. It is also somewhat distant from the control of the nuclei and so is a weaker bond than the
sigma bond joining the two carbons.
Important: Check your syllabus. Find out whether you actually need to know how a pi bond is formed. Do not forget
to look in the bonding section of your syllabus as well as under ethene. If you do not need to know it, there is no point in
learning it. You will, however, need to know that a pi bond exists–that the two bonds between the carbon atoms in ethene
are not both the same.
All double bonds (whatever atoms they might be joining) will consist of a sigma bond and a pi bond.
The shape of ethene
The shape of ethene is controlled by the arrangement of the sp2 orbitals. Notice two things about them:
 They all lie in the same plane, with the other p orbital at right angles to it. When the bonds are made, all of the sigma
bonds in the molecule must also lie in the same plane. Any twist in the molecule would mean that the p orbitals would
not be parallel and touching any more, and you would be breaking the pi bond.
There is no free rotation about a carbon-carbon double bond. Ethene is a planar molecule.
 The sp2 orbitals are at 120° to each other. When the molecule is constructed, the bond angles will also be 120°.
(approximately. There will be a slight distortion because you are joining two hydrogens and a carbon atom to each
carbon, rather than three identical groups. )
BONDING IN ETHYNE (ACETYLENE)

Ethyne, C2H2
The simple view of the bonding in ethyne
Ethyne has a triple bond between the two carbon atoms. In the diagram, each line represents one pair of shared electrons.
H-C ≡ C-H
If you have read the ethene page, you will expect that ethyne is going to be more complicated than this simple structure
suggests.
An orbital view of the bonding in ethyne
Ethyne is built from hydrogen atoms (1s1) and carbon atoms (1s22s22px12py1).
The carbon atom does not have enough unpaired electrons to form four bonds (one to the hydrogen and three to the
other carbon), so it needs to promote one of the 2s2 pair into the empty 2pz orbital. This is exactly the same as happens
whenever carbon forms bonds–whatever else it ends up joined to.
promotion

2s 2s
Each carbon is only joining two other atoms rather than four (as in methane or ethane) or three (as in ethene) and so
when the carbon atoms hybridise their outer orbitals before forming bonds, this time they only hybridise two of the orbitals.
They use the 2s electron and one of the 2p electrons, but leave the other 2p electrons unchanged. The new hybrid
orbitals formed are called sp1 hybrids (sometimes just sp hybrids), because they are made by an s orbital and a single p
orbital reorganising themselves.
sp1 hybrids 2py 2pz

What these look like in the atom (using the same colour coding) is:
py
pz
2 hybrid orbitals
Notice that the two light grey lobes are two different hybrid orbitals–arranged as far apart from each other as possible.
Do not confuse them with the shape of a p orbital.
The two carbon atoms and two hydrogen atoms would look like this before they joined together:
hydrogen carbon carbon hydrogen
The various atomic orbitals which are pointing towards each other now merge to give molecular orbitals, each contain-
ing a bonding pair of electrons. These are sigma bonds–just like those formed by end-to-end overlap of atomic orbitals in,
say, ethane. The various p orbitals are now close enough together that they overlap sideways.
sideways overlap between these p orbitals...
hydrogen
nucleus
...and sideways overlap between these as well
Sideways overlap between the two sets of p orbitals produces two pi bonds–each similar to the pi bond found in, say,
ethene. These pi bonds are at 90° to each other–one above and below the molecule, and the other in front of and behind the
molecule. Notice the different shades of grey for the two different pi bonds.
one pi bond above and below the molecule
another pi bond in front of and behind the molecule

NOTE:
In particular, these diagrams are not to scale. To get the p orbitals to overlap and still see what is going on at the back of
the molecule, you have to shorten the carbon-carbon distance completely out of proportion. In truth, the carbon-hydrogen
bond length is shorter than the carbon-carbon triple bond.
BONDING IN BENZENE
The Kekulé Structure for Benzene, C6H6
What is the Kekulé structure?
Kekulé was the first to suggest a sensible structure for benzene.

The carbons are arranged in a hexagon, and he suggested alternating double and single bonds between them. Each
carbon atom has a hydrogen attached to it.
This diagram is often simplified by leaving out all the carbon and hydrogen atoms.
In diagrams of this sort, there is a carbon atom at each corner. You have to count the bonds leaving each carbon to work
out how many hydrogens there are attached to it.
In this case, each carbon has three bonds leaving it. Because carbon atoms form four bonds, that means you are missing
a bond–and that must be attached to a hydrogen atom.
Problems with the Kekulé structure
Although the Kekulé structure was a good attempt in its time, there are serious problems with it.
Problems with the Chemistry

Because of the three double bonds, you might expect benzene to have reactions like ethene.
Ethene undergoes addition reactions in which one of the two bonds joining the carbon atoms breaks, and the electrons
are used to bond with additional atoms.
Benzene rarely does this. Instead, it usually undergoes substitution reactions in which one of the hydrogen atoms is
replaced by something new.
Problems with the Shape

Benzene is a planar molecule (all the atoms lie in one plane), and that would also be true of the Kekulé structure. The
problem is that C-C single and double bonds are of different lengths.
C-C 0.154 nm
C=C 0.134 nm
NOTE:
‘nm’ means ‘nanometre’, which is 10–9 metre.
That would mean that the hexagon would be irregular if it had the Kekulé structure, with alternating shorter and longer
sides. In real benzene all the bonds are exactly the same-intermediate in length between C-C and C=C at 0.139 nm. Real
benzene is a perfectly regular hexagon.
Problems with the stability of benzene

Real benzene is a lot more stable than the Kekulé structure would give it credit for. Every time you do a thermochemistry
calculation based on the Kekulé structure, you get an answer which is wrong by about 150 kJ mol-1. This is most easily
shown using enthalpy changes of hydrogenation.
HELP
It does not matter whether you have done any thermochemistry sums recently or not. This is all so simple that you could
understand it even if you had never done any.
Hydrogenation is the addition of hydrogen to something. If, for example, you hydrogenate ethene you get ethane:
CH2
CH2 CH
CH2 CH
CH2
CH2 = CH2 + H2 CH3CH3
In order to do a fair comparison with benzene (a ring structure) we are going to compare it with cyclohexene.
Cyclohexene, C6H10, is a ring of six carbon atoms containing just one C=C.
NOTE:
If you are a bit shaky on names: cyclohexene: hex means six carbons, cyclo means in a ring, ene means with a C=C
bond.
When hydrogen is added to this, cyclohexane, C6H12, is formed. The ‘CH’ groups become CH2 and the double bond is
replaced by a single one.
NOTE:
cyclohexane: six carbons in a ring, but the ane ending means NO C=C bond.
The structures of cyclohexene and cyclohexane are usually simplified in the same way that the Kekulé structure for
benzene is simplified–by leaving out all the carbons and hydrogens.
cyclohexene cyclohexane
In the cyclohexane case, for example, there is a carbon atom at each corner, and enough hydrogens to make the total
bonds on each carbon atom up to four. In this case, then, each corner represents CH2.
The hydrogenation equation could be written as:
+ H2
The enthalpy change during this reaction is –120 kJ mol-1. In other words, when 1 mole of cyclohexene reacts, 120 kJ
of heat energy is evolved.
HELP
‘Enthalpy change’ can be translated as ‘heat evolved or absorbed’. The negative sign shows that heat is evolved.
Where does this heat energy come from? When the reaction happens, bonds are broken (C=C and H-H) and this costs
energy. Other bonds have to be made, and this releases energy.
Because the bonds made are stronger than those broken, more energy is released than was used to break the original
bonds and so there is a net evolution of heat energy.
If the ring had two double bonds in it initially (cyclohexa-1,3-diene), exactly twice as many bonds would have to
be broken and exactly twice as many made. In other words, you would expect the enthalpy change of hydrogenation of
cyclohexa-1,3-diene to be exactly twice that of cyclohexene–, that is, -240 kJ mol-1.
NOTE:
The name (cyclohexa-1,3-diene) is unimportant.
+ 2H2
In fact, the enthalpy change is -232 kJ mol-1, which is not far off what we are predicting.
NOTE:
Thermochemistry sums often throw up discrepancies of this sort of magnitude, and you could not be sure whether there
was any significance in it.
Applying the same argument to the Kekulé structure for benzene (what might be called cyclohexa-1,3,5-triene), you
would expect an enthalpy change of –360 kJ mol-1, because there are exactly three times as many bonds being broken and
made as in the cyclohexene case.
+ 3H2
In fact what you get is –208 kJ mol-1, not even within distance of the predicted value.
This is very much easier to see on an enthalpy diagram. Notice that in each case heat energy is released, and in each
case the product is the same (cyclohexane). That means that all the reactions ‘fall down’ to the same end point.
E 152 kJ
n discrepancy
e
r
g real benzene
y
–240 –360
–208
–232
–120
Heavy lines, solid arrows and bold numbers represent real changes. Predicted changes are shown by dotted lines and
italics.
The most important point to notice is that real benzene is much lower down the diagram than the Kekulé form predicts.
The lower down a substance is, the more energetically stable it is.
This means that real benzene is about 150 kJ mol-1 more stable than the Kekulé structure gives it credit for. This in-
crease in stability of benzene is known as the delocalization energy or resonance energy of benzene. The first term (delo-
calization energy) is the more commonly used.
NOTE:
If you look at the diagram closely, you will see that cyclohexa-1,3-diene is also a shade more stable than expected. There
is a tiny amount of delocalization energy involved here as well.
BONDING IN CARBONYL COMPOUNDS
IMPORTANT
Do not try to read this unless you are sure that you fully understand the orbital view of the bonding in methane and the
bonding in ethene.
You may also find it useful to read the article on orbitals if you are not sure about the simple orbital theory.
The Carbonyl Group

The simple view of the bonding in carbon-oxygen double bonds
H
C O
H methanal
Where the carbon-oxygen double bond, C=O, occurs in organic compounds, it is called a carbonyl group. The simplest
compound containing this group is methanal.
We are going to look at the bonding in methanal, but it would equally apply to any other compound containing C=O.
The interesting thing is the nature of the carbon-oxygen double bond, not what it is attached to.
NOTE:
Methanal is normally written as HCHO. If you wrote it as HCOH, it looks as if it contains an-O-H group, and it does not.
Methanal is an aldehyde. All aldehydes contain the CHO group.
Naming: methanal: meth counts one carbon atom, an means no C=C, al says that it is an aldehyde and so contains CHO.
An orbital view of the bonding in carbon-oxygen double bonds

The Carbon Atom
p orbital
hybrid orbital
Just as in ethene or benzene, the carbon atom is joined to three other atoms. The carbon's electrons rearrange themselves,
and promotion and hybridisation give sp2 hybrid orbitals.
Promotion gives:
promotion

2s 2s
Hybridisation of the 2s orbital and two of the 2p orbitals means that the carbon atom now looks like the diagram on
the right.
Three sp2 hybrid orbitals are formed and these arrange themselves as far apart in space as they can–at 120° to each
other. The remaining p orbital is at right angles to them.
This is exactly the same as in ethene or in benzene.
IMPORTANT
If this is not really clear to you, you must go and read the article about the bonding in ethene.
The oxygen atom

Oxygen's electronic structure is 1s22s22px22py12pz1.
The 1s electrons are too deep inside the atom to be concerned with the bonding and so we'll ignore them from now on.
Hybridisation occurs in the oxygen as well. It is easier to see this using ‘electrons-in-boxes’.
2pz
2px 2py 2pz sp2 hybrids
2s
This time two of the sp2 hybrid orbitals contain lone pairs of electrons.
HELP
A ‘lone pair’ of electrons is a pair of electrons at the bonding level which is not being used to bond on to another atom.
p orbital
hybrid orbitals containing

lone pairs of
electrons
hybrid orbital
containing a single electron
The carbon atom and oxygen atom then bond in much the same way as the two carbons do in ethene. In the next
diagram, we are assuming that the carbon will also bond to two hydrogens to make methanal, but it could equally well
bond to anything else.
hydrogens
carbon oxygen
End-to-end overlap between the atomic orbitals that are pointing towards each other produce sigma bonds.
Notice that the p orbitals are overlapping sideways.
hydrogen lone
nuclei pairs
the carbon the oxygen

atom atom
This sideways overlap produces a pi bond. So just like C=C, C=O is made up of a sigma bond and a
pi bond.
Does that mean that the bonding is exactly the same as in ethene? No. The distribution of electrons in the pi
bond is heavily distorted towards the oxygen end of the bond, because oxygen is much more electronegative than
carbon.
highly distorted
π bond
carbon oxygen
This distortion in the pi bond causes major differences in the reactions of compounds containing carbon-oxygen double
bonds like methanal compared with compounds containing carbon-carbon double bonds like ethene.
ELECTRONEGATIVITY
This page deals with electronegativity in an organic chemistry context.
What is Electronegativity?
Electronegativity is a measure of the tendency of an atom to attract a bonding pair of electrons. The Pauling scale is the
most commonly used. Fluorine (the most electronegative element) is given a value of 4. 0, and values range down to cae-
sium and francium which are the least electronegative at 0.7.
What happens if two atoms of equal electronegativity bond together?

The most obvious example of this is the bond between two carbon atoms. Both atoms will attract the bonding pair to
exactly the same extent. That means that on average the electron pair will be found half way between the two nuclei, and
you could draw a picture of the bond like this:
line showing the

covalent bond
C C
electron pair
It is important to realize that this is an average picture. The electrons are actually in a sigma orbital, and are moving
constantly within that orbital.
HELP
A sigma orbital is a molecular orbital formed by end-to-end overlap between two atomic orbitals. If you are not happy
about this, read the articles on orbitals and the bonding in methane and ethane.
The carbon-fluorine bond

Fluorine is much more electronegative than carbon. The actual values on the Pauling scale are:
carbon 2.5
fluorine 4. 0
That means that fluorine attracts the bonding pair much more strongly than carbon does. The bond, on average, will
look like this:
C F
electron pair pulled
towards the fluorine
Why is Fluorine More Electronegative Than Carbon?
A simple dots-and-crosses diagram of a C-F bond is perfectly adequate to explain it.
carbon atom joined

to other atoms using C F
these single electrons
The bonding pair is in the second energy level of both carbon and fluorine, so in the absence of any other effect, the
distance of the pair from both nuclei would be the same.
The electron pair is shielded from the full force of both nuclei by the 1s electrons—again there is nothing to pull it
closer to one atom than the other.
But, the fluorine nucleus has 9 protons whereas the carbon nucleus has only 6.
Allowing for the shielding effect of the 1s electrons, the bonding pair feels a net pull of about 4+ from the carbon,
but about 7+ from the fluorine. It is this extra nuclear charge which pulls the bonding pair (on average) closer to fluorine
than carbon.
HELP
You have to imagine what the bonding pair ‘sees’ if it looks in towards the nucleus. In the carbon case, it sees 6 positive
protons, and 2 negative electrons. That means that there will be a net pull from the carbon of about 4+. The shielding would
not actually be quite as high as 2-, because the 1s electrons spend some of their time on the far side of the carbon nucleus,
and so are not always between the bonding pair and the nucleus.
Incidentally, thinking about electrons looking towards the nucleus may be helpful in picturing what is going on, but
avoid using terms like this in exams.
The carbon-chlorine bond

The electronegativities are:
carbon 2.5
chlorine 3.0
The bonding pair of electrons will be dragged towards the chlorine but not as much as in the fluorine case. Chlorine is
not as electronegative as fluorine.
Why is not chlorine as electronegative as fluorine?

Chlorine is a bigger atom than fluorine.
fluorine: 1s22s22px22py22pz1
chlorine: 1s22s22px22py22pz23s23px23py23pz1
In the chlorine case, the bonding pair will be shielded by all the 1-level and 2-level electrons. The 17 protons on the
nucleus will be shielded by a total of 10 electrons, giving a net pull from the chlorine of about 7+.
That is the same as the pull from the fluorine, but with chlorine the bonding pair starts off further away from the nucleus
because it is in the 3-level. Since it is further away, it feels the pull from the nucleus less strongly.
Bond Polarity
Polar bonds
Think about the carbon-fluorine bond again. Because the bonding pair is pulled towards the fluorine end of the bond, that
end is left rather more negative than it would otherwise be. The carbon end is left rather short of electrons and so becomes
slightly positive.
δ+ δ–
C F
The symbols δ+ and δ–mean ‘slightly positive’ and ‘slightly negative’. You read δ+ as ‘delta plus’ or ‘delta positive’.
We describe a bond having one end slightly positive and the other end slightly negative as being polar.
NOTE:
You should be aware of terms like ‘negative inductive effect’, but do not get bogged down in them. Provided that you
understand what happens when electronegative atoms like fluorine or chlorine are attached to carbon atoms in terms of the
polarity of the bonds, that's really all you need for most purposes.
Some Important Examples of Polar Bonds
Hydrogen bromide (and other hydrogen halides)
δ+ δ–
H Br
Bromine (and the other halogens) are all more electronegative than hydrogen, and so all the hydrogen halides have polar
bonds with the hydrogen end slightly positive and the halogen end slightly negative.
NOTE:
These reactions are explored in the section dealing with the addition of hydrogen halides to alkenes.
The carbon-bromine bond in halogenoalkanes
NOTE:
You may come across halogenoalkanes under the names ‘haloalkanes’ or ‘alkyl halides’.
Bromine is more electronegative than carbon and so the bond is polarised in the way that we have already described with
C-F and C-Cl.
δ+ δ–
C Br
The polarity of the carbon-halogen bonds is important in the reactions of the halogenoalkanes.
NOTE:
This link will take you to the nucleophilic substitution reactions of the halogenoalkanes in which this polarity is important.
The carbon-oxygen double bond

An orbital model of the C=O bond in methanal, HCHO, looks like this:
highly distorted
π bond
hydrogen lone pairs
nuclei
carbon oxygen
NOTE:
If you are not sure about this, read the part on bonding in the carbonyl group (C=O).
The very electronegative oxygen atom pulls both bonding pairs towards itself–in the sigma bond and the pi bond. That
leaves the oxygen fairly negative and the carbon fairly positive.
δ+ δ–
C O
VSEPR THEORY
Valence shell electron pair repulsion (VSEPR) theory is a model in chemistry used to predict the shape of individual
molecules based upon the extent of electron-pair electrostatic repulsion. It is also named Gillespie–Nyholm theory after
its two main developers. The acronym ‘VSEPR’ is sometimes pronounced ‘vesper’ for ease of pronunciation; however, the
phonetic pronunciation is technically more correct.
The premise of VSEPR is that the valence electron pairs surrounding an atom mutually repel each other, and will
therefore adopt an arrangement that minimizes this repulsion, thus determining the molecular geometry. The number of
electron pairs surrounding an atom, both bonding and nonbonding, is called its steric number.
VSEPR theory is usually compared and contrasted with valence bond theory, which addresses molecular shape through
orbitals that are energetically accessible for bonding. Valence bond theory concerns itself with the formation of sigma
and pi bonds. Molecular orbital theory is another model for understanding how atoms and electrons are assembled into
molecules and polyatomic ions.
VSEPR theory has long been criticized for not being quantitative, and therefore limited to the generation of ‘crude’,
even though structurally accurate, molecular geometries of covalent molecules. However, molecular mechanics force
fields based on VSEPR have also been developed.
Description
VSEPR theory mainly involves predicting the layout of electron pairs surrounding one or more central atoms in a
molecule, which are bonded to two or more other atoms. The geometry of these central atoms in turn determines the
geometry of the larger whole.
The number of electron pairs in the valence shell of a central atom is determined by drawing the Lewis structure of the
molecule, expanded to show all lone pairs of electrons, alongside protruding and projecting bonds. Where two or more
resonance structures can depict a molecule, the VSEPR model is applicable to any such structure. For the purposes of
VSEPR theory, the multiple electron pairs in a multiple bond are treated as though they were a single ‘pair’.
These electron pairs are assumed to lie on the surface of a sphere centered on the central atom, and since they are
negatively charged, tend to occupy positions that minimizes their mutual electrostatic repulsions by maximising
the distance between them. The number of electron pairs therefore determines the overall geometry that they will
adopt.
For example, when there are two electron pairs surrounding the central atom, their mutual repulsion is minimal when
they lie at opposite poles of the sphere. Therefore, the central atom is predicted to adopt a linear geometry. If there are three
electron pairs surrounding the central atom, their repulsion is minimized by placing them at the vertices of an equilateral
triangle centered on the atom. Therefore, the predicted geometry is trigonal. Similarly, for four electron pairs, the optimal
arrangement is tetrahedral.
This overall geometry is further refined by distinguishing between bonding and nonbonding electron pairs. A bonding
electron pair is involved in a sigma bond with an adjacent atom, and, being shared with that other atom, lies farther
away from the central atom than does a nonbonding pair (lone pair), which is held close to the central atom by its
positively-charged nucleus. Therefore, the repulsion caused by the lone pair is greater than the repulsion caused by the
bonding pair. As such, when the overall geometry has two sets of positions that experience different degrees of repulsion,
the lone pair(s) will tend to occupy the positions that experience less repulsion. In other words, the lone pair-lone pair
(lp-lp) repulsion is considered to be stronger than the lone pair-bonding pair (lp-bp) repulsion, which in turn is stronger
than the bonding pair-bonding pair (bp-bp) repulsion. Hence, the weaker bp-bp repulsion is preferred over the lp-lp or
lp-bp repulsion.
This distinction becomes important when the overall geometry has two or more non-equivalent positions. For example,
when there are five electron pairs surrounding the central atom, the optimal arrangement is a trigonal bipyramid. In this
geometry, two positions lie at 180° angles to each other and 90° angles to the other three adjacent positions, whereas the
other three positions lie at 120° to each other and at 90° to the first two positions. The first two positions therefore experi-
ence more repulsion than the last three positions. Hence, when there are one or more lone pairs, the lone pairs will tend to
occupy the last three positions first.
The difference between lone pairs and bonding pairs may also be used to rationalize deviations from idealized
geometries. For example, the H2O molecule has four electron pairs in its valence shell: two lone pairs and two bond pairs.
The four electron pairs are spread so as to point roughly towards the apices of a tetrahedron. However, the bond angle
between the two O-H bonds is only 104.5°, rather than the 109.5° of a regular tetrahedron, because the two lone pairs
(whose density or probability envelopes lie closer to the oxygen nucleus) exert a greater mutual repulsion than the two
bond pairs.
AXE Method
The ‘AXE method’ of electron counting is commonly used when applying the VSEPR theory. The A represents the central
atom and always has an implied subscript one. The X represents the number of sigma bonds between the central atoms and
outside atoms. Multiple covalent bonds (double, triple, etc.) count as one X. The E represents the number of lone electron
pairs surrounding the central atom. The sum of X and E, known as the steric number, is also associated with the total
number of hybridized orbitals used by valence bond theory.
Based on the steric number and distribution of X’s and E’s, VSEPR theory makes the predictions in the following
tables. Note that the geometries are named according to the atomic positions only and not the electron arrangement. For
example the description of AX2E1 as bent means that AX2 is a bent molecule without reference to the lone pair, although
the lone pair helps to determine the geometry.
Table 2.1
Steric No. Basic geometry 0 lone pair 1 lone pair 2 lone pairs 3 lone pairs
2 X A X
Linear
3 X (
X A $
X
; ;
Trigonal planar %HQW
4 X ( ( (
A $ $
X ;
X ; ; ;
X ;
Tetrahedral 7ULJRQDOS\UDPLG %HQW
5 X ( ( ( (
X
A X ; $ ; ; $ ; ; $ ;
X
X ; ; ; ( (
Trigonal bipyramid 6HHVDZ 7VKDSHG /LQHDU
6 X ; (
X X ; ; ; ;
A $ $
X X ; ; ; ;
X ( (
Octahedral 6TXDUHS\UDPLG 6TXDUHSODQDU
7 X E
X X X X
X A X A
X X X X
X X
Pentagonal bipyramid Pentagonal pyramid
8 Square antiprismatic
Table 2.2
Molecule Type Shape Electron arrangement† Geometry‡ Examples

AX1En Diatomic HF, O2
AX2E0 Linear BeCl2, HgCl2, CO2
AX2E1 Bent NO2−, SO2, O3
AX2E2 Bent H2O, OF2
AX2E3 Linear XeF2, I3−

AX3E0 Trigonal planar BF3, CO32−, NO3−, SO3
AX3E1 Trigonal pyramidal NH3, PCl3
AX3E2 T-shaped ClF3, BrF3
AX4E0 Tetrahedral CH4, PO43−, SO42−, ClO4−
AX4E1 Seesaw SF4
AX4E2 Square planar XeF4
AX5E0 Trigonal bipyramidal PCl5
AX5E1 Square pyramidal ClF5, BrF5
AX6E0 Octahedral SF6
AX6E1 Pentagonal pyramidal XeOF5−, IOF52− [7]
AX7E0 Pentagonal bipyramidal IF7
AX8E0 Square antiprismatic XeF2−8
† Electron arrangement including lone pairs

‡ Observed geometry (excluding lone pairs)
When the substituent (X) atoms are not all the same, the geometry is still approximately valid, but the bond angles
may be slightly different from the ones where all the outside atoms are the same. For example, the double-bond carbons
in alkenes like C2H4 are AX3E0, but the bond angles are not all exactly 120°. Similarly, SOCl2 is AX3E1, but because the X
substituents are not identical, the XAX angles are not all equal.
As a tool in predicting the geometry adopted with a given number of electron pairs, an often used physical demonstration
of the principle of minimal electrostatic repulsion utilizes inflated balloons. Through handling, balloons acquire a slight
surface electrostatic charge that results in the adoption of roughly the same geometries when they are tied together at
their stems as the corresponding number of electron pairs. For example, five balloons tied together adopt the trigonal
bipyramidal geometry just as do the five bonding pairs of a PCl5 molecule (AX5) or the two bonding and three non-boning pairs
of a XeF2 molecule (AX2E3). The molecular geometry of the former is also trigonal bipyramidal, while that of the latter is linear.
The methane molecule (CH4) is tetrahedral because there are four pairs of electrons. The four hydrogen atoms are
positioned at the vertices of a tetrahedron, and the bond angle is cos-1(-1/3) ≈ 109°28’. This is referred to as an AX4 type of
molecule. As mentioned above, A represents the central atom and X represents all of the outer atoms.
The ammonia molecule (NH3) has three pairs of electrons involved in bonding, but there is a lone pair of electrons
on the nitrogen atom. It is not bonded with another atom; however, it influences the overall shape through repulsions. As
in methane above, there are four regions of electron density. Therefore, the overall orientation of the regions of electron
density is tetrahedral. On the other hand, there are only three outer atoms. This is referred to as an AX3E type molecule
because the lone pair is represented by an E. The observed shape of the molecule is a trigonal pyramid, because the lone
pair is not ‘visible’ in experimental methods used to determine molecular geometry. The shape of a molecule is found from
the relationship of the atoms even though it can be influenced by lone pairs of electrons.
A steric number of seven is possible, but it occurs in uncommon compounds such as iodine heptafluoride (IF7). The
base geometry for this is pentagonal bipyramidal.
REPRESENTATION OF A CHEMICAL REACTION

An organic reaction is normally represented as follows:
Reagent
Substrate Product
Solvent
Reagent
NaOH Product
Substrate Cl OH
H2O
Solvent
Or,
Reagent Solvent
Substrate Product
Reagent
Solvent
NaO/H2O
Cl OH Product
Substrate
Substrate: It is the molecule undergoing the attack by the reagent.

Reagent: It is the species attacking the substance. There are reactions induced by photon (represented by ‘hν’ above the
arrow) or heat (represented by ‘∆’ below the arrow).
Solvent: It provides the medium for the reaction. There are reactions which may not require any solvent, the reactions take
place in the gaseous phase only.
Product: They are the outcome of the reactions.
Reaction Mechanism
What is a reaction mechanism and how does it differ from a balanced chemical equation?
A balanced equation provides the number of moles of both reactants and products but does not show how the reaction
proceeds. A reaction mechanism provides a detailed step-by-step description of a reaction.
1. In organic chemistry, a chemical change is said to have occurred when there is at least formation of a σ bond or cleav-
age of a σ bond.
2. If there is formation or cleavage of π bonds only, it is not actually a chemical change; we can call it ‘resonance’
(we will discuss later).
Reaction mechanism shows how the reaction proceeds. It provides a detailed step by step description of a reaction.
A complete description of the reaction mechanism can be found from the knowledge of the following:
(a) Movement of the electron(s)
(b) Types of bond cleavage
(c) Nature of reagent
(d) Nature of solvent
(e) Nature of the substrate–Factors affecting the electronic displacement in the molecule/ion
(f) Reaction intermediate
(g) Reaction condition–Kinetic and thermodynamic aspect (to be discussed later with the reaction)
A) Representation of Movement of Electrons: Using Curly Arrows in Reaction Mechanisms

Curly arrows are used in mechanisms to show the various electron pairs moving around. You must not use them for any
other purpose.
1. Double headed curved arrow represents movement of two electrons.
(the arrow should not be straight as it represent a chemical change from reactant to product)
donor acceptor
movement of two nonbonded electrons (lone pair)

NH3
movement of two π bonded electrons

CH3
2. Remember the arrow does not represent movement of positive charge. Hence the following representations will
be wrong.
NH4
3. Single headed curved arrow represents movement of one electron. It is normally involved in the reaction of radicals
(odd electron species).
CH3
Cl
 The arrow tail is where the electron pair starts from. That is always fairly obvious, but you must show the electron pair
either as a bond or, if it is a lone pair, as a pair of dots. Remember that a lone pair is a pair of electrons at the bonding
level which is not currently being used to join on to anything else.
 The arrow head is where you want the electron pair to end up.
For example, in the reaction between ethene and hydrogen bromide, one of the two bonds between the two carbon
atoms breaks. That bond is simply a pair of electrons.
Those electrons move to form a new bond with the hydrogen from the HBr. At the same time the pair of electrons in the
hydrogen–bromine bond moves down on to the bromine atom. There is no need to draw the pairs of electrons in the bonds
as two dots. Drawing the bond as a line is enough, but you could put two dots in as well if you wanted to.
CH2 CH2
H
Br
+
CH2 CH2
H
Br–
Notice that the arrow head points between the C and H because that is where the electron pair ends up. Notice also that
the electron movement between the H and Br is shown as a curly arrow even though the electron pair moves straight down.
You have to show electron pair movements as curly arrows, not as straight ones.
The second stage of this reaction nicely illustrates how you use a curly arrow if a lone pair of electrons is involved.
The first stage leaves you with a positive charge on the right hand carbon atom and a negative bromide ion. You can
think of the electrons shown on the bromide ion as being the ones which originally made up the hydrogen–bromine bond.
NOTE:
There are other three lone pairs around the outside of the bromide ion, making four in all. These are not normally shown
because they do not actually do anything new and interesting.
However, it is essential that you show the lone pair you are interested in as a pair of dots. If you do not, you risk losing
marks in an exam.
The lone pair on the bromide ion moves to form a new bond between the bromine and the right hand carbon atom. That
movement is again shown by a curly arrow. Notice again, that the curly arrow points between the carbon and the bromine
because that is where the electron pair ends up.
That leaves you with the product of this reaction, bromoethane:
CH2 CH2
H Br
Using curly arrows to show the movement of single electrons

The most common use of ‘curly arrows’ is to show the movement of pairs of electrons. You can also use similar arrows to
show the movement of single electrons, except that the heads of these arrows only have a single line rather than two lines.
VKRZVWKHPRYHPHQWRIDQHOHFWURQSDLU
VKRZVWKHPRYHPHQWRIDVLQJOHHOHFWURQ
The first stage of the polymerisation of ethene, for example, could be shown as:
Ra CH2 CH2 Ra CH2 CH2

You should draw the dots showing the interesting electrons. The half arrows show where they go. This is very much a
‘belt-and-braces’ job, and the arrows do not add much.
Whether you choose to use these half arrows to show the movement of a single electron should be governed by what
your syllabus says. If your syllabus encourages the use of these arrows, then it makes sense to use them. If not, if the syl-
labus says that they may be used, or just ignores them altogether, then they are as well avoided.
There is some danger of confusing them with the arrows showing electron pair movements, which you will use all the
time. If, by mistake, you use an ordinary full arrow to show the movement of a single electron you run the risk of losing marks.
B) Types of Bond Cleavage

Heterolytic bond fission or heterolysis
1. In heterolysis, the covalent bond is broken in such a way that one of the bonded atoms gains both the electrons.
⊕
A B A+B
2. Most of the times oppositely charged species are formed when the bonded atoms do not have formal charges.
3. If one of the atoms carries formal charge, the formal charge is neutralized after the bond cleavage. For example,
⊕ ⊕ ⊕
[R – N N R–N N] R+N N↑
4. The mode of cleavage depends on the nature of reagent. If the reagent takes up a pair of electrons from the substrate
(usually called an electrophile) or gives up a pair of electrons to the substrate (usually called a nucleophile), it is found
to induce heterolytic fission of bonds in the substrate.
5. If the induced bond cleavage is heterolytic, the more polar bond of the substrate is heterolytically cleaved. The factor
which favours heterolysis is a greater difference of electronegativity between bonded atoms.
6. Mechanism of the reaction in which heterolytic bond fission takes place is known as heterolytic mechanism or ionic
mechanism.
7. The energy required for heterolytic bond fission is always greater than that for homolytic bond fission due to electro-
static force of attraction between ions.
Homolytic bond fission
A B Aº + ºB
1. In this type of cleavage bond, pair is shared equally by both bonded atoms and the atoms depart with their own electrons.
Homolytic bond fission results in the formation of radicals.
2. The mode of cleavage depends on the nature of reagent. If the reagent (usually called a radical), shares only one elec-
tron in the reaction, it is found to induce heterolytic fission of bonds in the substrate.
3. It is also induced by photon, heat.
4. When induced cleavage is homolytic, the less polar bond of the substrate will be preferentially broken.
+ +
&O
+ &±&O &±&O+±&O
+ +
5. The radical reaction are preferred in the gaseous state and in less polar solvent.
Illustration
1. (a) Describe heterolytic (polar) covalent bond cleavage of (i) AgI, (ii) H3N:BF3, and (iii) Cu(:OH2)42+. Focus on
the indicated shared pair of e-’s. (b) What is the reverse of heterolytic cleavage called? (c) Describe homolytic
covalent bond cleavage of H3CO:OCH3.
Ans. (a) Both bonding electrons remain with the more electronegative atom.
(i) AgI → Ag++ I– When the bonded atoms have no charge, the more electronegative atom (or group) holding
the pair of e-’s has a negative charge, the other atom is positive.
(ii) H3N:BF3 → H3N= + BF3 Bonded atoms with formal charges give uncharged products.
(iii) Cu2++4:OH2 For positively charged reactants, the less electronegative atom acquires the positive charge
ensuring conservation of charge.
(b) Coordinate covalent bonding.
(c) Each bonded atom gets one unpaired electron to give species called radicals. Homolysis may be initiated by
uv light or heat.
H3CO:OCH3 → 2H3CO. A radical
C) Nature of Reagent
Organic reagents
Organic reagents can be classified in two categories:
(1) Electrophile: Electron deficient species or electron acceptor is electrophile, they tend to attack the substrate at a
position (or positions) of high electron density, are referred to as electrophilic reagents or electrophiles.
(2) Nucleophile: Electron rich species or electron donor is nucleophile, they tend to attack the substrate at a position
(or positions) of low electron, density, i.e.where the atomic nucleus is short of its normal complement of orbital electrons,
are referred to as nucleophilic reagents or nucleophiles.
Electrophiles
It can be classified into two categories:
(a) Charged electrophiles (E+)
(b) Neutral electrophiles (E)
(a) Charged electrophiles: Positively charged species, in which central atom has incomplete octet, is charged electrophile.
⊕ ⊕ ⊕ ⊕ O ⊕ ⊕
H , X ,R , N , N = O, SO3H
O
NOTE:
All cations may not be electrophiles. For example, oxygen in H3O+, cations of IA, IIA group elements, Al+++ and N+H4.
(b) Neutral electrophiles: It can be classified into three categories:

(i) Neutral covalent compound in which central atom has incomplete octet is neutral electrophile.
BeCl2, BH3, ZnCl2, AlX3, FeX3, CH3, CH2, CX2
(ii) Neutral covalent compound in which central atom has complete or expended octet and central atom has unfilled-
d-sub-shell is neutral electrophile.
SnCl4, SiCl4, PCl5, SF6, IF7

(iii) Neutral covalent compound in which central atom is bonded only with two or more than two electronegative
atoms is neutral electrophile.
BeCl2, BX3, AlX3, FeX3, SnCl4, PCl3
PCl5, NF3, :CX2, CO2, SO3, CS2, CX4
NOTE:
(i) Cl2, Br2 and I2 also behave as neutral electrophiles.
(ii) Electrophiles are Lewis acids.
Nucleophiles
Nucleophiles can be classified into three categories:
(a) Charged nucleophiles: Negatively charged species are charged nucleophiles.
H, OH, R O, CH3, X, SH, R S
(b) Neutral nucleophiles: It can be classified into two categories:

(i) Neutral covalent compound, in which central atom has complete octet, has at least one lone pair of electrons and
all atoms present on central atom should not be electronegative, is neutral nucleophile.
NH3, R NH2, R2NH, R3N, NH2 NH2 (Nitrogen nucleophile)
H O H, R O H, R O R (Oxygen nucleophiles)
H S H, R S H, R S R (Sulphur nucleophiles)
PH3, RPH2, R2PH, R3P (Phosphorus nucleophiles)
(ii) Organic compound containing carbon, carbon multiple bond/bonds behaves as nucleophile.
Alkenes, Alkynes, Benzene, CH2=CH—CH=CH2, CH2=CH—C ≡ CH
(c) Ambident nucleophiles: Species having two nucleophilic centres, one is neutral (complete octet and has at least one
lone pair of electrons) and other is charged (negative charge) behaves as ambident nucleophile.
C N, O N O, O S OH
NOTE:
(1) Organometallic compounds are nucleophiles.
(2) Nucleophiles are Lewis bases. Organic compounds which behave as electrophile as well as nucleophile.
Organic compound, in which carbon is bonded with electronegative atom (O, N, S) by multiple bond/bonds, behaves
as eleetrophile as well as nucleophile.
O O O O
R C H, R C R, R C OH, R C Cl
O O
⊕
R C OR, R C NH2, R C ≡ N, R N ≡ C
NOTE:
During the course of chemical reaction, eleetrophile reacts with nucleophile.
This electrophile/nucleophile dichotomy can be looked upon as a special case of the acid/base idea. The classical definition
of acids and bases is that the former are proton donors, and the latter proton acceptors. This was made more general by
Lewis, who defined acids as compounds prepared to accept electron pairs, and bases as substances that could provide such
pairs. This would include a number of compounds not previously thought of as acids and bases, e.g., boron trifluoride,
⊕
F3B + NMe3 F3B NMe3
which acts as an acid by accepting the electron pair on nitrogen in trimethylamine to form the complex, and is therefore
referred to as a Lewis acid. Electrophiles and nucleophiles in organic reactions can be looked upon essentially as acceptors
and donors, respectively, of electron pairs, from and to other atoms—most frequently carbon. Electrophiles and nucleo-
philes also, of course, bear a relationship to oxidising and reducing agents, for the former can be looked upon as electron
acceptors and the latter as electron donors. A number of the more common electrophiles and nucleophiles are listed below.
Illustrations
2. (a) Define (i) a nucleophile or electron-donor and (ii) an electrophile or electron-acceptor.

(b) What structural units make a molecule (or ion) (i) a nucleophile or (ii) an electrophile?
(c) What kind of reaction occurs between a nucleophile and electrophile?
Ans. (a) (i) Molecules having atoms with high electron density are called nucleophiles or electron donors. (ii) Molecules
having atoms with low electron density are called electrophiles or electron-acceptors.
(b) (i) The atom in question, called a nucleophilic site, may be the negative (d-) end of a polar covalent bond have
an unshared electron pair, or be part of a p bond. It may also have a combination of these features, (ii) The atom
in question, called an electrophilic site, may be capable of taking on more valence electrons or be the positive
(d+) end of a polar bond.
(c) Coordinate covalent bonding, Nu = + E → Nu : E.
3. Classify each of the following species as electrophile or nucleophile and explain your choice.
(a) CH3COO – (b) CH3O – (c) BF3 (d) Cl+ (e) (CH3)3C:– (f) Cl2C (g) SiF4 (h) Br – (i) P(CH3)3
(j) (CH3)2CH +
(k) H2C = CH2 and (l) HCl.
Ans. Electrophiles: (c), (d), (f), and (h) have six valence e-’s and can accept an electron pair from a nucleophile to
acquire the stable octet. (l), typical of all Bronsted acids is electrophilic because the H+ it donates is electron
deficient. Although (g) has eight valence e-’s, it can nevertheless be an acceptor of a nucleophile’s unshared pair
by expanding its d shell to 12 e-’s: SiF4 + 2 : F= → SiF6-2. This behaviour is observed with elements in the third
and higher periods of the periodic table that form covalent bonds.
Nucleophiles: (a), (b), (e), and (h) are anions, (i) has an unshared electron-pair, and (k) has two available electrons
in a p bond.
4. Which of the following species behave as (a) a nucleophile, (b) an electrophile, (c) both, or (d) neither? I-, H3N:,
BeCl2, CH4, Cr3+, CH3C = N:, H2, SnCl4, H2C = O:, and NO2+.
Ans. (a) Nucleophiles: :I:-H3N:. (b) Electrophiles: BeCl2 (bonded Cl’s are rarely nucleophilic), SnCl4, Cr3+, and NO+2
(the electrophilic character completely masks the potential nucleophilic behaviour of the unshared electron-pairs
on the O’s). (c) Both: CH3C = N:, H2C = O:. Since C in each of these species is p-bonded to a very electronegative
atom, N and O respectively, C is an electrophilic site. The electronegative N and O also have unshared e- pairs
and are nucleophilic sites, (d) Neither: CH4, H2.
5. Identify the species I and II as electrophiles (E) or nucleophiles (Nu) in the reactions:
Species I Species II
+ –
(a) (CH3)2O + BMe3 (CH3)2O –BMe3
– –
(b) CN + CH3Br H3C CN + Br
–
(c) H C C H + NH2– HC C + H NH2
+
(d) C2H5Br + AlBr3 [C2H5] [AlBr4]–
(e) CH3CH = O + SO3H – (bisulfite anion) CH3CH SO3H
–
O
Ans.
Reaction (a) (b) (c) (d) (e)
Species I Nu Nu E Nu E
Species II E E Nu E Nu
6. Formulate the following as a two-step reaction and designate the nucleophiles and electrophiles.
Ans.
H2C CH2 + Br2 H2CBrCBrH2
step 1 step 2
H 2C CH2 + Br Br H2CBr CH2+ + Br –
H2CBr CH2 Br
nucleophile electrophile electrophile nucleophile

Br2 is electrophilic since each electronegative Br prefers to have a full compliment of eight e–s.
NOTE:
Eight electrons is the maximum for B, C, N, or O

We now ought to spell out one thing that we have never stated but rather assumed. Most atoms in organic molecules, if
they are not positively charged, have their full complement of electrons (two in the case of hydrogen, eight in the cases of
carbon, nitrogen, and oxygen) and so, if you make a new bond with one of those elements, you must also break an exist-
ing bond. Suppose you just ‘added’ Ph3P to Mel in this last example without breaking the C-I bond: what would happen?
⊕
H
Ph3P CH3 I Ph3P C I
HH
wrong mechanism impossible structure
carbon has five bonds
This structure must be wrong because carbon cannot have five bonds—if it did, it would have ten electrons in the 2s
and the 2p orbitals. As there are only four of those (2s, 2px, 2py, and 2pz) and they can have only two electrons each, eight
electrons is the maximum, and that means that four bonds is the maximum.
 If you make a new bond to uncharged H, C, N, or O, you must also break one of the existing bonds in the same
step.
There is a serious trap when a charged atom has its full complement of electrons. Since BH −4 and NH +4 are isoelec-
tronic with methane and have four bonds and hence eight electrons, no new bonds can be made to B or N. The following
attractive mechanisms are impossible because boron has no lone pair in BH −4 and nitrogen has no empty orbital in NH +4 .
H H H H H H H
⊕ B X B H X B Y H B Y N
X H H H H H H H H H⊕H Y
impossible reaction impossible impossible impossible impossible

structure, boron structure, carbon structure, nitrogen reaction
has five bonds has five bonds has five bonds
Reactions with BH −4 always involve the loss of H and a pair of electrons using the BH bond as nucleophilc and reac-
tions with NH +4 always involve the loss of H without a pair of electrons using the NH bond as electrophile.
H H H H H H H H
B ⊕ B + HX N + HY N
X Y
H H H H H ⊕H
correct mechanism correct mechanism
Similarly, nucleophiles do not attack species like H3O+ at oxygen, even though it is the oxygen atom that carries the
positive charge. Reaction occurs at one of the protons, which also neutralizes the positive charge. Or, to put it another way,
H3O+ is an acid (electrophilic at hydrogen) and not electrophilic at oxygen.
H H
Y H H
Y ⊕O O + HY
O ⊕O
H H H H
H H H Y
impossible structure, impossible correct
oxygen has four bonds reaction mechanism
D) Factors Influencing Electron-Availability

Any factors that influence the relative availability of electrons (the electron density) in particular bonds, or at particular
atoms, in a compound might be expected to affect very considerably its reactivity towards a particular reagent: a position
of high electron availability will be attacked by electrophile, whereas a position of low electron availability is likely to be
attacked with ease by nucleophile. A number of such factors have been recognized.
Inductive and field effects
1. In a covalent single bond between unlike atoms, the electron pair forming the s bond is never shared absolutely
equally between the two atoms; it tends to be attracted a little more towards the more electronegative atom of the two.
Thus, in an alkyl chloride (20), the electron density tends to be greater nearer chlorine than carbon, as the former is
the more electronegative; this is generally represented as in (20a) or (20b).
δ+ δ−
C Cl C Cl
(20a) (20b)
2. If the carbon atom bonded to chlorine is itself attached to further carbon atoms, the effect can be transmitted further.
C C C C Cl
4 3 2 1
The effect of the chlorine atom’s partial appropriation of the electrons of the carbon-chlorine bond is to leave C1
slightly electron-deficient; this it seeks to rectify by, in turn, appropriating slightly more than its share of the electrons
of the s bond joining it to C2, and so on down the chain.
3. The effect of C1 on C2 is less than the effect of Cl on C1, however, and the transmission quickly dies away in a saturated
chain, usually being too small to be noticeable beyond C2. These influences on the electron distribution in s bonds are
known as inductive effects.
4. Inductive effect can be defined as the permanent polarization of the s bonds transmitted through the chain of s bonds.
5. It is a permanent effect.
6. It is transmitted through the s bonds only, it can not be transmitted through p bonds.
7. The intensity of the effect decreases significantly with increasing distance from the inducing group. It is almost
negligible after three carbon from the inducing group.
Negative Inductive Effect: (–I Effect)

This is due to electron-attracting groups (X); it develops positive charge on the chain and is said to exert a negative
inductive denoted by (– I)
δ+ δ−
C X
 (– I) effect decreases as one goes away from group X (electron attracting)

δδδ+ δδ+ δ+ δ–
C C C X
3 2 1
Examples of –I effect groups

(–I) effect group (electron attracting)
+ +
N Me3 > N H 3 > NO 2 > CN > COOH > F > Cl > Br > I > OAr > COOR > OR > OH
> C6 H 5 > CH = CH 2 > H
Positive Inductive Effect (+I)

This is due to electron-releasing group (Y). It develops an negative charge on the chain and is said to exert a positive
inductive effect denoted by (+I)
δ– δ+
C Y
 (+I) effect also decreases as we go away from group Y (electron-releasing)

δδδ– δδ– δ– δ+
C C C C Y
4 3 2 1
C1(δ–) > C2(δδ–) >C3(δδδ–)
Examples of +I effect groups

(+I) effect – group (electron – repelling)
O − > COO − > R 3 C > CHR 2 > CH 2 R > CH 3 > D > H
Illustrations
7. Inductive effect refers to

(a) electron displacement along a carbon chain
(b) complete transfer of one of the shared pair of electrons to one of the atoms joined by a couble bond
(c) complete transfer of electron hither to unshared
(c) none of the above
Ans. (a) partial displacement of electron takes place.
8. Which of the following groups has the highest +I effect?

(a) CH3 – (b) CH3 (c) (CH3)2 CH – (d) (CH3)3 C –
Ans. (d) ter. alkyl group have highest +I effect.
9. Maximum –I effect is exerted by the group
(a) C6H5 – (b) – OCH3 (c) Cl (d) NO2
Ans. (d)
10. Zero inductive effect is exerted by the group
(a) C6H5 – (b) H (c) CH3 – (d) Cl
Ans. (b)
APPLICATIONS OF INDUCTIVE EFFECT

(i) Effect on bond lengths: Since the inductive effect leads to ionic character in the bond, the increase in –I effect usually
decreases the bond length.
Increasing –I effect
CH3 F CH3 Br CH3 Cl CH3 F

2.14A 1.94A 1.78A 1.38A
Decrease in bond length

(ii) Dipole moment: Since, inductive effect leads to a dipolar character in the molecule, it develops some dipole moment
in the molecule, which increases with the increase in the inductive effect.
CH3 – I, CH3 — Br, CH3 — Cl
Increasing dipole moment
(iii) Reactivity of alkyl halides: Alkyl halides are more reactive than the corresponding alkanes due to presence of C––X
bond which is polar due to I effect, furthermore reactivity increases with increase of branching.
H 3C H 3C
H3C CH2 X < CH – X < H3C C–X
H3C H3C
Increasing reactivity due to increasing C — X bond polarity

(iv)  Due to (–I) effect (electron-withdrawing nature) electron-density decreases, hence,
– basic nature is decreased
– acidic nature is increased
 Chloro acetic acid is stronger than acetic acid since Cl shows (–I) effect, electron-density is decreased and O—H
bond is weakened causing ionisation of (–COOH) to a greater extent than CH3COOH.
O O
Cl CH2 C O H CH3 C OH
(–I)
 NH is a base due to lone-pair on nitrogen. Phenyl group is electron-withdrawing. What happens to electron-density
3
of nitrogen in aniline? Naturally electron-density is decreased. Hence aniline is weaker base than NH3.
H N H H N H
H
 Similarly acidic nature of phenol is greater than H2O due to electron-withdrawing nature of phenyl group.
H O H O H
 Due to (+I) effect (electron-withdrawing nature) electron-density decreases, hence,

– basic nature is increased
– acidic nature is decreased
Illustrations
11. Why CCl3COOH is a stronger acid than CH3COOH?
Ans.
Cl
Cl C C O
Cl O
Cl is the electron with drawing group which stabilize the anion by distributing the charge, whereas in case of
CH3COOH, CH3 is electron releasing group which destabilize the anion by increasing charge intensity. Therefore
CCl3COOH is a stronger acid than CH3COOH.
 Take examples of H2O, CH3OH and C6H5OH
H—O—HCH 3 → —O—H O—H
(+I) (–I)
w.r.t. H2O it is more basic it is more acidic
Ka (ionisation constant of acid) OH > H2 O > CH 3 OH

Illustrations
12. Arrange the following in the increasing order of their acidic strength.
CH3COOH, FCH2COOH, Cl – CH2COOH BrCH2COOH, I – CH2–COOH
Ans. Acidic strength increases with an increase in the strength of (–I) group, hence, the correct order is
CH3COOH<ICH2COOH<BrCH2COOH<ClCH2COOH<F–CH2COOH
13. Compare the acidic strength of the following:

CH3COOH ClCH2COOH Cl2HCCOOH CCl3COOH
H O H O
Ans. CH 3 COOH< Cl C—C O H < Cl C—C O H
H Cl
Cl
O
< Cl C—C O H
Cl
Increasing acidic strength due to increasing number of (–I) effect of the groups (el)
## Solved Example
1. Which among the following is the most acidic:
(a) H3C COOH (b) F
H3C
CH2COOH
F
COOH
(c) H3C COOH (d) F
SOLUTION
1. As the inductive effect of fluorine decreases with distance, (A) will be most acidic, because the
carboxylate ion which results after the loss of H+ can be stabilized by electron withdrawing nature
of fluorine (—I effect) which is strongest in which fluorine atom is at α carbon.
(v) Basic strength of amines

The basic character of amines is due to presence of unshared electron pair on nitrogen atom which accepts proton; the
readiness with which the lone pair of electrons available for protonotion determines the relative strength of amines.
Due to +I effect of alkyl group, the nitrogen atom becomes rich in electrons with the result the lone pair of electron
on nitrogen atom in amines is more easily available than in ammonia and hence generally, amines are stronger bases
than ammonia.
On the other hand (–I) groups or electron groups attached to nitrogen atom make it difficult for protonation.
NOTE:
Relative basic strength of amines is not in total accordance with the inductive effect, other factors like steric effect and
stabilization of cation by hydration also play important role to determine the basic strength of amines.
Illustrations
14. Compare the basic strength of the following:

NH3, CH3NH2 (CH3)2NH (CF3)3N
Ans. The increasing order of basic strength is as follows.
CF3
H CH3 H
F3 C N: < H — N < H — N < H3C N
H H CH3
CF3
CF3 group being –I effect groups attracts the electron pair of nitrogen, makes protonation difficult in primary and
secondary amine due to presence of +I effect group (CH3) which make protonation easy. Hence, the increasing
order of basic strength is as shown above.
All inductive effects are permanent polarisations in the ground state of a molecule, and are therefore, manifested
in its physical properties, for example, its dipole moment.
RESONANCE
If a molecule or ion can be shown by two (or) more structures differing only in the distribution of electrons, but none
of these structures truly explains all the properties of that molecule (or) ion, these structures are called resonating (or)
contributing or canonical structures and this phenomenon is called resonance.
For example, CO2 molecule can be shown by the following three contributing forms:
O=C=O O—C≡ O O ≡C—O
The actual structure of the molecule is a resonance hybrid. This fact is proved from the C—O bond distance. The actual
bond distance is 1.15Å while it should be 1.20Å. The bond shortening is attributable to the triple bond formation as shown
above.
Rules for Drawing Valence Bond Resonance Structues

We have already said that resonance effects are encountered mainly in molecules with multiple (i.e. p) bonds. Except in a
few special molecules, the σ-bond framework is not involved in significant resonance interactions.
This fact can be rationalized by noting that electrons in p bonds are higher in energy than those in σ bonds, making the
p-bonding electrons more reactive and also more polarizable than σ-bonding electrons.
When a species contains multiple bond(s) it may have several resonance contributors. For example, even a molecule as
simple as ethylene has several resonance.
But not all resonance structures contribute equally to the hybrid’s properties. For example, here are four structures we
might write for ethylene:
H H H H H H H H
C C C C C C C C
H H H H H H H H
(I) (II) (III) (IV)
The first structure (I) is by far the main contributor. Structure II and III are minor contributors for three reasons: the
p bond has been broken, there are charge separations not present in the major contributor, and the valence of the +vely
charged carbon is unsatisfied. Structure IV does not contribute at all. Not only are both carbons’ valences unsatisfied, but
previously paired electrons have become unpaired. From considerations such as these, we can devise a list of rules that
will help us determine if a given resonance contributor has a valid structure, and how important its relative contribution is.
(a) No real existence: Resonance structures exist only on paper. Resonance structures are useful because they allow us
to describe molecules, radicals and ions for which a single Lewis structure is inadequate. We write two or more lewis
structures, calling them resonance structures of resonance contributors. We connect these structures by double headed
arrows ( ) and we say that the real molecule, radical, or ion is a hybrid of all of them.
(b) In writing resonance structures, we are only allowed to move electrons.
Position of nuclei of the atoms must remain same in all resonance structures. For example,
+ + +
CH 3 — CH — CH = CH 2 CH 3 — CH = CH — CH 2 CH 2 — CH 2 — CH = CH 2
This is not a proper
R — Structures of allylic cation R-structure because
a H atom has been moved
(c) Lewis structures: All the canonical forms must be bonafide Lewis structures. For instance, none of them may have a
carbon with five bonds.
H
+
H—C=O
••
— H not a proper R-structure because
carbon is Penta valent
H
(d) The position of the nuclei must be the same in all the structures. This process means we are putting the electrons in
different way when we are drawing various resonating structures. It means the position of the atoms are fixed in all
resonating structures.
For this reason, shorthand ways of representing resonance are easy to devise.
+ + +
OH OH OH OH OH OH
⊝
.. ⊝
.. ≡
⊝
..
(e) All atoms taking part in the resonance, i.e., covered by delocalized electrons, must lie in a plane or nearly so. The
reasons of polarity is maximum overlap/of the p-orbitals.
(f) The energy of the actual molecule is lower than that of any form. Therefore, delocalisation is stabilising phenomenon.
(g) All canonical forms do not contribute equally to the true molecule. Each form contributes in different proportion to its
stability, most stable-form contributes most.
1 2 3 4 5
Ke kule structure Dewar structure
Structure 1 and 2 participate equally and contribute 39 per cent each to actual molecule and the other (3, 4 and 5) 7.3
per cent each.
(h) The most important resonance contributors are those with the maximum number of covalent bonds and the minimum
number of charge separations. Structures with more covalent bonds are more stable, than those of less number of
covalent bonds.
CH2 = CH – CH = CH2 CH2 CH = CH CH2

More stable Less stable
(i) Stability is decreased by an increase in charge separation. Structure with formal charge are less stable than uncharged
structures
• •• +
•
CH 2 = CH — Cl •CH 2 — CH = Cl
• ••
I II
(more stable)
(j) Structures which follow the octet rule are more stable than other structures which do not follow the octet rule.
(k) Structures that carry negative charge on a more electronegative atoms are more stable than those in which the charge
is on a less electronegative atom.
CH2 C H CH2 = C H
O O
less stable more stable
Illustration
15. Aniline is not as good a base as alkyl amines; why?

NH2
Ans. In aniline, the lone pair of electrons on nitrogen involves in the resonance of benzene
ring while in alkyl amine the nitrogen has increased electron density due to +I effect of R ••
group. R NH2
 Benzyl charbonium ion is resonance stabilised.
CH 2 CH 2 CH 2 CH 2
Classification of resonance: Resonance can be classified as

(1) Simple conjugation
(2) Mesomeric effect: This is resonance under the influence of a hetero atom (any atom other than carbon and hydrogen).
(3) Hyper conjugation or no bond resonance: It is different from normal resonance and it will be discussed later.
Here we now discuss simple conjugation and mesomeric effect as they follow all the same rules of resonance men-
tioned before.
Mesomeric effect and simple conjugation: Special properties are associated with systems in which a p-bond is
conjugated either with a second p-bond (or) with an atom which possesses a pair of electrons in a p-orbital. These are:
stabilization energy, single bond lengths which are shorter than those in non-conjugated compounds, and (in some cases)
the modification of dipolar properties.
(a) p-bond–p–bond conjugation: The simplest example is butadiene, CH2=CH–CH=CH2. This is symmetrical molecule
and conjugation does not lead to the appearance of a dipole. In valence bond language, contributions from the ionic
⊕ ⊝ ⊝ ⊕
structures C H 2 − CH = CH − CH2 and C H 2 − CH = CH − C H 2 are necessarily equal and their dipoles therefore,
nullify each other. This is not true, however, when p-bonds of different types are in conjugation. For example,
in an a, b unsaturated carbonyl compound, such as butenal, the contribution of structure (A) is greater than that
of (B) because oxygen significantly more electronegative than carbon. The carbonyl group thus polarizes the
C = C bond.
H3C O H3C O
[A] {B}
A group such as carbonyl which withdraws electrons from an adjacent group via the p-bonding frame work is described
as having a –M effect, the –ve sign indicating electron withdrawal and M standing for mesomeric. Other groups
of –M type include ester, nitrile and nitro etc., and the curved arrows in the representations denote the direction of the
mesomeric effect.
C C C
+
O N N O
O
(b) p-bond–p-orbital conjugation: In vinyl chloride (chloroethene) the p-orbital on the carbon which is attached to chlo-
rine can overlap with both the p-orbital on the second carbon atom, and one of the filled p-orbitals on chlorine three
delocalized MO’s are established of which the two of lowest energy are occupied. Since the p-orbital on chlorine is
initially filled, its participation in the delocalized p system leads to the partial removal of electrons from chlorine and
the appearance of a dipole moment directed from chlorine towards carbon. This is opposed to the dipole established in
C – Cl s bond as a result of the –I effect of chlorine, with the overall result that the dipole moment of vinyl chloride
(1.44D) is considerably smaller than that of ethyl chloride (2. 0D) in which the –I effect is operative. The capacity of
chlorine for donating electrons into a molecular p-system is described as a +M effect.
H
H
H H
C
H H2C
Cl
⊝ ⊕
Cl H2 C Cl
[A] [B] [C]
In ‘Valece Bond’ terminology, vinyl chloride is described as a hybrid of the structures (B) and (C), the latter symbol-
izing the +M effect of chlorine. Both descriptions also indicate that C—Cl bond should be shorter than in a saturated alkyl
chloride, as is found.
Other elements with unshared p-electrons which take part in forming delocalized π-systems include other halogens,
oxygen and nitrogen. For example,
CH 2 = CH − OCH3 CH2 = CH − N(CH3)2
In each case, the substituent has a +M effect.

Two further points should be noted. First, bond strength is dependent on the extent of the overlap of the combining
atomic orbitals, so that in these conjugated systems, the more nearly equal in size the p-orbitals are, the more effective
is the π-orbital overalp. Hence, fluorine is more effective than chlorine in conjugating with carbon, and oxygen is more
effective than sulphur. Secondly, as the nuclear charge in an atom is increased, so also is the hold of the nucleus on the sur-
rounding electrons so that, for comparably sized atoms, the ability to conjugate decreases as the atomic number increases.
Hence, the order of +M effects is
—NR 2 > — OR > — F
+M effect possessing groups are

—OH, — OR, — NH 2 , — NHR, — NR 2 , — SR, — X etc.
–M effect possessing groups are
—CHO, = CO, — CN, — NO 2 , — SO 3H etc.

The low reactivity of halogens bonded to unsaturated carbon is due to the +M effect of the halogen. The C—Br bond
in vinyl bromide has a partial double-bond character due to the +M effect of bromine with consequent low reactivity of
bromine.
CH 2 = CH — Br CH 2 — CH = Br
The acidity of phenol is due to the +M effect of OH group. The mesomeric transfer of the lone pair on the oxygen atom
of phenol to the π electrons of the benzene ring results in several resonance structures with positive charge on the oxygen
atom. This aids the hydrogen atom of OH group to leave as proton.
OH OH OH OH O
H 2O
+ H 3O +
The ionization is specially aided due to the formation of the relatively more stable phenoxide ion. The charge delocal-
ization in phenoxide ion affords greater stability over phenol in which charge separation occurs in the canonical forms.
O O O O
Hence, phenol prefers to ionize, i.e., it is acidic.

Resonance energy
The difference in energy between the hybrid and the most stable canonical structure is called as Resonance energy.
Other cannonical structure

Total energetic structure
36 kcal
Resonance energy of benzene
Electromeric effect: It is the temporary shift of π electrons under the influence of a reagent. When the reagent is removed,
the π bond is reformed. Therefore, electromeric effect is a temporary effect. There can be two types of electromeric effects
– Positive electromeric effect and negative electromeric effect. These two types are described below.
Positive electromeric effect
When p-electrons transfer takes place C to C (as alkenes, alkynes etc.), it is called Positive Electromeric effect (denoted by E+).
Electrophile
added
CH2 = CH2 CH2— CH2
Electrophile
removed
Electrophile
added
CH3 —CH=CH2 CH3—CH—CH2
Electrophile
removed
In this, there is also (+I) effect of –CH3 group, which causes p-electron transfer C2 to C1. What do you think in the
following case?
CH3 → CH=CH —←← CH2CH3
(+I) effect of CH3CH2— is larger than that of CH3–, hence p electron transfer is from C3 to C2
CH 3 —CH=CH—CH2 CH2
Negative electromeric effect
When p-electrons transfer takes place to more electronegative atom (O,N,S) joined by multiple bonds, it is called Negative
Electromeric Effect (denoted by E–).
Electrophile
added
C=O C—O
Electrophile
removed
Electrophile
added
—C ≡ N —C=N
Electrophile
removed
HYPERCONJUGATION
Hyper Conjugation
When (C – H) sigma electrons are in conjugation to π bond, this conjugation is known as s-(C – H) conjugation, excessive
conjugation or hyperconjugation. It is also called as no bond resonance because in the different canonical forms, no bond
exists between carbon and H atom of alkyl group.
H H
H+
H C CH = CH2 H C = CH CH2 H+ C = CH CH2
H H H
H
H C = CH CH2
H+
Occurrence
Alkene, alkynes
Free radicals (saturated type) carbonium ions (saturated type)
Structural requirement for hyper conjugation
(i) Compound should have at least one sp2 hybrid carbon of either alkene, alkyl carbocation or alkyl free radical.
(ii) a-carbon with respect to sp2 hybrid carbon should have at least one hydrogen.
Hyper conjugation is of three types

(i) σ(C – H) π conjugation: It occurs in alkenes.
CH3
α α
CH3 CH = CH2, CH3 CH CH = CH2, CH3 C CH = CH2
α
CH3 CH3
No hyperconjugation
(ii) σ(C – H), positive charge conjugation: It occurs in alkyl carbocatins.
α ⊕ α ⊕ α ⊕ α
CH3 CH2, CH3 CH CH2, CH3 C CH3
CH3 αCH3
(iii) σ(C – H), odd electron conjugation: It occurs in alkyl free redicals.
CH3 CH2, CH3 CH CH3
Example:
H H+ H H
H—C— CH = CH2 H—C—CH = CH 2 H+ C— CH = CH 2 H — C — CH = CH2
H (I) H (II) H (III) H+ (IV)
NOTE:
Number of hyperconjugative structures = (number of α-Hydrogen+1). Hence, in above examples, structures i,ii,iii,iv are
hyperconjugate structures (H-structures).
 Hyperconjugation is a permanent effect.
According to Hyperconjugation effect or Baker Nathen effect, the order of electron releasing of alkyl group is as
follows:
Me – > CH3CH2 – > isopro > t-Bu
Which is opposite to their inductive effect.
In tertiary Butyl benzene, alkyl group will exert only +I effect, which is lowest at para position and highest at ortho
position. But ortho position is not available for attack due to steric hindrance, so the attack of electrophile will take place
at meta position. Tert-alkyl group is meta directing and activating.
&+
&+ &+&+ &+ &+ +& &+
! ! !
Benzotrichloride shows reverse hyperconjugation effect due to which ortho and para positions will become electron
deficient, so it is meta directing and deactivating.
Cl Cl H H
⊕
Cl C Cl Cl C Cl H C H H C H
⊕
;
Stability of alkene ∝ No. of hyperconjugated structures
CH2 = CH2 < CH3 – CH2 – CH = CH2 < CH3– CH = CH2 < CH3 – C = C – CH3
H H
H CH3
CH3 C = C CH3 < CH3 C = CH2
H
Isobutene is more stable than trans–2-butene due to formation of more stable hyperconjugated structure.
+
CH3 H CH2
CH3 C = CH2 CH3 C CH2
1
Heat of hydrogenation of alkene/Heat of combustion ∝
Hyper conjugation
Electrophilic addition reaction of alkene will depend on stability of intermediate carbonium ion.
Effects of hyperconjugation
(i) Bond Length: Like resonance, hyperconjugation also affects bond lengths because during the process the single
bond in compound acquires some double bond character and vice-versa. E.g., C—C bond length in propene
is 1.488 Å as compared to 1.334Å in ethylene.
1.353Å 1.353Å
H
H⊕ ⊝ ⊝
H C CH = CH2 H C =CH CH2
H 1.488Å H 1.488Å
(ii) Dipole moment: Since hyperconjugation causes these development of charges, it also affects the dipole moment of
the molecule.
(iii) Stability of carbonium ions: The order of stability of carbonium ions is as follows:
Tertiary > Secondary > Primary
Above order of stability can be explained by hyperconjugation. In general, the greater the number of hydrogen atoms
attached to a-carbon atoms, the more hyperconjugative forms can be written, and thus, the greater will be the stability
of carbonium ions.
CH3 CH2H+
Tertiary carbonium ion H3C C+ H3C C
CH3 CH3
(9 equivalent forms)
CH3 CH2H+
Secondary carbonium ion H3C C+ H3C C
H H
CH3 CH2H+
+
Primary carbonium ion H C H C
H H
(vi) Stability of free radicals: Stability of Free radicals can also be explained as that of carbonium ion.
&+ &! &+ &+!&+&+!&+
(v) Orientation influence of methyl group: The o,p-directing influence of the methyl group in methyl benzenes is
attributed partly to inductive and party to hyperconjugation effect.
CH3
(orientation influence of the methyl group due to +I effect)

H H H H
H C H H+ C H H+ C H H+ C H
(orientation influence of the methyl group due to +I effect)
H H H H
H C H H+ C H H+ C H H+ C H
etc:
(Orientation influence of methyl group due to hyperconjugation)

The role of hyperconjugation in o,p,-directing influence of methyl group is evidenced by the part that nitration of p-iso
propyl toluene and p-tert-butyl toluene form the product, in which —NO2 group is introduced in the ortho position with respect
to methyl group and not to isopropyl or t-butyl group, although the latter groups are more electron donating than Methyl groups.
H H
H—C—H H—C—H
H—C—CH3 H3 C — C—CH3
CH3 CH3
Therefore, the substitution takes place contrary to inductive effect. Actually, this constitutes an example where hypercon-
jugation overpowers inductive effect.
 The greater the number of C—H bonds at a-carbon to the unsaturated system, the greater will be the electron-release,
and thus greater the hyperconjugation effect.
H
H—Cα—CH = C < maximum hyperconjugation due to three H-atoms at α – Carbon
H
H
CH3 —C —CH = C<

α
H
H
CH 3 —C —CH = C<
α
CH3
CH3
α
CH3 —C —CH = C
CH3
 Any primary radical (like the radial) has hyperconjugative interaction, which is not possible in the simple methyl
radical. Thus, ethyl radical is more stable than methyl radical. On the same line, 2° alkyl radical is more stable than 1°
alkyl radical, and 3° alkyl radial is more stable than 2° alkyl radical.
•
3° > 2° > 1° > CH 3
## Solved Example
2. Write the following Alkenes in increasing order of their stability with explanation R2C = CR2, R2C
= CHR, R2C = CH2, RCH = CH2, CH2 = CH2.
SOLUTION
Let R = CH 3
(a) CH 2 = CH 2 (no. α – H, no. Hyperconjugation)
(b) H3C H
C C
H H
(c) H3C H
C C
H3C H
(d) H3C CH3

C C
H 3C H
(e) H C CH3
3
C C
H 3C CH3 (12α – H, 12–H structures)
1. Compound Homolytic bond dissociation energy
⊕
CH3 Br CH3 + Br 219 Kcal/mo
⊕
CH3 CH2Br CH3 CH2 + Br 184 Kcal/mo
Notice the heterolytic bond dissociation energy of these compounds. Now, ignoring the contribution
of inductive effect, no-bond-resonance energy of ethyl caion can be calculated to be
(a) 35 Kcal/mol (b) 30 Kcal/mol (c) 25 Kcal/mol (d) 20 Kcal/mol
CH3
2. CH3 CH2
I II III
Which of the following orders is correct for heat of hydrogenation of these compounds?
(a) I > II > III (b) III > II > I (c) III > I > II (d) II > I > III
CH3 a CH3 b
3.
a and b are the length of C-H bonds in methyl groups encircled. Now, which of the following
orders is correct?
(a) a = b (b) a > b (c) b > a (d) not predictable
SOLUTIONS
1. (a), 2. (a), 3. (b)
AROMATICITY
1. Classification of Carbon Compounds

Combined State of Carbon
Organic compound Inorganic compound

Hydrocarbon & its derivatives
Oxide Sulphide Halides &
CO2 CS2 Carbides
CO
C3O2
Open chain or acyclic or aliphatic hydrocarbon Closed (cyclic) hydrocarbon
Saturated Unsaturated Carbocylic Heterocyclic
Alkane
(paraffins) Alkene Alkyne
Alicyclic Aromatic
(double bond) (triple bond)
[Olefins] [Acetylenes]
Alicyclic Aromatic
Benzenoid Non-Benzenoid
Mono cyclic compounds having alternate single and double bonds are called annulenes. They may be aromatic or alicyclic
e.g., Cyclobutadiene is [4] Annulene, Benzene is [6] Annulene, Cyclooctatetraene is [8] Annulene.
(1) Alicyclic Compounds: Cyclic compounds which resemble aliphatic compound in their chemical properties are called
alicyclic compounds.
Oxirane Cyclopropane Cyclobutane Cyclopentane
(2) Aromatic Compounds: These are the cyclic compounds which follow the conditions or aromaticity.
Aromaticity Character or Aromaticity is the property of the sp2 hybridized planar rings in which the ‘p’ orbitals (one
on each atom) allow cyclic delocalization or p electrons.
The modern definition of aromaticity is the ability to sustain induced ring current by a flat or nearly flat cyclic system
with (4n + 2) delocalized p electrons, where n is zero or any whole number.
Benzene is the ideal molecule possessing aromaticity. It has a planar hexagonal ring structure with (4 × 1 + 2) or 6p
electrons. There are six p-orbitals, one on each sp2 atom. All the six p electron orbitals being parallel to each other and
perpendicular to the plane of the molecule, they form a delocalised electron cloud below and above the plane.
When a magnetic field is applied perpendicular to the plane of the benzene molecule, the circulation of delocalized p
electrons takes place in one direction and thereby a ring current, which induces a counteraction magnetic field inside the
ring, is produced (see figure). The benzene has the ability to sustain induced ring current.
Induced magnetic field

inside the ring
Ring current
Applied Magnetic field
Ring Current
Fig.2.3 Induced ring current in benzene
Systems possessing aromaticity have some physical and chemical properties which are also collectively known as
aromatic character.
(i) Chemical stability is excess of analogous acyclic unsaturated system. For example,
(a) Although aromatic compounds have unsaturated ring, electrophilic substitution rather than addition reaction
occur and the unsaturated ring does not get ruptured.
(b) Resistance to oxidation by aqueous solution of normal oxidising agents except group VI oxidising agents (V2O5)
etc.
(ii) Unusual thermal stability
(a) Low heat of hydrogenation
(b) Low heat of combustion
(iii) Physical measurement

(a) Diamagnetic susceptibility
(b) Unique nuclear magnetic resonance spectra
There are three theories regarding the cause of aromaticity:
(i) Valence bond theory: This theory tells us that resonance stabilization of a planar cyclic structure is the cause of its
aromaticity.
(ii) Molecular orbital theory: According to this theory high delocalization energy is the cause of aromaticity of planar
cyclic systems.
Six p-orbitals, one form each sp2C atom remain perpendicular to the plane of the hexagonal benzene ring and parallel
to each other. All the six p A.O.s overlap to form six delocalized M.O.s–three bonding and three anti-bonding. The
three boding M.O.s accommodate all six electrons.
(iii) The Hückel 4n + 2 rule: On the basis of M.O. theory, Hückel stated that the presence of 4n+2 delocalized p electrons
in the flat or nearly flat cyclic systems is the cause of aromaticity and is known as Hückel’s rule. Here n may be
0, 1, 2, 3 etc. , whole number. According to him, 4n+2 delocalized p-electrons of a cyclic system develop high
delocalization energy or high resonance energy in it. Thus for a compound to be aromatic, it must be cyclic planar
structure containing (4n+2) delocalized p electrons in a closed shell. This rule is applicable to monocyclic, fused ring,
heterocyclic and cyclic ionic systems.
 Conditions for Aromaticity
i. Molecule must have an uninterrupted cyclic cloud of p e– s, it means molecules must be cyclic, every atom in the
ring must be planar (sp2 hybridized).
ii. p cloud must contain an odd number of pairs of p electrons.
 Huckel proposed odd pair of p e– s as (4n + 2) rule (n = 0, 1, 2. . . ). It means aromatic compound must have 1, 3, 5, 7,
9 etc. pair of p electrons.
If a cyclic compound has lower p electron energy than its open chain analogue, the compound is said to be an aromatic
compound. When 1, 3, 5 hexatriene is converted to benzene by the hypothetical abstraction of two H-atoms, the p-electron
energy diminishes in the system.
C
HC H
H CH CH −2H
C CH
H I II
I contains higher p-electron energy than II

+
+
+
,,, ,9
+
On the other hand, if a cyclic compound contains higher p-electron energy than its acyclic counterpart, the compound
is called anti-aromatic. In fact, planar cyclic conjugated systems with 4np-electrons are called anti-aromatic. Hence,
cyclobutadiene is an anti-aromatic compound.
If in the case of hypothetical conversion of an acyclic conjugated system into cyclic conjugated system, the p-electron
energy remains unchanged, the cyclic system is said to be non-aromatic.
 Anti-aromatic: Molecules which fulfil the first criterion for aromatically (Cyclic, planar conjugated or uninterrupted
π electrons) but not the second, having even number of pairs of p e– s
Stability: Aromatic compound > cyclic compound with localised e– s > antiaromatic compound. Anti-aromatic com-
pounds are even less stable than open chain compounds.
 The extent of aromaticity can be judged sometimes with the help of resonance energy.
 Theoretically, delocalization and electronegativity can be the basis of comparison. Pyrrole and Furan are quite similar
except the hetero-atom. As nitrogen in pyrrole electronegative than oxygen in furan, so its aromaticity is more than
furan.
O N S
H
Furan Pyrrole Thiophene
Aromatic compound are of two types

1. Benzenoid aromatic compounds: All the aromatic compounds having at least one benzene ring are called Benzenoid
compounds.
Molecules Nature Remarks

Aromatic [6] annulene
Benzene
Aromatic 4n + 2 = 10 p e–
where n = 2
Napthalene
Aromatic 4n + 2 = 14 p e–
n=3
Anthracene
Aromatic Nitrogen is sp2 hybridized. Nitrogen lone

pair is present in hybridized orbital, so it
will not be delocalized. pe– of 3 double
bonds participates in resonance.
.N.
2. Non-Benzenoid aromatic compounds: These are the aromatic compounds which do not contain benzene ring.
Molecules Nature Remarks
Not Aromatic Interrupted loope of π electrons.

Cycloprope
⊕
⊕ ⊕ Aromatic, n = 0 Aromatic ion
Cyclopropenyl ⊕
Antiaromatic , is more stable

Cyclobutadiene [4]
annulene
Annulene: cyclic, with a
ɵ
Aromatic 6p e– s
Cyclobutadiene
⊕
Antiaromatic 4p e– s
Cyclopentadienyl Cation
ɵ
Aromatic Carbanion is sp2 hybridized
6p e– s
Cyclopentadienyl anion
+ Aromatic Highly stable cation
Cycloheptatrienyl
cation
(Tropylium ion)
:N– Aromatic Nitrogen lone pair of electron is present in

unhybridised p-orbital and it will be delocalized.
Pyrrole
Non-aromatic Cyclic, conjugated 4n = 8 ⇒ n = 2 but not
antiaromatic due to non-planar structure. It is
tubshaped
Cyclo-octatraene [8]-
Cond.
Antiaromatic Corresponding open chain anion is more stable.
ɵ
Cycloheptatrienyl anion
Aromatic Fused ring. Dipolar compound due to stabili-

zation in cycloheptatrienyl cation as well as
cyclopentadienyl anion together.
Azulene
Aromatic 4n + 2 = 10 e– s ⇒ n = 2
.. Indole
N
H
H
N
..
Aromatic 4n + 2 = 6 ⇒ n = 1
.N.
Imidazole
Lone pair of electron involved in imparting aromaticity is almost not basic. For example, in imidazole, one nitrogen is
basic –other is not.
Non-aromatic 4n + 2 = 10 ⇒ n = 2
H But, non-aromatic due to non-planarity (arises
H with 1, 6-hydrogen repelling interaction
p-orbitals of the carbon atoms are not parallel
and therefore cannot overlap effectively around
Two trans [10]-annulene the ring.
Non-Aromatic Cyclotetradecaheptaene or [14] Annulene is

H
not aromatic due to the interaction of the four
H internal hydrogen atoms prevents the ring from
assuming a planar structure.
Four trans [14]-
RESONANCE ENERGY
A compound with delocalized electrons is more stable than that compound would be if all its electrons were localized. The
extra stability a compound gains as a result of having delocalized electrons is called delocalization energy or resonance
energy. Let us take a look at the resonance energy of benzene. In other words, let us determine how much more stable benzene
(with three pairs of delocalized p electrons) is than a hypothetical ‘cyclohexatriene’ (with three pairs of localized p electrons).
The heat of hydrogenation of cyclohexene, a compound with one localized double bond, has been experimentally
determined to be —28.6 kcal/mol. We would expect ‘cyclohexatriene,’ a hypothetical compound with three localized
double bonds, to have a heat of hydrogenation three times that of the compound with one double bond. Therefore, we can
calculate the heat of hydrogenation of ‘cyclohexatriene’ to be 3(–28.6) = –85.8 kcal/mol.
+ H2 ∆H° = –28.6 kcal/mol
cyclohexene
When the heat of hydrogenation was experimentally determined for benzene, it was found to be —49.8 kcal/mol, much
smaller than that calculated for the hypothetical ‘cyclohexatriene’ molecule.
If reaction coordinate diagrams are drawn for the addition of hydrogen to ‘cyclohexatriene’ and for the addition of
hydrogen to benzene, the energy of the product will be the same in both reactions coordinate diagrams because both reactions
produce the same product, cyclohexane (Figure ).
The only way to account for the difference in the heats of hydrogenation is for the reactants to have different stabilities.
Since the experimental heat of hydrogenation for benzene is 36 kcal/mol less than the heat of hydrogenation calculated for
‘cyclohexatriene’ (85.8 – 49.8 = 36), benzene must be 36 kcal/mol more stable than ‘cyclohexatriene. ’
Because benzene and ‘cyclohexatriene’ have different stabilities, they must be different compounds. Benzene has six
delocalized p electrons, whereas hypothetical ‘cyclohexatriene’ has six localized p electrons. The difference in energy
between them is the resonance energy of benzene. The resonance energy tells us, how much more stable a compound
with delocalized electrons is than it would be if its electrons were localized. Benzene, with six delocalized p electrons, is
36 kcal/mol more stable than hypothetical cyclohexatriene with six localized p electrons. Now we can understand why
nineteenth-century chemists, who did not know about delocalized electrons, were puzzled by benzene’s unusual stability.
Since the ability to delocalize electrons increases the stability of a molecule, we can conclude that a resonance hybrid
is more stable than the predicted stability of any of its resonance contributors. The resonance energy associated with a
compound that has delocalized electrons depends on the number and predicted stability of the resonance contributors.
The greater the number of relatively stable resonance contributors, the greater the resonance energy. For example, the
resonance energy of a carboxylate ion with two relatively stable resonance contributors is significantly greater than the
resonance energy of a carboxylic acid that has only one relatively stable resonance contributor.
O O
R C R C + H+
OH O
relatively stable relatively stable
O O
R C R C
OH O
+
relatively unstable relatively stable
resonance contributors resonance contributors
for a carboxylic acid for a carboxylate ion
Another example of the influence of aromaticity on chemical reactivity is the unusual chemical behaviour exhibited by
cycloheptatrienyl bromide. Typically, alkyl halides are relatively nonpolar covalent compounds and therefore are soluble
in nonpolar solvents and insoluble in water. Cycloheptatrienyl bromide is an unusual alkyl halide in that its behaviour is
typical of an ionic compound; it is insoluble in nonpolar solvents but readily soluble in water. Investigation has shown
that cycloheptatrienyl bromide is indeed an ionic compound because its ring is not aromatic in the covalent form, but is
aromatic in the ionic form. In the covalent form, it has three pairs of p electrons but it does not have an uninterrupted ring
of p orbital-bearing atoms. In the ionic form, however, the compound is composed of an aromatic cycloheptatrienyl cation
and a bromide ion.
+
Br Br–
covalent ionic
cycloheptatrienyl bromide cycloheptatrienyl bromide
tropylium bromide
The cycloheptatrienyl cation is aromatic because it is a flat cyclic ion with three pairs of delocalized p electrons. The
stability associated with the aromatic cation causes the alkyl halide to exist in the ionic form.
+ +
+ +
+ +
+
resonance contributors
δ+ +δ
δ+ +δ
δ+ +δ
δ+
resonance hybrid
The reaction of cyclooctatetraene with potassium metal is yet another example of how the drive for a compound to
become aromatic causes unusual chemical behavior. Each equivalent of potassium donates an equivalent of electrons to
cyclooctatetraene.
This reaction occurs because the nonaromatic cyclooctatetraene molecule becomes an aromatic dianion by accepting
two electrons. Cyclooctatetraene is not aromatic because it is not planar and it has four pairs of p electrons. The
cyclooctatrienyl dianion is aromatic because it is planar and it has five pairs of delocalized p electrons.
Heterocyclic Rings
Certain structural units containing heteroatoms can be substituted into conjugated systems in such a way that the system
remains conjugated and isoelectronic with the original hydrocarbon. The most common examples are –CH = N– and –
N=N– double bonds and divalent sp2 –O–, –S– and –NR– units. Each of these structural fragments can replace a –CH=CH–
unit in a conjugated system and contribute two p electrons. These compounds are called heteroaromatic to recognize both
the heterocyclic structure and the relationship to benzene and other aromatic structures.
MO calculations on compounds in which a –CH=N– unit replaces –CH=CH indicate that the resonance stabilization
is very similar to that of the original compound. For the –O–, –S– and –MR– fragments, the resonance stabilization
is somewhat reduced but, nevertheless, high enough to consider the resulting compounds to be aromatic in character.
Various approaches have been used to estimate the aromaticity of these compounds. Generally speaking, the various
approaches suggest that the aromatic stabilization of pyridine is similar to that of benzene. This is in agreement with
the non-chemical estimates of the pyridine stabilization energy. Typically, the five-member compounds are found
to be somewhat less stabilized than benzene, with resonance energies in the range of one-half to three-quarters
of that for benzene. Magnetic and polarizabiliry criteria put the order of aromaticity as thiophene > pyrrole >
furan.
N
N N N
N N
N N N N
pyridine pyrimidine pyrazine pyridazine s-triazine
RE 43.3 40.0 40.9 32.7 44.9
N N
O N S S N
H H
furan pyrrole thiophene thiazole Imidazole
RE 27.2 40.4 43.0 42.0 48.3
Structural isoelectronic with benzene
N N N
N
H H
quinoline isoquinoline indole benzimidazole
RE 81.0 81.0 73.8 78.9
O NH
O S
benzofuran isobenzofuran isoindole benzothiophene
RE 55.4 0.44
RE=Resonance Energy
Structural isoelectronic with naphthalene
Additional heteroaromatic structures can be built up by fusing benzene rings to the aromatic heterocyclic rings or by fus-
ing together heterocyclic rings. When benzene rings are fused to the heterocyclic five-member rings, the structures from
fusion at the 2,3-positions are much more stable than those from fusion at the 3,4-positions. The p-electron system in the
3,4-fused compounds is more similar to a peripheral 10-p-electron system than to the 10-electron system of naphthalene.
As a result, these compounds have a strong tendency to undergo reactions that restore benzene conjugation in the carbo-
cyclic ring. The isobenzofuran structure is known to be an exceptionally reactive diene.
## Solved Example
3. When the following compound is dissolved which of the following option is formed.
Cl
Cl Cl ⊕ Cl Cl
(a) (b) (c) (d)
SOLUTION
3. When the compound ionizes it will exist as Cation because the cation is highly
stable.
\ (c)
Illustrations
16. Define the term nonaromatic.

Ans. Completely conjugated carbocyclic polyenes whose stability is comparable to their open chain analogs are called
nonaromatic.
17. List aromatic, antiaromatic, and nonaromatic compounds in decreasing order of resonance energies (stabilities).
Ans. Aromatic > nonaromatic > antiaromatic.
18. (a) Why are the following substances not aromatic?

CH2
(i) (ii) (iii)

H H
Cycloheptatriene 3-Methylene-1,4-cyclohexadiene Cyclobutadiene
(b) Characterize these carbocyclic polyenes as antiaromatic or nonaromatic.

Ans. (a) (i) One of the C’s is sp3 hybridized, thereby system. (ii) The methylene C is preventing a completely cyclic
overlapping not part of the ring which has one sp3 electrons phybridized C. (iii) There are only four (n = 1/2, not
an integer), (b) (i) and (ii) are nonaromatic while (iii) is antiaromatic.
19. Explain why the hydrocarbon with an acceptable Hückel number of 10 (n = 2) is not aromatic.
Ans. Although it has a Hückel number, the molecule cannot adopt the necessary planar conformation. If the double
bonds are all cis [Fig.10-8(a)] or one is trans [Fig.10-8(b)] the angle strain is excessive. The isomer with two trans
double bonds cannot be flat because two of the H atoms interfere with each other [Fig.10-8(c)].
H
H H
H
H
(a) (b) (c)
Fig.10.8
20. Draw four-membered rings showing all C=C’s, H’s, unshared pairs of e‑’s, and charges that would result in
aromatic ions.
Ans. It is necessary to have a p AO on each C with a total of either two or six e‑’s for the overlapping π system.
H H H H
+ ⊝
or 2+ or 2–
+ ⊝
H H H H
Huckel number is 2 Huckel number is 6
(n = 0) (n = 1)
21. 7-Bromocycloheptatriene (tropylium bromide) completely dissociates in water and gives a precipitate of AgBr
instantaneously with AgNO3, unlike its open-chain analog, 3-bromo-1,4-pentadiene. Explain.
Ans. The cycloheptatrienyl carbocation formed by a loss of Br‑ is unusually stable. It has an empty p orbital, being sp2
hybridized. It is aromatic, having six π electrons delocalized in seven overlapping p orbitals.
Br
+ Ag+ + AgBr
H
22. Cyclooctatetraene is nonaromatic. Explain

Cyclooctatetraene is not planar; it is actually tub-shaped (see Fig.10-10). The p orbitals of one C=C are not
coplanar with those of a neighboring C=C, and there can be no effective overlap for delocalization. This
noncoplanarity avoids the antiaromaticity which requires coplanarity.
Fig.10.10
23. Which species is the smallest aromatic substance? (Hint : It is an ion. )

Ans. The cyclopropenyl cation is an aromatic substance because it has two p e–’s (n=0). It forms a stable salt that can
be stored in a bottle.
HC CH
HC+
24. Azulene (C10H8) is a deep-blue compound with the structure shown in Fig.10-ll(a). Account for (a) its aromaticity
and (b) its dipole moment of 1. 0 D.
Ans. (a) Although neither the cyclopentadiene nor the cycloheptatriene ring alone is aromatic, charged resonance
structures (figure below) show a preponderance of negative charge in the five-membered ring, making it
similar to the aromatic cyclopentadienyl anion. In these structures, the seven-membered ring bears a positive
charge, giving it the aromatic character of the cycloheptatrienyl cation.
– –
⊕ etc. or + –
(a) (b) (c)
(b) The main contributing structures to the hybrid show charge separation responsible for the observed dipole
moment.
25. (a) Show (i) the Kekule resonance structures and (ii) the resonance hybrid of benzene, C6H6. (b) What is the
C-to-C bond order? (c) How does the resonance hybrid differ from a hypothetical cyclohexatriene?
(i) (ii)
Ans. (a)
The bond order is 11/2.
(c) The resonance hybrid has only one C-to-C bond length and bond energy. This length is intermediate between
that of a single and double bond. ‘Cyclohexatriene’ would have two different alternating C—C and C=C
bond lengths, with different bond energies. The hybrid is more stable (less reactive) than the hypothetical
cyclohexatriene.
26. The experimentally determined enthalpy of hydrogenation of benzene is –49.8 kcal/mol. Given DHh = –28.6 kcal/
mol for cyclohexene, calculate the resonance energy of benzene.
Ans. If benzene contained three noninteracting double bonds, its DHh would be 3(–28.6) = –85.8 kcal/mol. Simple
conjugation would lower the value slightly. The extra stabilization in benzene is –49.8 – (–85.8) = 36. 0 kcal/mol,
which is the resonance energy. This is energy that benzene does not possess because of resonance.
27. (a) Calculate DHh for the addition of 1 mole of H2 to (i) benzene, and (ii) 1,3-cyclohexadiene from the data
given below and the value for DHh = –55.4 kcal/mol for 1,3-cyclohexadiene. (b) List the three hydrocarbons
(cyclohexene, 1,3-diene, and benzene) in order of decreasing rates of monohydrogenation. (c) If benzene is
reacted with one mole of H2, what would you expect to isolate from the reaction?
(a) Add the following reactions:
(i) C6H12 – 2H2 → 1,3-C6H8 ∆ Hh = + 55.4 kcal/mol
C6H6 + 3H2 → C6H12 ∆ Hh = –49.8
C6H6 + H2 → 1,3-C6H8 ∆ Hh = +5.6 kcal/mol
(ii) C6H12 – H2 → C6H10 ∆ Hh = +28.6 kcal/mol
1,3-C6H8 + 2H2 → C6H12 ∆ Hh = –55.4
1,3-C6H8 + H2 → C6H10 ∆ Hh = –26.8 kcal/mol
Ans.
(b) Since the change in the numbers of moles is the same for each hydrogenation, we assume that the DS’s for the
monohydrogenation of C6H6, C6H8, and C6H10 are about the same, and that the DHh’s are directly related to the
DH’s. Therefore, the reaction with the most negative DHh is the fastest, and the order is cyclohexene (–28.6
kcal/mol) > 1,3-cyclohexadiene (–26.8 kcal/mol) >> benzene (+5.6 kcal/mol).
(c) When benzene is converted to the diene, the diene is reduced all the way to cyclohexane before more benzene
reacts. For each mole of benzene, one third of a mole of cyclohexane would be isolated and two thirds of a
mole of benzene would be recovered.
28. The experimentally determined enthalpy of combustion, (DHc), of C6H6 is –789.1 kcal/mol. Theoretical values
for the ‘combustion’ contribution of each bond are: C = C, –117.7; C — C, –49.3; and C—H, –54. 0 kcal/mol.
(a) Write a balanced equation for the combustion of one mole of benzene, (b) From this data, calculate the DHc
for C6H6 and explain the difference.
15
Ans. (a) C6 H 6 + O 2 → 6CO 2 + 3H 2 O
2
(b) The contribution is calculated for each bond and then totaled for the molecule.
Six C — H bonds = 6(–54. 0) = –324. 0 kcal/mol
Three C — C bonds = 3(–49.3) = –147.9
Three C = C bonds = 3(–117.7) = –353.1
Calculated value = –825. 0 kcal/mol
The difference [–789.1 – (–825. 0) = 35.9 kcal/mol] is a measure of the resonance energy, the energy that benzene
does not have.
29. Give an orbital picture of benzene. How does it account for benzene’s extraordinary stability?
Ans. The ring (skeleton) is comprised of six sp2-bondedshybridized C’s, each to two C’s and an H. Each C
also has a p AO with one e‑; the AO’s project above and below the plane of the ring which is a nodal
plane. Rather than form three localized alternating double bonds (cyclohexatriene), these p system in
which pAO’s overlap laterally to form an extended the e‑’s are symmetrically delocalized over all six C’s,
making the C’s equivalent. Delocalization results in less electron repulsion, greater stabilization, and lower
energy.
H + +
H
C C
+ +
– –
H C C H
+ +
– –
C C
H – – H
+ +
– –
+ +
– –
+ +
– –
Some basic thermodynamics and kinetic concepts about reaction mechanism
30. What information is provided by a reaction mechanism?

Ans. 1. The bonds broken and formed.
2. The discrete steps in the conversion of reactant (substrate) A to products D and E which may proceed through
several steps. For example, A→ D + E may proceed through steps i, ii, and iii as follows:
A 
i
→ [B] 
ii
→ [C] 
iii
→ D+E
3. The reaction intermediates, i.e., [B] and [C], formed during the intermediate steps.
4. The relative rates of the discrete steps, especially the slowest one.
Note that once an intermediate is formed it must react further. If only some of it did, the balance would accumulate
and become a product.
31. Define transition state.

Ans. As reacting molecules with sufficient enthalpy and with the proper orientation begin to collide, they enter a
transitory state in which there is a repositioning of certain atoms in the molecules while some bonds are breaking
and others are forming. When this specific state is at its maximum energy, it is called a transition state (TS) or
activated complex. Once TS is reached, it can proceed to products (or intermediates) or reform the reactants.
When a structure is drawn for the TS, the breaking and forming bonds are shown with dashed lines because they
actually are partial bonds.
32. Give equations for DH+, DS+, and DG+ in terms of the transition state.
Ans. Although the TS is a hypothetical state, it nevertheless assumes thermodynamic functions, HTS, STS, and GTS,
leading to the following relationships:
∆H = H TS − H GS ∆S = STS − SGS and ∆G = G TS − G GS

‡ ‡ ‡
where GS stands for the ground state which is the average condition of the reactants.
33. (a) At a given temperature, how do ground-state molecules attain the extra energy needed for a successful collision?
(b) Must each colliding molecule have the extra energy? (c) Is the transition state a reaction intermediate?
(d) How many transition states are there in a multistep mechanism?
Ans. (a) During unsuccessful collisions between ground-state molecules, kinetic energy may be transferred from one
to another causing one to slow down and the other to speed up. When superenergetic molecules now collide,
they may have sufficient DH+. (b) No. The two together must have the extra energy, not necessarily individually.
(c) No. Transition states are not true intermediates because they have no finite time of existence and have
energymaxima, while intermediates are real and exist at energy minima, which indicate stability. Intermediates
may be detected experimentally while transition states are theoretical constructs based on experimentation,
not simply made up. (d) Each step in a multistep mechanism has its own transition state.
34. Write an equation showing the TS in the abstraction of an H-from CH4 by Cl-to form H3C-and HCl.
Ans.
H H partially broken H
H C H + Cl [H C H Cl ]+
+
H C + H Cl
H H partially formed H
Methane Transition state Methyl radical
The brackets show the transient character of the TS that is further indicated by the symbol+.
35. (a) Draw an enthalpy (energy) diagram for a reversible one-step exothermic reaction: A + B → C + D.
(b) Compare the relative values of DH+forward (DH+for) and DH+reverse (DH+rev). (c) Are DH+ and DHr related?
Ans. (a) Enthalpy diagrams show the relationship between the enthalpies of reactants, transition state, and products
along the y axis. The x axis shows the progress of the reaction. The y-axis may indicate free energy or potential
energy as well as enthalpy.
y
HTS
+
+
∆ Hfor
+
= HTS – HR ∆ Hrev
+
= HTS – HP
HR
(A + B) +
∆ Hr+= HP – HR
HP (C + D)
x
Because the reaction is exothermic, Hf < HR (DHr = HP – HR). (b) Both reactions must proceed through the same
TS. Since the reaction is exothermic and the enthalpy of the product is lower, DH+reverse > DH+forward. (c) They are
rarely related. An exception is when the TS shows only the breaking of bonds.
36. Explain how the enthalpy diagram in the above figure shows: (a) that the reaction is exothermic, (b) the number
of steps in the reaction, and (c) the position of equilibrium.
Ans. (a) HP is lower than HR and the difference (DHr = HP – HR) is negative as expected for an exothermic reaction. Had
the reaction been endothermic, HP would have been greater than HR. (b) One transition state indicates a single
step reaction involving both reactants. (c) The negative DHr means the equilibrium favors the forward reaction
providing DHr is more significant than DSr.
37. Draw an enthalpy diagram for the endothermic reaction in which DH+ = 4 kcal/mol and DHr = 1 kcal/mol.
Ans. The transition state energy DH+ is greater by 4 kcal/mol than the ground state HR. Hp is greater by 1 kcal/mol
than HR.
TS
+
∆ H+
P
∆ Hr
R
38. Use the listed DH+ and DHr values, derived from enthalpy diagrams for various reactions, to determine whether
the corresponding reactions are fast or slow, and exothermic or endothermic.
(a) (b) (c) (d)
∆H‡ small large small large
∆Hr negative negative small positive positive
Ans. (a) fast, exothermic; (b) slow, exothermic; (c) fast, endothermic; (d) slow, endothermic
39. Account for the behaviour of a catalyst in terms of (a) HGS,HTS, and DH+ and, (b) SGS, STS, and DS+.
Ans. (a) Catalysts invariably speed up reactions by lowering DH+. This can be done by lowering HTs, raising HGS, or
doing both, (b) Catalysts can also increase reaction rates by increasing DS+. This can be achieved by increasing
STS, lowering SGS, or doing both.
40. (a) Explain why the rate constant k in a rate equation increases with temperature. (b) State the drawback in
increasing a reaction rate by raising the temperature? (c) What attempts are made to overcome this problem?
(d) Why do all natural biochemical reactions take place at the body temperature of the organism?
Ans. (a) Increasing the temperature increases the kinetic energy of molecules, making them move faster thereby
increasing the number of collisions. More molecules now also have sufficient energy for more effective collisions.
(b) At higher temperatures all rates increase, including those of side and reverse reactions. (c) Temperatures are
selected to encourage the preferred reaction to take place at an acceptable rate with a minimum of side reactions.
This can often be achieved by searching for catalysts, (d) Practically every natural biochemical reaction occurs
with the aid of some catalyst, e.g., an enzyme.
41. Draw an enthalpy diagram for an exothermic two-step reaction when (i) the first step is slow and rate-determining
and (ii) the second step is rate-determining. (a) Label the intermediate as I. (b) Compare the enthalpies of
intermediates IA and IB with the transition states. (c) When may an intermediate be isolated? (d) Compare
enthalpies of TS1 and TS2 in (a) and (b).
Ans. (a) See figure below.
(b) In both (i) and (ii) the enthalpies of TS1 and TS2 are greater than the enthalpies of IA and IB.
(c) If the DH+rev and DH+for for the intermediates are both large enough for the rates to be slowed sufficiently, the
intermediate may accumulate permitting isolation. Under such circumstances the intermediate would be a
byproduct.
(d) (i) TS1 > TS2, (ii) TS2 > TS1. In both cases the TS of the slower (or slowest) step has the higher (or highest) HTS.
TS1
Enthalpy
Enthalpy
TS2
TS2
TS1
IA
R R IB
P P
Progress of Reaction Progress of Reaction
(i) (ii)
42. (a) Define molecularity of a reaction. (b) What are the types of molecularity encountered and which type is rare?
(c) Can molecularity be determined from the rate equation?
Ans. (a) Molecularity is the number of reactant particles colliding in a step. Unlike the order of a reaction, the
molecularity of a step must be an integer. (b) When one particle is the reactant in a step, the step is unimolecular. If
a single species must collide with solvent molecules, the reaction will appear to be unimolecular because solvent
does not appear in rate equations. Collision of two reacting particles is a bimolecular step. Temolecular reactions,
involving the simultaneous collision of three species, are rare. (c) In multistep reactions, the molecularity of any
single step is likely not to be related to the rate equation.
Reaction Intermediates
Reaction intermediates are generated by the breaking of covalent bond of the substrate. They are short-lived species and
are highly reactive. There are six important types of reaction-intermediates.
(1) Carbocation (2) Carbanion (3) Free radical
(4) Carbene (5) Benzyne and (6) Nitrene
Table 2.3 Reactive Carbon Intermediates
Carbene
Carbocation Carbanion Radical Singlet* Triplet† Radical cation
+ – +
Structure C C C C C C
Formal 4–3–0=+1 4–3–2=–1 4–3–1=0 4–2–2=0 4–2–2=0 4–2–1=+1
charge
bonds 3 3 3 2 2 2
lone pairs 0 1 0 1 0 0
HON 3 4 3 3 2 2
HO’s used sp2 trigonal sp3 sp2 trigonal sp2 sp sp
Shape coplanar pyramidal coplanar bent linear linear
(i) Wedge projection (ii) Orbital representation
sp2
+
C
(a) Carbocation sp2 C+
120°
sp2
p
sp3
C
– sp3
(b) Carbnaion C–
109° sp3
sp3
Carbocation
Carbocations
Carbocations are cations which are obtained by the removal of one of the four groups attached to the carbon atom along
with its bonding electrons. Thus, they may be defined as organic species which have a positive charge on a trivalent
carbon atom bearing only six electrons. They are short lived and highly reactive species. Untill the early 1970s, the ions
with positively charged carbon atoms were known as carbonium ions. As this name does not follow the usual pattern of
nomenclature, the term carbocation was introduced to describe such ions. The term carbocation is consistent with the well-
accepted name for the related anions, i.e., carbanions. However, both these terms—carbocation and carbonium ion—are
being used to describe an ion with a carbon atom having no unshared pair of electrons and only three covalent bonds. It
has a positive charge.
In most of the cases Carbocations cannot be isolated but this instability does not minimize their importance as reactive
intermediates in a great number of chemical reactions.
Classification of carbocations
Alkyl Carbocations are classified into three categories i.e., primary (l°), secondary (2°) and tertiary (3°) depending upon
whether the cationic carbon is primary, secondary or tertiary. Methyl carbocation with one carbon is a special case.
⊕ ⊕
CH3 CH3CH2
Methyl carbocation Ethyl carbocation (1°)
⊕ ⊕
(CH3)2CH (CH3)3C
iso-Propyl carbocation (2°) tert-Butyl carbocation (3°)
Structure
Normally carbon atom of the carbocation is sp2-hybridized and it uses the three hybrid orbitals for singly bonding to three
substituents; the remaining unhybridized p-orbital is empty. The carbocation thus has a planar structure having all the three
covalent bonds in one plane with the bond angles of 120° between them. The empty p-orbital is at right angle to the plane
of sp2-hybridized orbitals.
R
sp2-hybridized carbon
⊕
C empty p-orbital
R 120° R Orbital picture of a carbocation
Carbocations have a strong tendency to complete the octet of carbon and consequently, they are highly reactive species
and participate in many chemical reactions, i.e., in unimolecular substitution and elimination reactions, in the decomposi-
tion of diazonium salts and in various rearrangements.
Stability of carbocations
Any factor which tends to disperse the positive charge must increase the stability of Carbocations while, any factor which
tends to intensify the positive charge must decrease the stability of the carbocation.
⊕ ⊕
D C A C
D = Electron-donatin group; A = Electron-withdrawing group;

disperses the positive charge and intensifies the positive charge and
hence stabilizes the carbocation. hence destabilizes the carbocation.
1. Stability of saturated Carbocations (alkyl Carbocations): The stability of alkyl carbocations decreases in the following
order:
Tertiary > Secondary > Primary
⊕ ⊕ ⊕
(R3C ) (R2C H) (RC H2)
This order can be explained on the basis of the following factors:
(i) Inductive effect: There is strong evidence, both physical and chemical, that alkyl groups are electron-donating,
i.e., they exhibit +I-effect. Thus, when these groups are attached to the electron-deficient carbon of the carbocation,
they release electrons towards this carbon. The positive charge thus gets dispersed over the alkyl groups and this
dispersal of charge increases the stability of the carbocation. Obviously, the greater is the number of such alkyl
groups attached to the cationic carbon, the more is the dispersal of positive charge and hence the stabler will
be the carbocation. Thus a tertiary carbocation having three alkyl groups, should be more stable than secondary
having two alkyl groups which in turn should be more stable than primary having one alkyl group.
R R H
⊕ ⊕ ⊕
R C > R C > R C
R H H
Most stable Least stable
(three +I-groups) (one +I-groups)
(ii) Hyperconjugation effect: The greater stability of alkyl substituted carbocations can also be explained on the basis
of the phenomenon of hyperconjugation. According to this, the s-electrons of aC—H bonds are delocalized
into vacant p-orbital of the positively charged carbon. This disperses the positive charge over all such bonds.
Thus, it is reasonable to say that the greater is the number of asC—H bonds the stabler is the corresponding
carbocation. In agreement with this the tertiary butyl carbocation having nine such aC—H bonds is most stable
followed by isopropyl carbocation having six such sC—H bonds. The ethyl carbocation having only three such
sC—H bonds is the least stable in this series. These cations are regarded as hybrids of various hyperconjugative
resonance contributing forms and the number of these contributing forms depends upon the number of as C—H
bonds. Thus greater is the number of asC—H bonds, the greater is the number of hyperconjugative resonance
contributing forms and hence the stabler the is the carbocation.
⊕
H H H H
⊕ ⊕
H C C CH3 H C C CH3 H C C CH3 H C C CH3
α α
⊕
H CH3 H CH3 H CH3 H CH3
tertiary-Butyl cation
Six more such
equivalent structures
(Nine ασC H bond, nine equivalent hyperconjugative structures, most stable)
⊕
H H H H
⊕ ⊕
H C C CH3 H C C CH3 H C CH3 H C CH3
α α
⊕
H H H H H H H H
iso-Propylcation Three more such
equivalent structures
(Six a s C—H bonds, six equivalent hyperconjugative structures, less stable than tert-butylcation).
⊕
H H H H
⊕ ⊕
H C CH2 H C CH2 H C CH2 H C CH2
⊕
H H H H
Ethylcarbocation
(Three as C–H bonds, three equivalent hyperconjugative structures, least stable of the three)
(iii) Steric effects (or better steric relief): Steric effects play a key role in the ease of formation as well stability of
carbocations. We know that carbocations are planar with bond angles of 120° (i.e., having maximum distance
between the substituents attached to the positively charged carbon) but the substrates from which they are formed
have sp3-hybridized carbon and have bond angles of 109.5° (i.e., lesser distance between substituents, thus
causing congestion or steric crowding): Now, if the four substitutents attached to an sp3-hybridized carbon are
bulky, the molecule will be highly strained* due to congestion. However, when such molecule ionises to produce
a carbocation, the bond angles expand from 109.5° (sp3) to 120° (sp2) thereby resulting in the relief (removal of
congestion) due to increase in space between the bulky substituents. A typical case of steric relief is the ionisation
of tri-isopropylmethyl chloride.
H 3C CH3
H3C CH3 CH
CH 109.5° 120° 120°
109.5° ⊕
H3C C Cl C
HC 109.5° CH3 CH3
H C 109.5°
3 CH CH 120° CH
CH3
H3C CH3 CH3
iso-Propyl group closer in space The distance between isopropyl groups increases
(Highyl strained) (Steric relief)
The order of stability of simpler 3°, 2°, 1° and methyl cations is also in tune with the concept of steric relief.
2. Stability of unsaturated and other types of carbocations: The carbocations having a double bond or a non-bonding
pair of electrons next to the positively charged carbon are stabilized by resonance which involves the delocalization
of p or n-electrons into vacant p-orbital of this carbon. For example,
(i) Allyl and benzyl cations, diphenylmethyl and triphenyl methyl carbocations: In these cations the positiv-
ely charged carbon atom is in conjugation with a double bond. This arrangement leads to increase in de-
localization due to resonance and because of this the positive charge is dispersed over the carbon skeleton.
Thus,

Allyl cation
⊕ ⊕
H2C CH CH2 CH2 CH CH2
(Resonance stabilized allyl cation)
Benzyl cation
⊕
CH2 CH2 CH2 ⊕ CH2
⊕ ⊕
* This type of strain is caused by pushing of the substituents together in the limited space and is called as B strain (or back strain)
3. Effect of substitutents on the stability of benzyl carbocation

The presence of various substituents at o-and p-positions of benzene ring in benzyl carbocation greatly influence
the stability of substituted benzyl carbocations. Electron-donating groups such as alkyl groups, –OH, –OR,
–NH2, –NHR, –NR2 etc. , stabilize these cations. This may be attributed to the dispersal of positive charge by
resonance (+R-effect) in case of groups having unshared pair of electrons and hyperconjugative effect of alkyl
groups (CH3 group having highest effect). In contrast, electron-withdrawing groups such as –CN, –NO2, –CHO,
–COR, –COOH, –COOR, etc. , destabilize these cations. This may be due to the fact that electron-withdrawl by
these substituents would intensify positive charge on the cationic carbon. Thus, for example, p-methoxybenzyl
cation is more stable than benzyl cation whereas p-nitrobenzyl cation is less stable than this.
⊕ ⊕ ⊕
CH3O CH2 > CH2 > O2N CH2
p-Methoxybenzyl cation Benzyl cation p-Nitrobenzyl cation

(Dispersal of charge on methoxy (Intensificaiton of charge due to
group due to resonance, electron-withdraw by nitro group,
more stable than benzyl cation) less stable than benzyl cation)
The diphenyl and triphenyl carbocations are much more stable than benzyl cation. Obviously, the larger the
number of phenyl groups attached to cationic carbon, the greater is the dispersal of positive charge. Hence, more
stable are such carbocations. The decreasing order of stability of benzyl, diphenylmethyl and triphenylmethyl
carbocations is as follows:
⊕ ⊕ ⊕
(C6H5)3C > (C6H5)2CH > C6H5C H2
Diphenylmethyl carbocation is more stable compared to benzyl carbocation due to the greater number of
resonating structures.
⊕ Three more
CH CH CH CH
such
⊕ ⊕ resonating
structures
Diphenylmethyl ⊕
(Resonance structures of diphenylmethyl carbocation)
carbocation
Similarly, triphenylmethyl carbocation is more stable than diphenylmethyl carbocation due to the larger number
of resonating structures, which can be written for this as shown below:
⊕
C C C C Six more
such
⊕ ⊕ resonating
structures
⊕
(Resonance structures of triphenylmethyl carbocation)
The high stability of triphenylmethyl carbocation is reflected in the fact that salts such as perchlorates,
fluoroborates, etc., have been isolated and stored for a very long time.
Similary, triphenylcyclopropenyl cation is more stable than diphenylcyclopropenyl cation which in turn is more
stable than phenylcyclopropenyl cation.
C6H5 C6H5 C6H5

⊕ ⊕ ⊕
> >
H5C6 C6H5 H5C6

Triphenylcyclopropenyl Diphenylcyclopropenyl Phenylcyclopropenyl
carbocation carbocation carbocation
(i) Stability of tropylium ion or cycloheptatrienyl cation: Tropylium ion is unusually stable. The reason for its unusual
stability is that it is an aromatic cation containing 6p-electrons. As shown below the 6p-electrons are completely
delocalized over all the seven sp2-hybridized carbon atoms below just in the same manner as the 6p-electrons are
devocalized in benzene ring. Various resonance contributing forms of tropylium ion are as under.
⊕
⊕ ⊕
⊕
⊕
⊕
⊕
⊕
⊕
(Resonance structures of tropylium ion)
Actually the tropylium is so stable that its reaction with nucleophiles such as water, alcohols, etc. , is very slow.
(ii) Cyclopentadienyl carbocation: Like cycloheptatrienyl cation, it is expected that cyclopentadienyl cation should
also be stabilized by resonance because the cationic carbon is conjugated with two double bonds. Actually
this carbocation is highly unstable. The reason for this instability is that it has 4p-electrons and hence is anti-
aromatic. This is an example of a species which is destabilized by resonance.
(iii) Stability of alkoxyalkyl carbocations: Carbocations in which the positively charged carbon atom is attached
to a heteroatom (carrying non-bonding pair(s) of electrons) such as oxygen, nitrogen, halogen etc., are also
stabilized by resonance. For example,
R R
⊕ ⊕
C Ο CH3 C Ο CH3
R R
The stability conferred by resonance on⊝this carbocation is reflected in the fact that methoxymethyl cation can be
⊕
isolated as a stable salt, [CH3O C H2Sb F6].
(iv) Stability of acyl cations: Like alkoxyalkyl cations, acyl cations can also be regarded as hybrids of the following
contributing forms and hence are stabilized:
⊕ ⊕
R C O R C O
I II
Although having positive charge on the more electronegative oxygen atom, the contribution of canonical structure
(II) is less than that of structure (I) to the resonance hybrid, yet acetyl cation, CH3CO+ is almost as stable as tert-
butyl carbocation.
(v) Vinyl and phenyl carbocations: Carbocations having positive charge on the doubly bonded carbon atom as in
the case of vinyl (CH2 = CH+) and phenyl (C 6 H 5+ ) cations are not stabilized by resonance because the positively
charged sp2-orbitaI of the carbon atom is perpendicular to the p-orbitals of the p-bonds. Thus, these cations
are very short lived. However, vinyl cations are more stable than methyl carbocation but less stable than other
primary carbocations (Table 2.2).
(vi) Cyclopropyl methyl carbocations: They are more stable than benzyl carbocations.
Stability of cyclopropyl methyl carbocations increases with every cyclopropyl group. Thus, additional cyclopropyl
group has commulative additive effect on the stability. Thus,
⊕ ⊕ ⊕
C CH CH2
Stability in decreasing order
The special stability is a result of conjugation between the bent orbitals of the cyclopropyl ring and the vacant-p-
orbital of the cationic carbon (so called bent bond resonance or, banana bond resonance).
(vii) Important notes on + M effect:
If a-atom with respect to cationic carbon has lone pair of electrons, then lone pair of electrons strongly stabilizes
a carbocation due to the delocalization.
Alkoxy and amino groups are important substituents for such types of carbocations.
⊕ ⊕
(CH3)2 N – CH2 is more stable than R3C
⊕ ⊕
CH3 – O – CH2 is more stable than R – C – R
R
1.
⊕ ••
H ⊕ •• ⊕ ••
C N C OH C F ••
•• ••
H
I II III
⊕
H ⊕ ⊕
C N C O H C F
•• ••
H
When the +M donor atoms belong to the same period, the less electronegative atom will exert stronger +M effect.
Hence, the order of intensity of +M effect is N > O > F. So the carbocation stability will follow the order I > II > III.
2.
⊕ •• ⊕ •• ⊕ ••
C F •• C Cl •• C Br ••
•• •• ••
I II II
⊕ ⊕ ⊕
C F •• C Cl •• C Br ••
•• •• ••
π2p–2p π2p–3p π2p–4p

strong π bond weak π bond
When the + M donor atoms belong to the same group, electronegativities of atoms are not important, rather the size of
the p-orbitals becomes the more important factor. We know large p-orbitals form weaker p bond, therefore, their +M
effects will also become weaker. Hence, the order of intensity of +M effect is F > Cl > Br. So the carbocation stability
is I > II > III.
Relative Stability of Carbocations

The relative stability of carbocations can be easily assessed by determining bond dissociation energy for heterolytic
fission. The lower the value of this energy, the greater is the stability of the carbocation. The bond dissociation
energies of some alkyl/aryl halides are given in Table 2.4.
Table 2.4 Bond dissociation energies for some alkyl/aryl chlorides for heterolytic fission (kJ mol–1)
Alkyl/aryl chloride Bond dissociation energy

CH3 — Cl 952
CH3CH2 — Cl 799
CH3CH2CH2 — Cl 744
(CH3)2CH — Cl 711
(CH3)3C — Cl 657
CH2 = CH — Cl 866
CH2 = CHCH2 — Cl 724
C6H5— CI 916
C6H5CH2 — Cl 695
A look at the data listed in Table 2.4 reveals that the order of stability of carbocation is:
⊕ ⊕ Tert-butyl > 1° Benzyl > 1° Allyl > n-Propyl > Ethyl >
C CH
Vinyl > Methyl > Phenyl
⊕
Relative Stabilities of Carbocation
R R H H
+ + +
R C+ CH2 ⇒ CH2= CHCH2 ⇒ R C+ > R C+ > CH2= CH ⇒ H C+
R R H H
tertiary benzyl allyl secondary primary vinyl methyl
carbocation cation cation carbocation carbocation cation cation
increasing stability
4. Characteristics of carbocations (except vinyl carbocation)

(i) It has three bond pairs with empty p-orbital. Its hybridisation is sp2.
(ii) Shape of carbocation is trigonal planar.
+
Note: Triphenyl methyl carbocation has propeller shape.

(iii) There are six electrons in the outermost orbit of carbocationic carbon, hence its octet is incomplete. All the six
electrons are paired.
(iv) It is charged electrophile.

(v) It is diamagnetic in character.
(vi) It is formed by heterolytic bond fission.
(vii) It reacts with nucleophiles.
## Solved Examples
4. Give the order of stability of the following carbocations.
CH 3+ , CH 3 CH +2 , CH 3 CH 2 CH +2 , CH 3 CH + CH 3 (CH 3 )3 C +
5. Which of the following carbocation is least stable?

+
CH2
+
(a) (b) CH = CH 2
CH3
+
(c) CH 2 = CH − C H 2 (d) CH3 C
+
SOLUTIONS
4. The decreasing order of stability
(CH 3 )3 C+ > CH 3CH + CH 3 > CH 3CH 2 CH +2 > CH 3CH +2 > CH 3+ . In CH 3CH 2+ , CH3 group donates
electron’s by +I effect. As the number of CH3 group increases distribution of charge and hence the
reduction of charge density on C bearing +ve charge is more effective. So (CH3)3C+ is most stable-
most number of alkyl groups-most stable.
5. Positive charge is on sp hybridized carbon.
\ (b)
5. Reactions which take place by the formation of carbocation as reaction intermediate: In the following type of
reactions, product formation takes place by the formation of carbocation as reaction intermediate.
(i) SN1 reactions
(ii) E1 reactions
(iii) Electrophilic addition reactions of alkenes and alkynes.
Carbocations are the key intermediates in several reactions and particularly in nucleophilic substitution reactions.
Structure
Generally, in the carbocations, the positively charged carbon atom is bonded to three atoms and has no lone pairs on car-
bon.
Carbon has six valence electrons.
It is sp2 hybridized with a planar structure and bond angles of about 120°.
R
⊕
C
R R
Orbital picture of carbocation
+
There is a vacant unhybridized p orbital which in the, case of CH3 lies perpendicular to the sp2 hybridized plane.
Formation of carbocation
Carbocations can be generated in a variety of ways, some of the reactions in which carbocations are formed are summa-
rized below.
(i) By addition of electrophile to p-bonds:
H H H
H⊕ H2O –H⊕
CH = CH CH CH CH CH CH CH
⊕
⊕OH OH
2
The reaction is reversible, the reverse being perhaps better known as acid-catalysed dehydration of alcohols.
Protonation can also occur on oxygen in a carbon-oxygen double bond.
OH
δ+ δ− Η⊕ ⊕ ⊕ Η 2Ο
C=O C = OH C OH C + H⊕
OH
⊕
C = O + H2SO4 C OH + HSO4
Deamination of amines by nitrous acid.
R − NH 2 HNO
 2
→ RN ⊕2 
→ R ⊕ + N2
Protonation of alcohols followed by dehydration.

⊕ ⊕
R − OH H→ R O H 2 
→ R ⊕ + H2O
A stable carbonium ion formation will be preferred in a process (as formation of carbocation is a rate determining
step)
CH3 CH3
H+
CH3 C CH2 CH3 C CH 3
⊕
(Stable tert carbocation)
CH3
H+ ⊕
CH3 CH CH2
(Primary carbocation will
⊕ not be preferred)
CH = CH2 CH – CH3
H+ (Aromatic sec.
carbocation)
(Markovni Koff’s Rule: richer becomes more richer)

(ii) By attack of electrophile on lone pair:

H+ ⊕
e.g. C O H C O H C ⊕ + H2O
H
H+ ⊕ ⊕
C SH C SH2 C + H2S
(iii) If both lone pair and π bonds are present:

⊕ ⊕
CH2 = CH O H CH2 = CH
H+ H
CH2= CH – O – H (unstable)
(attack on π-bond ⊕ ⊕
be preferred) CH3 – CH OH CH3 CH = O H
(Stable Carbocation)
⊕ ⊕ ⊕
CH2 = CH CH2 O H → CH2 = CH – CH2 CH2 CH = CH2
(Stable)
CH2= CH – CH2 – OH H+ H
(attack on lone pair
⊕
preferred) CH3 CH CH2OH
(Less stable)
(iv) From other cations:

Carbocations may be obtained from the decomposition of other cations, e.g., diazonium cations from the action of
NaNO2/HCl on RNH2
⊕ ⊕ ⊕
[R N = N R N ≡ N] R + N ≡ N↑
and also by the use of a readily available carbocation to generate another that is not so accessible.
H H
⊕ ⊕
Ph3 C + Ph3 C –H +
(v) The most common cation is H⊕, adding to unsaturated linkages, i.e., protonation, in for example the acid-catalysed
hydration of alkenes.
(vi) The obvious example is simple ionisation, the group attached to carbon departing with its bonding electrons to form
an ion pair, R⊕YΘ:
⊕
Me3C – Br Me3C Br
Ph2CH – Cl Ph2CH⊕Cl
MeOCH2 – Cl MeOCH2⊕Cl
I n each case, a highly polar (high ∈) powerful ion-solvating medium is generally necessary. In a similar context, the
effect of Ag⊕ in catalysing reactions, often by a shift from SN2 → SNl mode,
Ag⊕ + R – Br → AgBr↓ + R⊕
(vii) Reaction of halides with super acids (SbF5, FSO3H, etc.)
⊕
R — F + SbF5 R + SbF6
REARRANGEMENT IN CARBOCATIONS
Carbocation Rearrangement
A carbocation formed in a reaction rearrange itself to a more stable carbocation, if proper structural features are present.
Unlike resonance, rearrangement is a real chemical change as it involves cleavage and formation of σ bond.
(a) Hydride shift
Let us consider the following reaction:
CH3
H
CH3 ⊕
H⊝ shift
(the hydrogen is
⊕ migrating with the CH3 CH3
bond pair, hence it Has 8th
is a hydride) (more stable)
Remember,
(1) Only ‘pH’ with respect to carbocation, can be shifted (1, 2-shift).
(2) The resulting carbocation must be more stable.
(3) There can be number of hydride shifts possible as long as the resulting carbocation in each step is more stable.
H CH3
⊕
C H2 CH3 ⊕
H⊝ shift H⊝shift
⊕ CH3 CH2
H
2αH 4αH 8αH
(most stable)
H ⊕ H
H⊝ shift ⊕
⊕
C H2 ⊕
3αH 8αH
2αH H
(less stable) (Not formed)
5αH
(Final carbocation)
(more stable)
If a single step is energetically not favourable, the rearrangement of carbocation will stop.
(b) Methyl shift
Let us consider the following reaction.
CH3 CH3
α α
CH2 ⊕ H CH2
CH3 Me shift
CH3 ⊕ CH3–group CH3

Is migrating with
its bond pair in CH3
Me groupα-C 3αH −
7αH
attached to the form of CH 3 (more stable)
Remember,
(1) Only CH3 group attached to a-carbon can be shifted (a-CH3 group)
(2) The resulting carbocation should be more stable.
(3) There can be a number of CH3 shifts possible as long as the resulting carbocation is each step is more stable.
Now the question arises that whether we should go for a methyl shift or hydride shift when both the rearrangments are
possible with a carbocation.
Let us consider the following rarrangement:
CH3 H ‘a’ CH3
⊕ H α
Me shift ⊕
CH 2 H– shift
b α
CH3 ‘b’
CH3 ⊕ CH3 CH2
b
3αH
4αH 8αH
Since, hydride shift provides a more stable carbocation, hybride shift will be favoured over the methyl shift.
⊕
4. The exceptional stability of CH2 can cause an exceptional ring contraction of four membered ring.
⊕
⊕
ring ⇒ CH2
contfraction
⊕CH2 cyclopropyl
methyl cation
(very stable)
For the same reason, the ring expansion of three membered ring to four membered ring through carbocation is not complete.
⊕
⊕
CH2
Major products are obtained from both the cations.

Generally, when the same a-carbon has hydrogen and methyl group attached to it, the hybride shift provides the more
stable carbocation.
Let us consider another example.
CH3 CH3
⊕
CH3 Me shift
⊕ a
CH3
6αH
H H
b
H– shift
⊕
4αH
This time, Me shift provides a more stable carbocation and Me shift will be favoured over the hydride shift.
(c) Ring expansion

Most of the rings suffer from angle strain as the ∠C–C–C (angle) deviates from ideal sp3 (109o28′) value. The six membered
ring is the strain free ring, as it remains in the form of chair conformation.
θ ~ 109o
The thermal stabilities of the saturated carbon can be as follows:

3<4<5< 6 >7>8
membered
Therefore, the rings smaller than six membered ring tend to undergo ring expansion to gain more stability. The rings
larger than six membered ring tend to undergo ring contraction to gain more stability.
Let us consider the following rearrangement:
+
C H –CH3 CH3
‘a’ ‘b’ CH3
H ⊕ ⊕
‘a’ or
ring expansion
3αH
4αH
‘b’ H– shift
⊕
H
CH3
As we can see here that ring expansion occurs in preference to hydride shift. We can conclude that ring stability is a
more important factor as compared to the stability of carbocation attained through hyperconjugation.
Important
1. For ring expansion, the positively charged carbon (carbocation) should be directly attached to the ring (or next to the
ring) 1, 2 shift). No ring carbon can be carbocation for ring expansion.
2. Ring should be smaller than six membered ring.
3. Since it is 1, 2 shift, ring size increases by one unit, i.e., 4 → 5 or 5 → 6 etc. but not 4 → 6.
(d) Ring cantraction

Let us consider the following rearrangement:
⊕
⊕ CH2
⊕
CH2
CH2
or
4αH 1αH
The reaction shows that hyperconjugation of carbocation is less important than ring contraction. Ring contraction can
be preferential depending on the stability of carbocation formed. The following example explains it.
+
&+ &+ &+
&+
&+
µE¶ µD¶
µE¶ µD¶
D+ D+
Important
1. For ring contraction, one ring carbon should be carbocation and it is 1, 2 shift.
2. Ring should be larger than six membered ring.
3. Since it is 1, 2 shift ring size decreases by one unit, i.e., 7 → 6 or 8 →7, but not 8 → 6.
If the ring is that enough, the possibility of carbocation formation processes.
Comparitively more stable
If the bridgehead carbons are directly attached through a bond, carbocation can be formed because bonds become
coplanar.
⊕
This above carbocation can be formed.
Illustrations
43. Compare the reactivities of the following alcohols towards acid catalyzed dehydration.
OH
OH
OH
Ans. OH
I II III IV
⊕
⊕ ⊕
⊕ CH2
4αH 9αH 0αH 6αH
Remember, the reactivity of the substrate depends on the stability the first Carbocation formed, not on the final
rearranged carbocation. It is because the formation of the first carbocation is the rate determining step.
Therefore, the correct order of reactivities will be
II > IV > I > III
44. Compare the reactivities of the alkenes towards the addition of HBr.
CF3
Ans. I II III IV
H⊕ H+
⊕ ⊕
CF3 ⊕
6αH 9αH ⊕
5αH 3αH
but unstable Stable due to + I
due ot – I effect effect of tutiorry
of - CF3 group butyl group.
Remember, the –I effect of halogen can be more significant beacause of the slight difference in hyperconjugative
effect.
Therefore, the order of reactivity will be
II > I > IV > III
Number of rearrangements
Remember, hydride shift, methyl shift, ring contraction, ring expansion all can occur one by one in carbocation rearrange-
ments as long as stability conditions are satisfied.
Let us consider the following examples.
CH3
⊕
CH2 CH3 CH3 H
H Shift
–
Me Shift ⊕
⊕
H CH3
2αH 3αH 7αH
(Final most
stable cation)
CH3 CH3
H
⊕ ⊕
ring ⊕ ⊕
CH3
expansion
H
⊕ CH3
⊕ ⊕
CH2
ring
contraction
1αH (Final cation and the
most stable)
Fate of carbocation
The more the stability of the carbocation, the more is the lifetime of the carbocation. The most stable carbocation formed
at the end of the rearrangement produces the major product. All the carbocations, those initially formed or formed during
the course of rearrangement can produce insignificant minor products. Therefore, the final carbocation is important to us.
The formation of the first initial carbocation is usually the rate determining step. Therefore, the first initial carbocation
is important to us to compare the reactivity of the reactant. Remember that reactivity is a kinetic factor and depends on
how fast the reactant can react, not how far the reaction can proceed.
There are two different ways through which carbocation can produce the product.
Case I
Carbocation can combine with a nucleophile to produce product.
nu
C ⊕ C nu
Under thermally excited condition, carbocaation can lose a-H in the form of proton to form p bond.
H
⊕ –H
+
C C C C
If we have a choice of carbocation, the most stale alkene is normally the major product.
Reactions involving carbocation as the intermediate
Case II
Example 1
Br
HBr
O–H Formation of
product.
+
H
H
⊕
–H2O H–shift
⊕ Rearrangement
⊕ 8αH
O H formation of 4αH
carbocation
H
Example 2
I
H1
H+ CH3
formation of r
carbocation Me shift
⊕
⊕
3αH
Example 3
CH3 CH3
Cl
⊕
HCl Cl–
Formation of
product
Formation of H+
carbocation
CH3
H
⊕
⊕
rearrangement ⊕
ring expansion ≡
Example 4
OH CH3
CH3 Br
HBr (major Product)
H⊕
H ⊕ H
O
CH3 Br
‘b’
CH3 a CH3
⊕ Η
‘α’ ⊕
H shift
1αΗ 4αΗ
Me shift ‘b’ CH3
CH3
Η ⊕
⊕ –
H shift
6αΗ
4αΗ
Here we can see that methyl shift followed by
hydride shift provides the more stable carbocation.
Example 5
OH
H⊕
H⊕
H ⊕ H ∆
O b
⊕
b ⊕
α ⇒
α
When a five members ring is converted
⊕ to six membered ring the angle strain is
realeased by (109° – 108°) = 1° 28’
When a four members ring is converted
to a five membered ring, the angle strain
H is reduced by (108 – 90) = 18°. Therefore,
⊕ ⊕
H shift the ring expansion of four members ring
is preferred.
⇒
⊕
⇒
This five
membered ring
has a carbocation
directly attached to it;
therefore, ring expansion
is possible.
H
⊕
⇒
8αH
This five
membered ring
can undergo ring expansion
for the same reason.
Non classical Carbocation
A carbocation attached Carbocation can not be

to three bonds is formed at the bridge head of a
sp2 hybridized and bicyclic molecule as the three
requires planar bonds attached to the carbocation
bonds attached to it. are not coplanar.
Unstable carbocation
at the bridgehead.
Therefore, the following reaction can not take place.
⊕
H
∆
OH
no hydride shift
⊕
H
Illustration
45. Find the product of the reaction.
⊕
1. H
2. nu
O
⊕
H nu
Ans.
⊕ nu
O O O O
⊕
When lone pair
and π bond are The carbocation
conjugation, the is stabilized by
electrons are donated the +M effect.
through the π bond.
A common mistake
QX
5HPHPEHUWKDWWKHSRVLWLYHO\FKDUJHGR[\JHQKDV
2 FRPSOHWHRFWHWDQGLWFDQQRWUHFHLYHDQ\PRUH
HOHFWURQV
QX
Case II
Example 1
Example 2
+ + +
4. I. – CH -CH=CH3 II. – CH -O-CH3 III. – CH -CH3
Which of the following orders is correct about the stability of cation?
(a) I > II > III (b) III > II > I
(c) III > I > II (d) II > I > III
⊕ ⊕ O ⊕
5. O
I II III
Which of the following orders is correct for the stability of these carbocations?
(c) II > I > III (d) II > III > I
⊕ ⊕ O ⊕
6. I II III
O N
CH3
⊕
7. ⊕ ⊕
I II III
⊕
8. ⊕ ⊕
I II III
(c) I > III > II (d) II > I > III
⊕ ⊕
9. I C CH2
⊕
II CH2 III
(c) II > III > I (d) III > I > II
⊕
⊕ ⊕
10.
I II III
⊕
CH2
⊕ CH3 ⊕
11. I II CH3 C III CH3 CH CH3
CH3
(c) II > I > III (d) II > I ≈ III
CH3
⊕C CH
3
⊕ CH3 ⊕
12. I II CH3 C III CH2 CH CH2
CH3
(c) II > I > III (d) II ≈ III ≈ I
⊕ ⊕ ⊕
13. CH2 F CH2 Cl CH2 Br
I II III
14. ⊕
CH2
III
⊕
CH3
I ⊕
II CH3 CH CH3 OCH3
(c) III > I ≈ II (d) II ≈ I ≈ III
15.
CH3
⊕ CH3
Rearrangement in this carbocation predominantly leads to
(a) (b)
⊕ ⊕
C CH3 CH3
CH3
CH3
(c) both a and b (d) none of these
SOLUTIONS
4. (c) 5. (c) 6. (c) 7. (b) 8. (c) 9. (a) 10. (d) 11. (d)
12. (a) 13. (a) 14. (c) 15. (a)
CARBANIONS
Carbanions are unions of carbon which are obtained by the removal of one of the groups attached to the carbon
leaving behind the bonding electrons on it. Thus organic species carrying negative charge on one of the carbon atoms is
called a carbanion. In contrast to carbocations in which the positively charged carbon atom has six electrons, in these
anions the negatively charged carbon atom has eight electrons (6 bonding and 2 non-bonding). These ions are also short
lived highly reactive species. Their reactivity is believed to be due to the presence of the formal negative charge on carbon
atom.
Classification
Alkyl carbanions are classified into three categories, i.e., primary (l°), secondary (2°) and tertiary (3°) depending
upon whether the anionic carbon is primary, secondary or tertiary. Methyl carbanion with one carbon atom is a special
case, e.g.,
H3C
CH H3C C CH3
CH3 CH3 CH2 H3C CH3
Methyl carbanion Ethyl carbanion (1°) iso-Propyl teri-Butyl
carbanion (2°) carbanion (3°)
Structure
Depending upon their nature and source from which they are formed, the carbanions can have any one of the following
two geometries:
(i) Pyramidal
(ii) Planar
(i) Pyramidal: Simple alkyl carbanions possess one unshared pair of electrons and three pairs of bonding
electrons around the central carbon atom which is sp3-hybridized. Thus, it is expected that a carbanion
would have tetrahedral structure with unshared pair of electrons occupying one apex of the tetrahedron.
Actually, they have been shown to have pyramidal structure similar to ammonia or amines with which they are
isoelectronic.
Unshared pair of electrons

sp3-orbital
C sp3-hybridized N
carbon
R R′ R″ H H H
(Isoelectronic with NH3) Pyramidal
Pyramidal Structure of Carbanion and ammonia
The pyramidal structure of carbanion can be explained on the basis of the fact that it possesses one pair of non-
bonding electrons and three pairs of bonding electrons. Due to non-bonding—bonding repulsions, which are greater
than bonding-bonding repulsions, there is a reduction of bond angles between bonding pairs to a value which is
lesser than the tetrahedral value of 109.5°. Hence, the simple carbanions such as methyl anion are pyramidal, (with
bond angles between 97°-100°), like ammonia with which they are isoelectronic. If this is the picture of a carbanion,
then a carbanion in which three groups are different (R, R” and R’ in figure above) should be chiral and any reaction
in which such a carbanion is an intermediate should proceed with retention of configuration. However, it has been
shown that the reaction involving such anions results in loss of optical activity, i.e., they produce racemic mixture.
(For detail of ‘optical activity’ see ‘isomerism’)
Θ
Reason for loss of optical activity in reactions involving carbanions of the type ( C RR’R’).
In order to explain the above observation, it has been proposed that the unshared pair and the central carbon atom
rapidly oscillate from one side of the plane to the other, i.e., the two enantiomeric pyramidal structures are in a state
of rapid equilibrium due to which there is a loss of optical activity.
R R
R′ C C R′
R″ R″
(ii) Planar: Resonance stabilized carbanions, in which the orbital containing unshared pair of electrons overlaps with
the p-orbital of the neighbouring multiple bond, are essentially planar. This is due to the feet that planarity is essential
for resonance to occur. Thus, in this type of carbanions the anionic carbon is sp2-hybridized. For example,
R′ R″ R′ R″ R′ R″
–H
R C C O R C C O R C C O
H
sp2 sp2
Resonance stabilized;essentially planar
Similarly, allyl anion is also resonance stabilized.
CH2 CH CH2 H2C CH CH2
The following molecular orbital depiction of the above type of overlaping makes this concept more clear:
H
H
C C
H C–
H H
All carbon atoms are Sp2 – hybridized. Hence, the anion is planar.
It has been shown that if this type of anions are generated on a chiral carbon atom, there is a loss of optical activity.
The reason for this is that the chirality of anionic carbon is destroyed by the formation of a carbon-carbon double bond.
In conclusion, it may be said that the carbon atom of an unconjugated carbanion is, sp3-hybridized and it has a pyra-
midal structure. On the other hand, in a resonance stabilized carbanion the carbon is sp2-hybridized and the anion is es-
sentially planar. In both cases, there is a loss of optical activity in those reactions which involve optically active reactants.
Stability
Generally speaking carbanions are stabilized by dispersal of negative charge on the neighbouring atoms or groups. Main
factors which stabilize carbanions are as follows:
(a) Inductive effect
(b) Resonance effect
(c) Increase in s-character of carbanionic carbon
(d) Aromatization
(a) Inductive effect: As expected electron-withdrawing groups (–I-effect) stabilize the carbanions by dispersal of
negative charge, whereas electron-donating groups (+I-effect) destabilize them by intensifying the negative charge.
For example,
Θ Θ
(i) The anions C F3 and C (CF3)3 are quite stable, the latter being more stable due to-I-effect of highly electronegative
F atoms (3 in first case and 9 in the second case)
F F F
F C F C C C F
F FF C FF
Less stable
(3 F atoms)
F
More stable
(9 F atoms)
(ii) The order of stability of simple alkyl anions is as follows:
CH3 > H3C CH2 > H3C CH > H3C C CH3
CH3 CH3
This is due to the intensification of negative charge on anionic carbon by +I-effect of methyl groups. Here, it may be
mentioned that the above order of carbanion stability is just the reverse of carbocation stability.
(b) Resonance effect: If a multiple bond (say C = C, C = O, NO2, C = N, etc.) is located a-to the anionic carbon, it stabilizes
the anion by resonance involving dispersal of charge. Some examples of resonance stabilized carbanions are:
(i) Alkyl and benzyl anions: They are stabilized by dispersal of negative charge due to resonance as depicted below.
CH2 CH CH2 CH2 CH CH2

Allyl anion (resonance stabilized)
CH2 CH2 CH2 CH2
Benzyl anion (Resonance stabilized)

Effect of substituents on resonance stabilized carbanions: The presence of electron donating groups (such as
alkyl, OH, NH2 having +R-effect) at o-and p-position of the ring with respect to anionic centre results in destabi-
lization of the anion as they intensify negative charge on anionic carbon. Whereas electron withdrawing groups
(such as—NO2, CHO, COR, COOH, COOR, etc.) on o-and p-position of the ring with respect to anionic centre
stabilize the anion by –R-effect. Thus, decreasing order of stability of p-nitrobenzyl, benzyl and p-methoxy benzyl
anion is
O2N CH2 > CH2 > CH3O CH2
Here, it may be mentioned that the order of stability of carbanions is the reverse of the stability of carbocations.
The resonance stabilization of benzyl anion suggests that the greater is the number of benzene rings attached to
the anionic carbon, the stabler is the anion. Thus diphenylmethyl anion is more stable than benzyl anion and tri-
phenylmethyl anion is more stable than diphenylmethyl anion. This is due to increasing number of resonance
structures.
Diphenylmethyl anion
CH CH CH CH etc.
Three more contributing forms
Triphenyl Methyl anion

It is more stable than diphenylmethyl anion due to larger number resonating forms.
C C C C etc.
Six more contributing forms
(ii) Anion derived from nitromethane
⊕ O ⊕ O
H 2C N H2C N
O O
(iii) Enolate anion derived from acetoacetic ester
O O O O
H3C C CH C OC2H5 H3C C CH C–OC2H5
O O
H3C C CH C OC2H5
(iv) Etiolate ion of acetaldehyde

O O
CH2 C H CH2 C H
It is due to increase in stability of anions due to resonance that diphenylmethane (pKa 33.5), triphenylmethane (pKa
31.5), acetaldehyde (pKa 16. 0), nitromethane (10. 0) and ethylacetate (pKa 9. 0) are acidic in nature.
(c) Increase in s-character of the carbanionic centre: Another factor which contributes to the stability of carbanions is
s-character of the orbitals of anionic carbon. The observed carbanion stability, in decreasing order is as follows:
Highest stability of acetylide anion is attributed to the fact that in acetylide ion the electron pair occupies sp orbital
and hence is less available for combining with acids as compared to electron pair or sp2 or s-p3 hybrid orbitals which
have more p-character. This is the reason why terminal alkynes (pKa 25) are stronger acids than alkenes (pKa 43) or
alkanes (pKa 50).
(d) Aromatization: Cyclopentadiene readily loses a proton (pKa 16) to form cyclopentadienyl anion which is quite stable
(Resonance energy = 130 kJ mol–1 compared to 151 kJ mol–1 for benzene).
CH3O
Stable
H H H
High stability of this anion is due to the fact that it constitutes an aromatic system having 4q + 2p-electrons
(4 from two double bonds and 2 from non-bonding pair).
Stability of different types of carbanions in decreasing order:
⊝
aromatic carbanion (the ring becomes aromatic when the carbanion is formed) H – C ≡ C > Benzyl anion > Allylanion >
⊝ R R
H2C = C– H > Alkyl carbanion ( CH > R – CH > CH > R C )
3 2
R R
Formation: As there is little difference between the electro negativities of carbon and hydrogen (2.5 and 2.1, respectively)
the polarity of the C—H bond is very small. The heterolytic fission of this covalent bond to form an anion and a proton should
then be a very difficult process. In other words, a hydrogen atom bound to an sp3 carbon atom shows negligible acidity.
However, the presence of electron attracting substituents such as nitro, cyano or carbonyl groups on the same carbon renders
the hydrogen relatively acidic. The increase in acidity is not only due to the electron-withdrawing ability of these substituents,
but also due to their ability to delocalize the negative charge of the anion. Thus hydrogens on the carbon atom alpha to nitro,
cyano or carbonyl groups have acidic character and can be removed as protons leaving resonance stabilized anions.
O O O
– H⊕
H3C N H2C N H2C N
O O O
– H⊕ –
CH 3 — C ≡ N ]CH2 — C ≡ N CH2 = C = N ]
O O O
H3C C H – H⊕
H2C C H H2C C H
Carbanions are also formed when a nucleophile adds to a carbon-carbon double bond.
C 2 H 5OCH 2 — CH — C ≡ N
C2 H 5O + CH 2 = CH — C ≡ N
C 2 H 5OCH 2 — C = C = N
Stability: As we have already seen, carbanions are stabilized by electron-withdrawing substitutents. Generally speaking,
a carbanion is stabilized by resonance if a double bond is located α to the anionic carbon. This explains the stability of
the allyic and benzylic carbanions.
R CH CH CH2 R CH CH CH2
CH2 CH2 CH2 CH2
Ready conversion of triphenylmethane to the triphenylmethyl carbanion can be similarly explained.

Na
(C6 H 5 )3 CH (C6 H 5 )3 CΘ : Na ⊕
(C6H5)2 C (C6H5)2 C etc
The order of stability of the simple carbanions is:

methyl > primary > secondary > tertiary
Another factor that contributes to the stability of carbanions is the extent of s-character of the bonding orbitals of the
carbanionic carbon. Carbanion stability, thus, has been found to be in the order: RC ≡ CΘ > R 2 C = CH Θ > R 3 C − CH Θ2 .
We have already seen that the carbon atom in acetylene is sp hybridized (50% s character) and hence hydrogen atom at-
tached to it should be more acidic than that of ethylene where the carbon is sp2 hybridized (33% s character).
An interesting example is cyclopentadiene which readily loses a proton to form the cyclolpentadienyl anion.
CH3O –
≡
H H
H H
The unusual stability of cyclopentadienyl anion is explained by the fact that althought it has only four p electrons, two
more electrons become available to it by the heterolysis of the C—H bond thus forming a system of six electrons. These
electrons are spread over all the five carbon atoms like the delocalized aromatic system of benzene ring, thus conferring
on it stability so characteristic of the aromatic compounds.
Carbanions and their reactions
It is also possible to add two electrons to the non-planar, non-aromatic cyclooctatetrane (17) by treating it with potassium,
thereby converting it into the isolable, crystalline salt of the cyclooctatetraenyl dianion (18):
2K
2
(17)
(18)
This too is a Huckel 4n + 2 p electron system (n = 2, this time) and shows quasi-aromatic stability; stabilisation by
aromatisation has again taken place, remarkably this time in a doubly charged carbanions (18).
Illustrations
46. Give the relative order of solubility of carbanions. CH 3– , CH 3CH 2– , CH 3CH – CH 3 ,(CH 3 )3 C –
Ans. The decreasing order is

CH 3– > CH 3CH 2– > CH 3CH – CH 3 > (CH 3 )3 C – . The order is opposite to that proposed for cations +I effect of
alkyl group increases the –ve charge on C.
Electron releasing groups destabilize anions.
O O
|| ||
47. Why CH 3 – C– CH 2 – C – CH 3 is known as active methylene compound?
Ans. The – CH2 – group (methylene group) is acidic in nature, i.e., these hydrogens can be easily lost as H+, on action
of a base because the resulting carbanion can be resonance stabilized.
2 2
__ __

&+ ± &±&+± & ±&+
2± 2
__
&+ ±& &+± & ±&+
2 2
__

&+ ± & ±&+ &±&+ Ł
± į
±
2 į 2
&+ ±& ±±±± &+±±±± & ±&+
CH2
16. CH3 – CH2 CH2 = CH – CH2
I II
III
Which of the following orders is correct for the stability of these carbanions?
(a) I > II > III (b) III > II > I (c) II > III > I (d) II > I > III
CH2 CH2
CH2
17.
NO2
NO2 NO2
I II III
(a) I > II > III (b) III > II > I (c) II > I > III (d) II > III > I
18. CH CH CH2 CH HC ≡ C
3 2
I II III
(a) I > II > III (b) III > II > I (c) II > I > III (d) III > I > II
19. CH2 CH CH2

I II III
(a) I > II > III (b) III > II > I (c) I > III > II (d) II > III > I
O OO O
20. O O
I II III
Which of these carbanions is sp3 hybridized?
(a) I (b) II (c) III (d) none of these
NO2 NO2 NO2
21.
I II III
(a) I > II > III (b) III > II > I (c) II > III > I (d) II > I > III
SOLUTIONS
16. (b) 17. (c) 18. (b) 19. (b) 20. (c) 21. (d)
Carbanion Formation
The most general method of forming carbanions is by removal of an atom or group X from carbon, X leaving its bonding
electron pair behind:
R3C – X + Y ⇄ R3C⊖ + XY⊕
By far the most common leaving group is X = H where, as above, it is a proton that is removed.
Some important methods of their formation are:
(i) Abstraction of hydrogens attached to the carbon atoms alpha to nitro, cyano or carbonyl groups with a strong base.
For example,
(ii) Abstraction of hydrogen from terminal alkynes using a strong base.
H2N + H C CH C CH + NH3
Amide ion Acetylene
(Stronger base)
Other leaving groups are also known, e.g., CO-from the decarboxylation of RCO2Θ (3), or ClΘ from Ph3C—Cl to
yield the blood-red, ether soluble salt (4):
∆
R C O R + CO2
O
(3)
Na/Hg
Ph3C Cl Ph3C Na⊕
(4)
Hardly surprisingly, the tendency of alkanes to lose proton and form carbanions is not marked, as they possess no
structural features that either promote acidity in their H atoms, or are calculated to stabilise the carbanion with respect to
the undissociated alkane. Thus CH4 has been estimated to have a pKa value of ≈ 43, compared with 4.76 for MeCO2H. The
usual methods for determining pKa do not, of course, work so far down the acidity scale as this, and these estimates have
been obtained from measurements on the iodide/organometallic equilibria.
RM + R′I RI + R′M
The assumption is made that the stronger is an acid, RH, the greater will be the proportion of it in the form RM (e.g.,
M = Li) rather than as RI. Determination of the equilibrium constant K allows a measure of the relative acidity of RH and
R’H, and by suitable choice of pairs it is possible to ascend the pKa scale until direct comparison can be made with an RH
compound whose pKa has been determined by other means.
Thus Ph3C—H (5) is found to have a pKa value of 33, i.e., it is a very much stronger acid than CH4, and the carbanion
(4) may be obtained from it, preparatively, by the action of sodamide, i.e., ΘNH2, in liquid ammonia.
hq
Ph3C H + Na⊕ NH2 Ph3C Na⊕+ NH3
NH3
Addition of nucleophiles to a, b-unsaturated compound leads to carbanion formation.
H5C2OCH2 CH C N
C2H5O + CH2 CH C N
Ethoxide ion Vinyl cyanide
H5C2OCH2 CH C N
Resonance stabilized anion
Carbanion configuration
O O O O
O H O
H H H H
(20) (21) (22)
The H atom flanked by the two C=O groups (in 22) exhibits hardly any more acidic character than the analogous one in the
corresponding hydrocarbon. The different behaviour of (22) stems from the fact that after proton removal, the carbanions’s
lone pair would be in an sp3 orbital more or less at right angles to the p orbitals on each of the adjacent carbonyl carbon
atoms: no sp3/p overlap could thus take place, consequently there would be no stabilization of the -ve charge through
delocalization, and the (unstabilised) carbanion does not, therefore, form.
Reactions of carbanions
Carbanions undergo three basic types of reactions as follows:
(a) Combination with an electrophile
(b) Nucleophilic substitution and addition
(c) Rearrangements
(a) Combination with an electrophile: The most common reaction of carbanions is combination with a positive species
(electrophile) usually a proton.
O O
⊕
R C CH2 + E R C CH2 E
(b) Nucleophilic substitution and addition: (i) Carbanions may act as nucleophiles and push out one of the four groups
on a saturated carbon atom (SN2 reactions).
H H
–Br
HC C + H3C C Br HC C C CH3
H H
(ii) Carbanions frequently add to the carbonyl double bond (aldol condensation).
O O
⊕
–H
CH3 C H CH2 C H
O O O O
CH3 C H + CH2 C H CH3 C CH2 C H
H
H2O
OH O
CH3 C CH2 C H
H
(Aldol)
(c) Rearrangements: Carbanions also undergo rearrangement reactions, though they are rare, e.g.,
C 6H 5
C6H5 C CH2 C6H5 C CH2C6H5
C6H5 C6H5
FREE RADICALS
In addition to heterolytic cleavage of a covalent bond, which produces carbocations and carbanions rupture of this bond
may be homolytic, in which each of the two fragments possesses an unpaired electron.
X Y X+Y
These fragments carrying an odd or unpaired electron have no charge and are called free radicals.
Although free radicals are electrically neutral but due to the presence of an odd electron they are weakly attracted by the
magnetic field and hence are paramagnetic in nature. They are extremely reactive and yield a variety of products depending
upon the experimental conditions.
Classification of Free Radicals

Free radicals are classified as 1°, 2°, or 3° similar to carbocations
H 3C
CH3 H3CCH2 CH (CH3)3C
H 3C
Methyl 1° 2° 3°
Structure
There are two possible structures for simple alkyl radicals.
(i) Planar: A free radical may be a planar species in which the carbon atom bearing the odd electron is sp2-hybridized
(as in carbocation) and the odd electron remains in the p-orbital. The p-orbital containing this odd electron is always
perpendicular to the plane of sp2-carbon.
sp2-hybridized carbon
R
C p-orbital containing
upaired electron
120°
R′ R″
Planar structure of free radical
(ii) Pyramidal: Free radical can also aquire a shape resembling a shallow pyramid, which is neither planar nor tetrahedral
and the orbital containing unpaired electron is some sort of a hybrid between a. p and sp3-orbital.
R R
Fast
R′ C C R′
R″ (Rapid equilibrium between two pyramidal forms) R″

Pyramidal structure of free radical
The question as to whether free radicals exist in planar configuration or in a rapid equilibrium between the two
pyramidal forms is difficult to answer with certainty. However, available evidence indicates that the unpaired electron is in
a‘p’-orbital. Resonance stabilized free radicals certainly exist in planar configuration.
Some important points regarding carbon free radicals
(1) Carbon free radicals are odd electron species in which carbon atom bears the odd electron.
(2) Homolytic bond fission of a covalent single bond gives rise to free radicals.
(3) There are seven electrons in the out most orbit of carbon of carbon free radicals.
(4) Owing to the presence of an odd electron; a carbon radical is paramagnetic in nature. Due to this reason free radicals
are highly reactive.
(5) The structure of the carbon free radicals is very difficult to predict. They have planar to pyramidal geometry depend-
ing upon the groups and atoms attached to the carbon atom having odd electron. For example, methyl free radical is
planar. On the other hand trifluoro methyl free radicals is pyramidal. Alkyl free radicals have also pyramidal geometry.
(6) Free radicals are neutral electrophiles.
(7) Free radicals generally react with free radicals. All free radical reactions are chain reactions.
(8) Initial generation of free radical is difficult, but once a radical is generated, it can give rise to a number of radicals.
• •
(9) Radicals of alkylic R – CH – C H 2 and benzylic C6H5 C H 2 are more stable and less reactive than simple alkyl radicals
because of delocalisation of the unpaired electrons.
R– CH CH CH2 CH – R
•
Both are essentially planar with sp2 hybridisation, Ph3C (trityl) is highly stable radical. Rate of free radical reactions
depends on stability of free radicals.
Stability of free radicals
Similar to carbocations, the stability of free radicals can be explained on the basis of hyperconjugation, resonance and
steric factors.
1. Hyperconjugation: In general, it has been found that the stability of alkyl radicals is in the order: 3° > 2 > 1°. This is
due to the fact that in going from methyl to t-butyl, there is increasing tendency for electron release due to hyperconju-
gation. As we have seen that the carbon atom carrying an unpaired electron has a half-filled orbital that gives the radical
its characteristic instability; the hyperconjugative mechanisms tend to fill this orbital and thus stabilize the radical to
some extent. Various hyperconjugative contributing forms of ten-butyl radical, for example, are given below.
CH3 CH2 H CH3
C C C etc.
H 3C CH3 H 3C CH3 H3C CH2 H
2. Resonance: Allyl, benzyl, diphenylmethyl and triphenylmethyl radicals are particularly stable because of resonance
involving p-electrons of the double bond or aromatic ring.
CH2 CH CH2 CH2 CH CH2

(Resonance forms of allyl radical)
CH2 CH2 CH2 CH2 CH2
(Resonance structures of benzyl radical)

Four more
CH CH CH such resonating
structures
(Resonance structures of diphenylmethyl radical)
Triphenylmethyl free radical is still more stable due to larger number of resonating structures.
Six more
such
C C C C resonating
structures
(Resonance structures of triphenylmethyl radical)
•
The free radicals having the odd electron on a doubly bonded carbon atom such as vinyl (CH2 = CH) or phenyl
•
(C6 H 5 ) radicals, cannot be stabilized by hyperconjugation or by resonance and hence are usually highly reactive.
These radicals are even less stable than methyl free radical.
3. Steric factor: Another factor that is responsible for the increased stability of tertiary radicals may be steric. Formation
of a tert-butyl radical by removal of a hydrogen atom from iso-butane, (CH3)3CH, is favoured as the steric repulsion
between the methyl groups is relieved to a certain extent by an increase in bond angles from 109.5° to about 120°.
Clearly this steric relief should be the greatest in the formation of tertiary free radicals (cf. stability of carbocations).
Relative stability
On the basis of all the above factors, we conclude that the order of relative stability of different free radicals follows the
sequence: Benzyl > Allyl > f-Butyl > iso-Propyl > Ethyl > Methyl > Phenyl > Vinyl.
Stability of different free radicals in decreasing order:
(C6H5)3 C > (C6H5)2 CH > C6H5 CH2 > CH2 CH C CH3 >
CH3
CH2 CH CH CH3 > CH2 CH CH2 > Ter alkyl free radical
> See alkyl free radical > P-alkyl free radical > CH3
(8) Stability of the same type of alkyl free radical (=) Number of carbons in alkyl free radical.
(9) Rearrangement takes place in primary-free radical in a chemical reaction. There are two possible structures for
simple alkyl radicals. Either a free radical may be a planar species (A) in which the carbon atom bearing the odd electron
in sp2 hybridized (as in carbocations) and the odd electron remains in the p-orbital, or it could have a shape resembling a
shallow pyramid (B) which is neither planar nor tetrahedral and the orbital containing unpaired electron is some sort of a
hybrid between a p and an sp3 orbital.
R' R" R R
fast
C or R' C C R'
R" R"
R
(A) (B)
Formation of free radicals

Free radicals are often produced when a molecule is supplied with sufficient energy—thermal, photochemical or
electrochemical—to cause homolysis of a covalent bond. Free radical are also produced in redox reactions. Some typical
reactions producing free radicals are given below.
(a) Thermolytic cleavage (pyrolysis): Any organic molecule, when heated at high temperature in the gas phase, produces
free radicals. Some examples are as follows:
(i) Thermolysis of tetramethyl lead.
(ii) Thermolysis of azo compounds.
(iii) Thermolysis of aryl peroxides
O O O
∆
C6H5 C O O C C6H5 2C6H5 C O 2 C6H5 + 2CO2
Benzoyl peroxide Benzoyloxy radical Phenyl radical
(b) Photolytic cleavage: The energy content of light ranging from 600–300 nm is 200–400 kJ mol–1. This is sufficient to
cleave a covalent bond in hemolytic manner to produce free radicals. Some typical example are as follows:
(i) Photolysis of halogens
•
hν
Cl − Cl 2 Cl
(ii) Photolytic of ketones
• •
hν
CH 3COCH3 C H3 + CH3 C O
Acetyl radical
• •
CH 3 C O C H 3 + CO
(iii) Photolysis of azo compounds
hν •
H3C – N = N – CH3 2 C H3 + N2
(iv) Photolysis of aryl peroxides
O O O
C6H5 C O O C C6H5 hv C6H5 C O

O
C6H5 C O hv C6H5 + CO2
(c) Electrolytic cleavage (Kolbe’s electrolysis):

O O
at anode
R C O R C O R + CO2
–e
(d) Redox reactions: These reactions, involving single electron transfer, are known to generate from radicals. These
reactions involve metal ions such as Fe2+/Fe3+ and Cu+/Cu2+. Some examples are
(i) Decomposition of aryl peroxides
O O O O
Ar C O O C Ar + Cu+ Ar C O + Cu2+ + Ar C O
Acyloxy free radical Acyloxy anion
(ii) Sandmeyer reaction

The Cu+ ion is also involved in generation of aryl radicals from arenediazonium salts.
⊕
Ar − N ≡ N + Cu+ Ar• + N2 + Cu2+
(iii) Auto-oxidation
Auto-oxidation of benzaldehyde, is catalyzed by Fe +
O O
⊕
C6H5 C H + Fe3+ C6H5 C + H + Fe2+
Reactions
Reactions of free radicals frequently yield stable products by a process called termination reaction. Some typical reactions
of free radicals are as follows:
(a) Addition reactions
(b) Substitution reactions
(c) Disproportionation reactions
(d) Rearrangements.
(a) Addition reactions: (i) Free radicals, being electrophilic in nature add to a carbon-carbon double bond forming
another radical.
5& & 5±&±&
The radical formed above may add to another double bond and this may continue further. This is one of the main
routes of vinyl polymerisation.
(ii) The most celebrated example of free radical addition is the abnormal addition of hydrogen bromide to olefins
which takes place in the following steps:
H hv H + Br
Br
H — Br
CH3 CH CH2 + Br CH3 CH CH2Br CH3CH2 Br + Br
Propene
(b) Substitution reactions: (i) In aliphatic compounds, e.g., halogenation of alkanes takes place by free radical chain
mechanism taking place in three stages as under with example of chlorinatioc of methane.
Chain Initiation
hν
Cl – Cl
Chain Propagation
• •
CH 4 + C l CH 3 + HCl
• •
CH 3 + Cl − Cl CH 3Cl + C l
Chain Termination
Cl + Cl Cl Cl
CH3 + Cl CH3 Cl
CH3 + CH3 CH3 CH3
(ii) In aromatic compounds

H R R
R
+R +R H
Slow Fast
(c) Disproportionation reactions: Two free radicals may react with each other in such a way that one is transformed to
alkane and other to alkene.
• •
CH 3 − C H 2 + CH3 – C H 2 CH2 – CH3 + CH2 = CH2
(d) Rearrangements: Less stable radicals attain stability by a 1, 2 shift of an alkyl/aryl radical to îve more stable radical.
R
R C CH2 R C CH2 R
R R
Although a primary radical may sometimes produce a tertiary radical by the migration of a substituent from the neigh-
bouring carbon atom, in practice radical rearrangements have been found to be distinctly less common than carbocation
rearrangements. This diminished tendency for rearrangements is due to the fact that the difference in stability between a
primary and a tertiary radical is not as much as that between a primary and a tertiary carbocation.
22. CH2 = CH – CH2 CH3 – CH2
I II
CH3
CH3 – C
CH3
III
Which of the following orders is correct for the stability of these radicals?
(c) I > III > II (d) III > I > II
CH3 CH3 CH3
23.
CH3 CH3 CH3
Which of the following orders is correct for the stability of these radicals?
(c) II > I > III (d) I > III > II
H
24. I II
H
Which of the following orders is correct for the energy required for hemolytic cleavage of indicated
C-H bonds?
OCH3 OCH3 NO2
25. I II III
CH2 – Cl CH2 – Cl CH2 – Cl
Which of the following orders is correct for the energy required for heterolytic cleavage of indicated
C-Cl bonds producing carbocations?
(c) III > I > II (d) II > I > III
SOLUTIONS
22. (c) 23. (c) 24. (c) 25. (b)
Illustration
48. Identify the 1-2 and 1-4 addition products of free radical addition of CBrCl3 to 1,3-butadiene.
Ans. CH 2=CH–CH=CH2 • CCl 3

Cl3 C–CH2 –CH–CH=CH2
Br (I)
Cl3C–CH 2 –CH–CH=CH2 Cl3 C–CH2–CH=CH–CH2

Br
Br
1,2 addition product Cl3 C–CH2 –CH=CH–CH 2 Br
1,4 addition product
CARBENES
Carbenes can be defined as neutral, bivalent carbon intermediates in which a carbon is covalently bonded to two atoms
and has two non-bonding orbitals containing two electrons between them. These are also called methylenes, e.g., :CH2
(methylene) and :CC12 (dichlorocarbene or dichloromethylene).
Types of Carbenes
Theoretical considerations suggest that there are two possible kinds of carbenes.
(i) Singlet carbene
(ii) Triplet carbene
In the singlet carbene, a carbon atom is presumed to approximate sp2-hybridization. Two of the three sp2 hybrid
orbitals are utilized in forming two covalent bonds whereas the third hybrid orbital contains the unshared pair of electrons.
The unhybridized p-orbital remains vacant. Thus, singlet carbene resembles a carbocation very closely and is represented
as CH2 (figure below). The two electrons have opposite spins in singlet carbene.
empty p-orbital
R
C
sp2-hybridized
R′ orbital
Structure of singlet carbene
On the other hand, carbon atom of a triplet carbene is sp-hybridized and it is a linear or nonlinear species. These two
hybrid orbitals are involved in the bond formation with two groups, and the two electrons are placed, one each, in the
equivalent, mutually perpendicular pv and pz orbitals. Since these electrons have parallel spins, a carbene with this structure
is said to be in a triplet state and represented as CH2 (see figure below).
R1 One electron in
each p-orbital
C
sp-hybridized carbon
R
Structure of triplet carbene
Stability of carbenes
At the first sight, it appears that a singlet carbene has lower energy as the unshared electron pair is in a sp2 hybrid orbital;
but the consideration of the electron pair repulsion energy, which must be overcome to place two electrons in a single
orbital put it at the higher energy level than a triplet structure. It is, therefore, resonable to believe that the triplet state of a
carbene is more stable than singlet state and should be expected to be the ground state. This is supported by the observa-
tion that triplet methylene is about 35.5 kJ mol–1 more stable than the singlet methylene.
Carbenes in which the carbene carbon atom is attached to two atoms, each bearing an unshared pair of electrons, are
somewhat more stable due to resonance.
R2N R2N R 2N
C C C
R2N R2N R2N
The decreasing order of stability of different types of singlet carbenes are as follows:
ii ii ii ii
CH 2 > CF2 > CCl2 > CBr2
Formation of carbenes
Some of the important reactions generating carbenes are as follows:
1. α-Elimination: a-Elimination is a reaction involving first a loss of group without its lone pair (usually a proton),
which is followed by loss of an anion usually a halide ion. Some examples of a-elimination are:
(a) From chloroform
Cl Cl
Base –Cl
H C Cl ⊕ C Cl CCl2
–H
Dichlorocarbene
Cl Cl
(b) From sodium salt of trichloroacetic acid
∆ Θ
Cl3C – COOΘ :CCl2 + CO2 + Cl
2. Photochemical or thermal cleavage of three membered rings
(a)
(b)
3. Decomposition of certain compounds having multiple bonds

Compounds such as ketenes, diazoalkanes and diazirines on decomposition give rise to carbenes. For example,
hv ⊕
(a) H2C C O CH2 + C O
Ketene
(b)
N
(c) R2C R 2C + N N
N
Diazirine
(Isomeric with diazomethane)
Reactions
Carbenes are highly reactive electrophilic species. They undergo the following reactions:
(a) Cycloadditions
(b) Insertion reactions
(c) Rearrangements
(a) Cycloadditions: Carbenes readily add to olefinic double bond to form cyclopropane derivatives. Their reactivity is
reflected in the fact that they even add to aromatic systems. In latter cases, the products (norcaradiene derivatives)
undergo ring expansion.
H H
R C R
R2C CR2 + CH2 C C
R R
Ring
+ CH2 CH2
Expansion
Norcaradiene Cycloheptatriene
(Unstable) (Stable)
(b) Insertion reactions: Carbenes (in singlet state) are so reactive that they even insert themselves into s C — H
bonds.
H H
R C H + CH2 R C CH2 H
H Singlet carbene H
These reactions are synthetically useless but are important because they reflect their extreme reactivity.
However, triplet carbenes abstract hydrogen or other atoms to produce radicals which couple to give products.
CH2 + CH3CH3 CH2 + CH2CH3 CH3CH2CH3

Triplet carbene
(c) Rearrangements: Alkyl carbenes can undergo rearrangements involving 1, 2-shift of hydrogen or alkyl group.
CH3 CH2 CH CH CH3 CH2 CH CH2
R C CH R CH C O
Acylcarbene Ketene
Unlike other rearrangements, most of the carbene rearrangements give rise to stable products.
When a carbene is generated in a three membered ring, allenes are formed by rearrangement. However, a similar
formation at a cyclopropylmethyl carbon gives ring expansion. Carbenes are also involved in Reimer —Tiemann reac-
tion.
Carbene CH 2
electrocylic
rearrangement
benzene norcaradiene cycloheptatriene

intermediate
26. A singlet carbine is
(a) unhybridized (b) dp3-hybridized
(c) sp2-hybridized (d) sp-hybridized
27. A triplet carbine is

(a) unhybridized (b) sp3-hybridized
(c) sp2-hybridized (d) sp-hybridized
28. In singlet carbine CH2, bond angle is

(a) 120o (b) less than 130o
(c) 180o (d) more than 120o
29. In triplet carbine C H2, bond angle is
(a) 120o (b) les than 180o

(c) more than 120 and less than 180 (d) 180o
o o
30. Which of the following carbenes is more stable?
(a) CH2 (singlet) (b) CH2(triplet )
(c) both are equally stable (d) stability of carbenes is unpredictable

31. Which of the following difluorocarbenes is more stable?
(a) CF2 (singlet) (b) CF2(triplet )
(c) both are equally stable (d) stability of carbenes is unpredictable
32. Which of the following statements is most suitable about singlet difluorocarbene (:CF2)?
(a) It has an empty 2p-orbital on carbon atom
(b) It has a lone-pair of electrons in a 2p-orbital on fluorine atoms.
(c) Due to a and b resonance involving electron-donation from F to C becomes possible as
⊕
F C F C F C
F F F ⊕
(d) Factors a, b andc combined together makes CF2 (singlet) more stable than CF2(triplet).
33. Which of the following singlet carbenes is most stable?
(a) CF2 (b) CCl2
(c) CBr2 (d) CI2

34. Which of the following reactions generating carbine intermediates is correct?

(a) CHCl3 KOH/Δ :CCl2 + KCl + H2O
O
|| − +
(b) CCl 3 – C – O Na Δ :CCl2 + CO 2 + NaCl
(c) both a and b
(d) none of these
35. Which of the following reactions generating carbene intermediates is correct?
(a) CH2N2 ∆ :CH 2 + N2 (b) CH 2 = C = O ∆ :CH2 + CO
(Ketene)
(c) both a and b (d) none of these
SOLUTIONS
26. (c) 27. (d) 28. (b) 29. (c) 30. (b) 31. (a) 32. (d) 33. (a)
34. (c) 35. (c)
ARYNES
Arynes may be defined as aromatic compounds containing a formal carbon-carbon triplet bond. The best known aryne
is benzyne which may be regarded as the aromatic counterparts of acetylene, or in other words, it is benzene minus two
ortho hydrogens and can also be called as dehydrobenzene. In benzyne, the newly formed p-bond is very weak and hence
benzyne is a highly reactive molecule.
Benzyne
or
Dehydrobenzene
Structure
The benzyne bond is not like the triple bond of acetylene where the two carbons form a s-bond using sp-orbitals and the
remaining p-orbital are used to form two mutually perpendicular p-bonds. Such a structure is not possible in benzyne
because of the hexagonal geometry associated with the benzene ring. Most probably, the new bond of benzyne is formed
by the ‘overlap’ of sp2-orbitals belonging to two neighbouring carbon atoms.
These sp2-orbitals are orthogonal to the p-molecular orbital of the benzene ring, i.e., the triple bond in benzyne consists
of one sp2-sp2 s-bond, one p-bond formed by sideways overlap of two unhybridized p-orbitals and another p-bond by
sp2-sp2 overlap.
Stability: The new bond of benzyne, formed by the overlap of sp2-orbitals belonging to two neighbouring carbon atoms is
very weak, and therefore, arynes are extremely reactive chemical species.
Detection: Arynes are usually detected either through spectroscopy or by their participation in such reactions as dimeriza-
tion and by trapping through cycloaddition to substances such as furan.
Dimerization
(Self trapping)
Biphenylene
O
Diels-Alder
+ O
reaction
Formation of arynes
1. By the action of strong bases on halo hen/cries: Benzyne has been shown to be intermediate in several important
organic reactions. For example, in the presence of strong base, aryl halides eliminate HX from 1, 2-positions to
produce benzyne, which then rapidly reacts with the available nucleophile to regenerate the aromatic system. For
example, treatment of bromobenzene with sodamide gives aniline.
Br
+ NH2 + NH3 + Br (Elimination step)
H
NH2 NH2
+ NH2
NH3 (Addition step)
The above mechanism is called elimination-addition mechanism.

Similarly, the intermediacy of benzyne in the Dow’s method for industrial production of phenol from chlorobenzene
and strong alkali has clearly been demonstrated by using (1-14C) chlorobenzene.
(2-14C) phenol
H2O
Cl
OH
623 K
+ NaOH
H OH
H2O
(2-14C) phenol
2. Thermal method: A convenient procedure for generating benzyne consists of heating benediazonium 2-carboxylate.
⊕
NH2 N N
HNO2 –N2 ⊕ –CO2
–2H2O
COOH C—O C—O
Anthranilic acid O O
Benzenediazonium-2-carboxylate
Reactions: In addition to dimerization reaction, benzyne reacts with olefins and dienes to yield different types of products.
Some important reactions of benzyne are:
(a) Cycloaddition reactions

(b) Nucleophilic addition reactions
(a) Cycloaddition reactions: Benzyne reacts with both olefins and conjugated dienes to produce of products, e.g.,
CN
(i) + CH2 CHCN
(ii) +
Triptycene
(iii) +
(b) Nucleophilic addition reactions: Benzene undergoes nucleophilic addition with a variety of nucleophilies.
NHR OH
RNH2 H 2O
(i)
–H⊕ –H⊕
(ii) +
NITRENES
Nitrenes are uni valent neutral nitrogen species having a sextet of electrons on nitrogen. Out of these six electrons four
are present as two pairs of non-bonding electrons and two electrons are used for bonding with a monovalent atom or
group. They can be said to be nitrogen analogs of carbenes. Like carbenes, they are also short-lived highly reactive
chemical species. Thus, like carbenes, they also behave as electrophiles (Lewis acids) and are intermediates in many
organic reactions. They are represented by formula.
•• ••
R−N (cf R – R−C – R)
••
Structure of nitrenes
Like carbenes, these intermediates also exist in two states, viz; singlet and triplet. These states are depicted below:
R N ( ) R N ( ) or R N
Singlet Triplet
In singlet nitrene, the nitrogen is sp2-hybridized. Out of three sp2-hybridized orbitals, one having single electron,
is utilized in s-bond formation with a monovalent atom or group, and the remaining two are occupied by two pairs of
electrons. An unhybridized p-orbital is empty and this is responsible for their electrophilic character. On the other hand,
in triplet nitrene, the nitrogen is sp-hybridized. Out of two sp-hybrid orbitals, one having single electron is used in s-bond
formation and the other is occupied by a pair of electrons. The two unhybridized p-orbitals are occupied by one electron
each. The orbital picture of both the species is as follows:
Empty p-orbital p-orbital
R σ
N sp2-hybridized σ sp-hybridized
R N
orbitals orbital
Singlet Triplet
Generation
Following methods of generation of nitrenes are analogous to those used for generation of carbenes:
1. a-Elimination: Treatment of hydroxylamine-O-sulphonates results with alkali in the formation of nitrenes by the
elimination of sulphonic acid group from nitrogen.
H OH
R N R N + H2O + ArSO3
OSO2Ar
2. Decomposition of azides: Azides eliminate nitrogen either on heating or irradiating with light to produce nitrenes.
⊕ ⊕ ∆ or hv
(i) R N N N R N N N R N + N2
O
⊕ ∆ or hv
(ii) N N N C OEt N2 + NCOOEt
Ethyl azidoformate Ethoxycarbonyl
nitrene
3. Decomposition of Isocynates
KYRU$
5±1 & 2 5±1& 2
Reactions
The chemical reactions of nitrenes closely resemble those of carbenes. Here it may be pointed out that many reactions
where a nitrene intermediate can be proposed may not involve free nitrene. So, it is not easy to conclude that a particular
reaction involves a nitrene intermediate or not. However, some of the reactions in which nitrenes may be intermediates are:
(a) Addition reactions

(b) Insertion reactions
(c) Rearrangements
(d) Abstraction of hydrogen
(e) Dimerization
(a) Addition reactions: Both singlet and triplet nitrenes add on to C = C bonds forming aziridines.
R′
R R R N R
C C + R′ N C C
R R R R
Aziridine
(b) Insertion reactions: Some nitenes, e.g., acyl nitrenes and sulphonyl nitrenes can insert into C–H or other sigma
bonds, e.g., formation of amides when acyl nitrene is generated in hydrocarbon solvent.
O O
R′ C N + R3CH R′ C N CR3
H
(c) Rearrangements: Alkyl nitrenes readily undergo rearrangement to give imines instead of undergoing the above two
reactions.
R CH N R CH NH
Imine
H
A typical example of a rearrangement: A reaction where a nitrene seems to be involved as an intermediate is Hoff-
mann rearrangement for which the following mechanism may be proposed.
Br2
Br
R C NH2 R C N OH R C N Br
NaOH
H
O O O
Amide N-Bromoamide
–Br
O
R — N == C == O R C N
Isocyanate
Acylnitrene
However, it may be pointed out here that a nitrene has not yet bean detected in this reaction. Hence, the following
concerted mechanism may be proposed.
O
R C N Br O C N R
(d) Abstraction of hydrogen: The triplet nitrenes (like triplet carbenes) are capable of abstracting a hydrogen atom from
a s C—H bond or other such group to form a pair of radicals which may couple.
H H
R N+R H R N +R R N+R
(e) Dimerisation: One of the major reaction of the parent nitrene H N is its dimerisation gives diimide.
2H N R N N H
Diimide
Similarly, aryl nitrenes produce azoarene in the reactions where these nitrenes are involved.
CONCEPT OF ACIDS AND BASES

By the 1884 definition of Svante Arrhenius (Sweden), an acid is a material that can release a proton or hydrogen ion (H+)
in aqueous solution. Hydrogen chloride in water solution ionizes and becomes hydrogen ions and chloride ions. If that
is the case, a base (or alkali) is a material that can ionize to produce hydroxide ion (OH–). Sodium hydroxide in water
solution becomes sodium ions and hydroxide ions. By the definition of both Thomas Lowry (England) and J. N. Bransted
(Denmark), working independently in 1923, an acid is a material that donates a proton, that is, it is protogenic and a base
is a material that can concept a proton, that is, it is protophilic. Was Arrhenius wrong? No. The Arrhenius definition serves
well for a limited use. We are going to use the Arrhenius definition most of the time. The Lowry-Bronsted definition is
broader, including some ideas that might not initially seem to be acid and base types of interaction. The Lowry-Bronsted
definition is more general than the Arrhenius definition, since the former applies to any type of solvent, whereas the latter
is restricted to aqueous solutions. Every ion dissociation that involves a hydrogen or hydroxide ion could be considered an
acid-base reaction. Just as with the Arrhenius definition, all the familiar materials we call acids are also acids in the Lowry-
Bronsted model. G. N. Lewis’ (1923) idea of acids and bases is broader than that of Lowry-Bronsted. The Lewis definitions
are: Lewis acids are molecules or ions which are capable of coordinating with unshared electron-pairs and Lewis bases are
molecules or ions having unshared electron-pairs available for sharing with acids.
We can consider the same idea in the Lowry-Bronsted fashion. Each ionizable pair has a proton donor and a proton
acceptor. Acids are paired with bases. One can accept a proton and the other can donate a proton. Protic acid, by donating
proton (ionizable hydrogen), is converted into its conjugate base. When the acid ionizes, the hydrogen ion is the acid and
the rest of the original acid is the conjugate base. Nitric acid, HNO3, dissociates (splits) into a hydrogen ion and a nitrate
ion. The hydrogen almost immediately joins a water molecule to make a hydronium ion. The nitrate ion is the conju-
gate base of the hydrogen ion. In the second part of the reaction, water is a base (because it can accept a proton) and the
hydronium ion is its conjugate acid.
A free proton is encountered only in a vacuum or in a very dilute gas; it cannot exist in solution.
Acid Base Conjugate base Conjugate acid
HNO3 + H2O → NO
−
3
+ H3O+
CH3COOH + H2O → CH3COO– + H3O+
HCI + H2O → Cl– + H3O+
NH +4 + H2O → NH3 + H3O+
Ph3CH + NH −2 → Ph3C– + NH3
In a way, there is no such thing as a hydrogen ion or proton without anything else. They just do not exist naked in water
solution. Remember that water is a very polar material. There is a strong partial negative charge on the side of the oxygen
atom and a strong partial positive charge on the hydrogen side. Any loose hydrogen ion, having a positive charge, would
quickly find itself near one of the oxygen of water molecule. At close range from the charge attraction, the hydrogen ion
would find a pair (its choice of two pairs) of unshared electrons around the oxygen that would be capable of filling its outer
shell. Each hydrogen ion unites with a water molecule to produce a hydronium ion (H3O+), the real species that acts as an
acid. The hydroxide ion in solution does not combine with a water molecular in any similar fashion. As we write reactions
of acids and bases, it is usually most convenient to ignore the hydronium ion in favour of writing just a hydrogen ion. We
can summarize these as follows:
1. Acids and bases may be neutral or charged.
2. Solvents such as water, which can undergo autoprotolysis, are called amphiprotic solvents.
3. The cA (of the solvent) is often called the lyonium ion, and the cB the lyote ion.
4. Solvents which are neither proton donors nor acceptors are called aprotic solvents.
Acid pKa
Definition of pKa
pKa tells us how acidic (or not) a given hydrogen atom in a compound is. This is useful because, if the first step in a reac-
tion is the protonation or deprotonation of one of the reactants, it is necessary to know where the compound would be
protonated or deprotonated and what strength of acid or base would be needed. In order to measure the strength of an acid
relative to H2O, we must look at the equilibrium constant for the reaction.

AH (aq ) + H 2 O (I)
+ −
H 3 O (aq ) + A (aq )
[H 3 O + ] [A − ]
Keq = (equilibrium constant)
[AH][H 2 O]
The concentration of H2O remains essentially constant (at 55.56 mol dm–3) with dilute solutions of acids wherever the
equilibrium may be, and a new equilibrium constant, ka, is defined and called the acidity constant.
[H 3 O + ][A − ]
Ka =
[AH]
Like pH, this is also expressed in a logarithmic form, pKa

pKa = – log ka
Because of the minus sign in this definition, the lower the pKa, the larger the equilibrium constant ka and, hence, the
stronger the acid. The pKa of the acid is the pH where it is exactly half dissociated. At pH values above the pKa, the acid
HA exists as A– in water; at pH values below the pKa, it exists as undissociated HA. Very weak acids, those with pKa greater
than 17, will not be detectable as acids at all in water, because the hydronium ion produced will be less than that produced
by the autolysis of water itself.
+ −
H 2O + H 2O H3 O + O H
The acid character, though dependent on the nature of HA, will also depend upon the nature of the base present. This
is illustrated by the acidity of carboxylic acids in aqueous solution: the acidity is enhanced in ammonia. The stronger the
acid, the weaker must be its conjugate base.
CH3COOH + Cl– No reaction (Since weaker acid already has the proton)
RCOOH + H2O RCOO– + H3O+ . . . (1)
RCOOH + NH3 RCOO– + NH4+ . . . (2)
Ammonia being a better base (proton acceptor) than water, the equilibrium in (2) lies more to the right side as compared
to (1). Besides carboxylic acids, phenols and alcohols, sulphonic acids (RSO3H) and nitroalkanes (RNO2) also show acidic
behaviour.
Their relative acidities (pKas) thus can not be measured in water at all. Further, when acids are sufficiently strong (low
enough pKa), they will all be essentially fully ionised in water, and will thus all appear to be of the same strength, e.g., HCl,
HNO3, HClO4 etc. This is known as the levelling effect of water.
The range of comparative pKa measurement can, however, be extended by, in the first case, providing a stronger, and
the latter case a weaker, base than H2O as solvent. By carrying out measurements in a range of solvents of increasing ba-
sicity (and by using an acid that is near the bottom limit of the acidity range in one solvent and near the top of the range
in the next as a common reference in each case) is possible to carry determination of acid strengths on down to acids as
weak as methane (pKa 43).
According to the Bronsted-Lowry concept, an acid is the proton donor and a base is an acceptor of proton. In acid-base
reactions, the acid dissociates to its conjugate base and a proton. Since protons never exist as separate entities, a base must
be present to remove protons from acids. The acidic character of different compounds can be compared by their ability to
give protons to any given base, which is usually water. This change can be represented as:
Acid Base Conjugate base Conjugate acid
HA + H2O → A– + H3O+
CH3COOH + H2O → CH3COO– + H3O+
The strength of acid HA will be dependent on the extent to which the equilibrium is shifted to the right that is, how good
a proton donor HA is. Acid strength may be defined as the tendency to give up a proton, and base strength as the tendency
to accept a proton. Every acid has a conjugate base associated with it and every base has a conjugate acid associated with
it.
+
CH3COOH + NH3 NH4 + CH3COO–
acid base conjugate acid conjugate base
1. The stronger the acid HA the weaker its conjugate base A–.
2. The stronger the base A–, the weaker its conjugate acid AH.
3. The most important factor in the strength of an acid is the stability of the conjugate base–the more stable the conjugate
base, the stronger the acid.
4. An important factor in the stability of the conjugate base is which element the negative charge is on — the more
electronegative the element, the more stable the conjugate base.
Effect of Structure on Strength of Acids

Carbon acids
Acids in which protons are lost from the carbon are termed as carbon acids. A carbanion is the conjugate base of a carbon
acid. They are very weak acids (pKa above ~ 17); they are weaker than oxygen acids because carbon is less electronegative.
Increasing the number of phenyl groups decreases the pKa due to delocalization of charge over all the rings.
H H Ph Ph
H H H Ph
H H H Ph H Ph H Ph
pKa 48 40 33 32
The electronegativity of carbon atoms decreases in the order sp > sp2 > sp3, which shows that ethyne is a stronger acid than
ethene, which is stronger than ethane [C2H2 (pKa~26), C2H4 (pKa~44), C2H6 (pKa~50)].
Nitrogen acids
Oxygen acids and carbon acids are very common. Before we move on to bases, it would be worthwhile to discuss nitrogen
acids. The pKa of NH3 is much greater than the pKa of H2O because oxygen is more electronegative than nitrogen and so
can stabilize the negative charge better, Carboxylic acid has a lower pKa than amide: a strong base is needed to deprotonate
an amide. Amines are not acidic, amides are weakly acidic (as alcohols) and imides are acidic (as phenols).
O O
O H
O N H R N N–H
H H R H H H
O H
O
pKa 15.74 ca. 5.0z ca. 33.0 ca. 17.0 8.3
Field effect
The Field Effect operates through space or solvent molecules and depends on the geometry of the molecule. For example,
nitroacetic acid is about a thousand times stronger and trichloroacetic acid is about ten thousand times stronger than acetic
acid, because the field effect spreads the negative charge of CC13COO– all over the molecules.
CH3COOH (pKa = 4.76), O2NCH2COOH (pKa = 1.68), CC13COOH (pKa = 0.65)
Groups that withdraw electrons by the field effect increase acidity and decrease basicity, whereas electron-donating
groups act in the opposite direction. For example,
O O O O O
O2N + O O
H 3C OH H OH OH Me3N NC
OH OH
pKa 4.76 3.70 1.76 1.80 OH
2.40 3.60
OH
F3C CF O2N CF3
NO2
OH OH H C OH F3C OH F C
3
3 3 OH F3C OH
pKa 17.1 16.0 15.5 12.40 9.30 5.40 0.70
NO2
Indeed, virtually all ortho-benzoic acids are stronger than the corresponding para-isomer, regardless of whether the
group on the ring is electron-donating or electron-withdrawing because of the ortho effects.
Resonance effect
Resonance that stabilizes a base but not its conjugate acid results in the acid having a higher acidity than otherwise
expected, and vice-versa. We know that carboxylic acid is a much stronger acid than an alcohol. For example, the pKa of
acetic acid is 4.80, whereas the pKa of ethyl alcohol is 15.9. Substituents that withdraw electrons from the oxygen of the
OH group increase the acidity of a compound by making the O-H bond easier to break.
The carboxylate ion has greater resonance energy than carboxylic acid because the anion has two equivalent resonance
contributors that are predicted to be relatively stable, whereas carboxylic acid has only one resonance contributor that is
predicted to be relatively stable. Therefore, the loss of protons from a carboxylic acid is accompanied by an increase in
resonance energy. In contrast, all the electrons in an alcohol and its conjugate base are localized, so loss of protons from
an alcohol is not accompanied by resonance stabilization.
+
O OH
R C R C
–
OH O
Relatively stable Relatively unstable
–
O O
R C OH R C R C
–
O O
O
–
R CH2OH→ R CH2 O
Thus, amides (RCONH2) are more acidic than amines (RCH2NH2); esters (RCH2COOR’) more acidic than ethers
(RCH2CH2OR’) and ketones (RCH2COR) more acidic than alkanes (RCH2CH2R’). The effect is enhanced when two
carbonyl groups are attached to the same carbon: e.g., b-ketoesters are more acidic than simple ketones or esters.
–
R C C C OR R C C C OR R C C C OR R C C C OR
H2 H H H
O O O O –O O O O
–
The extreme examples of this effect can be visualized in the molecules tricyanomethane, (NC)3CH (pKa = –5) and
2-(dicyanomethylene)-1,1,3,3-tetracyanopropene, (NC)2C=C[CH(CN)2]2 (pKa1 = –8.5, pKa2 = –2.5).
In general, resonance effects lead to the same result as field effects. Where both resonance and field effects operate,
charge dispersal leads to greater stability. The acids HC1O, HC1O2, HClO3 and HC1O4 have pKa values 7.5, 2, –1 and
about –10, respectively. The negative charge on the perchlorate anion can be delocalized equally over all the four oxygens.
Oδ⊝
O O O O
etc. O O
Cl Cl Cl
O O H O O Cl ≡ δ⊝
–
O δ⊝
O O O
B Oδ⊝
Resonance effects are also important in aromatic amines. m-Nitroaniline is a weaker base than aniline due to –I effect
of the nitro group. But p-nitroaniline is weaker still, though the-I effect should be less, because of the greater distance. The
lower basicity of p-nitroaniline is due to resonance that diminishes the availability of a lone pair for attack by a proton.
+
NH2 NH2 NH2 NH2
NO2
N – N+ –
pKa of O O
–
O O
conjugate acid 4.60 2.47 1.11
Delocalization of the negative charge stabilizes the conjugate base.

⊝
O
H – O H O O O
O O
etc. ⊝ ⊝
⊝
pK a = 16 localized pK a = 10 phenoxide delocalized (phenolate ion)
anion anion
Notice that the following oxygen acids have pKa values that conveniently fall in units of five (approximately).
Acid RSO2OH RCO2H ArOH ROH
Approx. pKa 0. 0 5. 0 10. 0 15. 0
Another interesting group of examples is the series squaric acid, croconic acid and rhodizonic acid; these are among
the relatively few strong dibasic organic acids. Thus, squaric acid has a pKa ~1 and pK2 ~3, which makes it comparable to
sulphuric acid in strength.
O O
HO O HO HO O
O
HO O HO HO O
O O
squaric acid croconic acid rhodizonic acid
Periodic Table Correlation

Comparing acids and bases that differ in the position of an element in the periodic table, the following generalizations can
be made.
(a) Acidity increases and basicity decreases in going from left to right across a row of the periodic table, that is, acidity
increases in the order CH4 < NH3 < H2O < HF and basicity decreases in the order CH3– > –NH2 > –OH > F–. This is
because electronegativity increases from left to right across the table. The great difference in acidity between carboxylic
acids, amides and ketones (that is, RCOOH >> RCONH2 >> RCOCH3) is due to this effect.
(b) Acidity increases and basicity decreases in going down a column of the periodic table, despite the decrease in
electronegativity. Thus, acidity increases in the order HF < HC1 < HBr < HI (pKa 3.2, –7, –9t –10) and H2O < H2S
and basicity decreases in the order NH3 > PH3 > AsH3 (due to the size of the species involved). That occurs because
the atoms get larger as we move down a column, and the size of the atom bonded to hydrogen is more important than
its electronegativity in determining the acidity.
(c) Acids that require only one electron pair to complete an outer shell are stronger than those that require two. Thus,
GaCl3 is stronger than ZnCl2. This results from the relatively smaller energy gain in adding an electron-pair that does
not complete an outer shell and from the build up of negative charge if two pairs come in.
(d) Other things being equal, the acidity of MXn decreases in going down the periodic table because as the size of the
molecule increases, the attraction between the positive nucleus and the incoming electron pair is weaker. Thus, BC13
is a stronger acid than A1C13.
(e) For cations, increased charge and decreased radius increases acidity. Thus, the decreasing order of some Lewis acids is
in the order Al(H2O)53+ > A1(H2O)4C12+ > A1(H2O)3C12+. For anions, increased charge and decreased radius increases
basicity, i.e., O22– is a stronger base than either OH– or Se2–.
Statistical effect
In a symmetrical diprotic acid, the first dissociation constant is twice as large as expected, as there are two
equivalent ionizable hydrogens, whereas the second constant is only half as large as expected because the conjugate
base can accept a proton at two equivalent sites. So K1/K2 should be 4 and approximately this value is found for
dicarboxylic acids, where the two groups are sufficiently far apart in the molecule that they do not influence each
other.
In the gas phase, where solvation effects are completely or almost completely absent, acidity orders may also differ
greatly, e.g., in the gas phase, toluene is a stronger acid than water and t-butoxide ion is a weaker base than methoxide
ion. Temperature also affects the acidity order, e.g., above 50°C, the order of base strength is BuOH > H2O > Bu2O; from
1–50°C, the order is BuOH > Bu2O > H2O; while below 1°C, the order becomes Bu2O > BuOH > H2O.
Hydrogen bonding
Internal hydrogen bonding can greatly influence acid or base strength, e.g., pKa for o-hydroxy benzoic acid is 2.98, while
the value for the p-isomer is 4.58. Intramolecular hydrogen bonding between the OH and COO– groups of the conjugate
base of the o-isomer stabilizes it and results in increased acidity.
COOH COOH COOH –

H
OH O O
O
OH
Similarly, maleic acid has a lower pKa value (1.92) for the first ionization constant than the trans-isomer, fumeric
acid (pKa 3. 0), because the electrostatic effect of one carbonyl dipole facilitates the departure of the first proton from the
other carboxyl group that is in its proximity; this is coupled with the fact that the singly charged cis anion is stabilized by
intramolecular hydrogen bonding.
O –
–H+ O
H H H COOH
O O
H H
H O H O HOOC H
O H O
In many 2-substituted heterocyclic acids, the hydrogen bond has the opposite effect, i.e., it reduces the strength of the
acid. The H-bonding stabilizes the acid and decreases the dissociation constant.
O
N
H O
Steric effect
The steric effect profoundly affects the molecular conformation and reaction mechanism, and its study is fundamental to a
proper understanding of structure and reactivity. The strain caused by the formation of a covalent bond when the two atoms
Involved each have three large groups is called face strain or F strain. Steric effects may indirectly affect acidity or basic-
ity by affecting the resonance, e.g., o-t-butyl benzole acid that is ~10 times as strong as the p-isomer because the carboxyl
group is forced out of the plane by the t-butyl group.
Factors affecting acidic strength of Alcohols and Phenols:

(i) Alcohols are weaker acids than thiols even though oxygen is more electronegative than sulphur conjugate base of
alcohol, i.e., RO– is more basic than RS– as in RO– –ve charge is placed on smaller oxygen atom, so it will have more
charge density. But in RS– –ve charge is dispersed on bigger sulphur, so it is a poor base and its conjugate acid will
be more acidic. Order of Acidic strength of some of the compound are given as:
RSO3H > RCOOH > phenol > H2O > ROH > HC ≡ CH > NH3 > CH2 = CH2 > CH3 – CH3
In a period electronegativity factor dominate, i.e., more the electronegativity of an atom, the weaker will be the base.
− −
CH 3 > CH = CH 2 > NH 2 > HC ≡ C > OR > OH > F
RSO3– is more resonance stabilized than RCOO–. As negative charge can be dispersed on three oxygen atoms.
(ii) All alcohols (except CH3OH) are weaker acids than H2O due to +1 effect of alkyl group. CH3OH is slightly stronger
than H2O. Phenols are stronger than alcohol due to e– withdrawing benzene ring and resonance stabilized base
phenoxide ion. Alkoxide ions, the conjugate base of alcohol have no resonance, so it is less stable and more basic.
Phenol is weaker than carboxylic acid, which have strong electron withdrawing carbonyl group and more stable
conjugate base (resonance stabilized and its resonating structures are more stable than phenol)
Alcohol
The acidic behaviour of alcohol is due to the polar nature of O – H bond. An electron donating group (–CH3, –C2H5) tends
to increase the electron density on oxygen, which in turn decreases the polarity of O – H bond and the acidic strength.
Alcohols are very weak acids (Ka = 10–16 – 10–18) even feeble than water (Ka = 10–14) and they do not turn blue litmus red.
The order of acidic strength among various types of alcohols is
Primary > Secondary > Tertiary
The order can be explained in terms of electron releasing inductive effect of alkyl groups. Greater is the number of alkyl
group attached to carbon carrying —OH group lesser shall be polarity of —OH group, and hence, lesser will be acidic
character. In tertiary alcohols the carbon atom carrying –OH group is attached to three alkyl groups, due to which electron
density on oxygen is minimum in their case, and hence the loss of H+ is most difficult. Thus, tertiary alcohols are least
acidic; whereas primary alcohols are most acidic.
Presence of electron withdrawing groups (eg: CF3,-NO2,-CN,-X) tends to decrease the electron density on oxygen,
which in turn increases the polarity of O-H bond and will increase the acidic strength
Thus,
F3C CH2 OH > Me CH2 OH
PKa = 12.4 PKa = 18
(Note that compounds with large PKa are less acidic)

Alcohols also show an ability to act as Bronsted base due to the presence of unshared electron pairs on oxygen, which
make them proton acceptors.
R O +H O H R O H+ OH
Base Acid Conjugate Conjugate
acid base
Acidic strength of phenols

Phenols are fairly acidic compounds, and in this respect, markedly different from alcohols, which are even more weakly
acidic than water. Aqueous hydroxides converts phenols into their salts; aqueous mineral acid convert the salts back into
the free phenols.
–
OH –
ArOH ArO
+
H
A phenol A phenoxide ion
(acid) (salt)
Insoluble in water Soluble in water
Most phenols have Ka values in the neighbourhood of 10–10 and are thus weaker acids than the carboxylic acids
(Ka values about 10–5).
Phenol does not displace CO2 from carbonate and bicarbonates, but RCOOH and RSO3 give brisk effervescence of
CO2, which proves that RCOOH and RSO3H are stronger acids that Na2CO3. Trinitrophenol is highly acidic due to strong
electron withdrawing effect of three nitro groups. It is acidic strength is comparable to that of carboxylic acids, which is
why it is called Picric acid. Its anion is highly resonance stabilized.
–+
OH ONa
O2N NO2 O2N NO2
+ NaHCO3 + CO2 + H2O
NO2 NO2
- +
RCOOH + NaHCO3 RCOONa + CO2 + H2O
Ph – OH + NaHCO3 no reaction.
1. The most notable characteristic property of phenols is their acidity. Phenols are more acidic that alcohols, which are
even more weakly acidic than water, but phenols are less acidic than carboxylic acids.
R — COOH > Ar — OH > H — OH > R — OH
O O
R C O R C=O
equivalent resonating structure
Phenols are less acidic than Carboxylic acids, because in carboxylate anion, the resonance is involved between identical
atoms having same energy level. Thus, we can say that carboxylate ion is a resonance hybride of two equivalent resonating
structures. So its stability will be more.
O O O O
(non equivalent
structure)
However, in case of phenol, its conjugate base phenoxide ion have non equivalent structure, where the charge is delo-
calized from more electronegative oxygen to less electronegative carbon. Resonating structure phenoxide ion is less stable
than carboxylate ions.
A summary of the acidic characters of phenols is given here.

(i) Greater acidity of a phenol than an alcohol is due to the possibility of resonance in phenol, which leads to electron-
deficient oxygen atom. Presence of electron-deficient oxygen atom (see structures II, III and IV) in turn weakens the
+
— O — ← H bond, and thus facilitates the release of proton.
O—H O—H O—H O—H
I II III IV
Such structures are not possible in alcohols.
(ii) Once hydrogen atom is removed from phenol, the ion (phenoxide) is very much stabilized due to delocalization of its
negative charge.
O O O O
V VI VII VIII
Resonance in phenoxide ion (note that structures VI to VIII are equivalent)
Remember that phenoxide ion is very much more stable than the parent compound phenol because phenoxide ion
does not involve charge separation, while in phenol three equivalent resonanting structures (II to IV) involve charge
separation.
(iii) Electron-withdrawing substituents increase the acidity of phenols; while electron releasing substituents decrease
acidity. Thus substituents affect acidity of phenols in the same way as they affect acidity of carboxylic acids; it is, of
course, opposite to the way these groups affect basicity of amines.
G withdraws electrons, thus disperses the –ve charge of the ion, stabilizes it and hence increases ionization of the
parent phenol.
OH O
H+ +
G G
+
(where G = —NO2, —CN, —CHO, —COOH, —N R 3 , —X)
G releases electrons, thus intensifies the –ve charge of the ion, destabilizes it and hence decreases ionization of the

parent phenol.
OH O
H+ +
G G
(where G = —R, —OR, —NR2)
(I) lf a group exerts -R and-I effects, it will increase acidic strength. For Example, The of acidic strength of nitrophenol
follows the order:
P-nitrophenol > O-nitrophenol > m-nitrophenol > phenol
This is because when NO2 group is attached in meta position, it does not exhibit (-R) effect, only (-1) effect is
operated. Thus, we can say that m-nitrophenol is more acidic than phenol due to -I effect of -NO2 group.
Similarly, when –NO2 group is attached to O and P positions, it shows –R effect. Thus, stabilizes phenoxide ion through
both –I and –R effects. Between O-nitrophenol and P-nitrophenol, P-nitrphenol is more acidic as in O-nitrophenol
hydrogen bond between hydrogen and oxygen decreases the removal of H+ ions.
H
O O
N=O
⊕
Electron donating groups destablize carbanion and will decrease acidic strength.
(II) If a group exert + R or (+M) and –I effects, it will decrease acidic strength. For example,
OH OH OH OH
OCH3
> > >
OCH3
at meta position more (-1) effect OCH3
only –1effect but +M effect
less (-1) effect and
also +M effect
(III) If a group has +I effect and Hyperconjugation, it will decrease the acidic strength.
For examples all cresols are less acidic than phenol due to electron donating effect (+I) and hyperconjugation effect
of alkyl group.
(IV) Halogen exerts both + R and –I effect but –I effect dominates over + R effect, so all halophenols are stronger than
phenol, except p-Fluorophenol, which has almost same strength as phenol. Among o-halophenols + R and –I effects
are cancelled.
o-chlorophenol > o-Bromophenol > o-iodophenol > o– fluoro phenol ([due to inability of F to exert –M effect as it
has no ‘d’ orbital and it is also due to intra molecular H-bonding] ≈ phenol).
(V) Thiophenols are less acidic than phenol. Due to Bigger size of sulphur, its +M effect is less, so it will not get
positively charged like phenol.
S–H O–H
(IV) Small oxygen can easily overlap through its 2p orbital with carbon of benzene and gets positively charged that makes
the adjoining hydrogen more acidic.
pKa
O O
C6H5OH 9.95
o-O2NC6H4OH 7.23
m-O2NC6H4OH 8.35
p-O2NC6H4OH 7.14
N N
2,4-(O2N)2C6H3OH 4. 01 O ⊕ O O ⊕ O
2,4,6-(O2N)3C6H2OH 1. 02
pKa
C6H5OH 9.95
o-MeC6H4OH 10.28
m-MeC6H4OH 10. 08
p-MeC6H4OH 10.19
Illustrations
49. Use chemical equations to compare the reactions of RCOOH (pKa = 5) and PhOH (pKa = 10) with aqueous
(a) NaHCO3 and (b) Na2CO3 (pKa’s of H2CO3 and HCO^ are 6.4 and 10.3, respectively).
Ans. The equilibria of Bronsted acid-base reactions favor the side with the weaker acid and base. In each case, write
the ionic equation as if it occurs and place the pKa values under each acid. If the weaker acid is on the right side,
the reaction occurs but if the weaker acid is on the left side, the reverse reaction occurs.
The last reaction above occurs. However, the result is borderline and any substituted phenol that has pKa > 10.5
may not react.
(a) RCOOH+ HCO3– → RCOO– + H2CO3 (H2O + CO2) This reaction occurs.
pKa = 5 pKa = 6.4 (weaker acid)
PhOH+ HCO –
3
× PhO –
+ H2CO3 (H2O + CO2) No forward reaction.
pKa = 10 pKa = 6.4 (stronger acid)
(b) RCOOH+ CO32– → RCOO– + HCO3– This reaction occurs.

PhOH+ CO32– ⇄ PhO– + HCO3–
50. Use ionic chemical equations to compare the reactions of RCOO-Na+ and ArO-Na+ with CO2.
–
Ans. RCOO– + CO2 + H2O RCOOH + HCO3
–
ArO– + CO2 + H2O ArOH + HCO3
pKa = 6.4 pKa = 5 pKa = 6.4 pKa = 10
(stronger acid) (weaker acid)
No forward reaction This reaction occurs
51. Explain why a substituent such as NO2 bonded ortho or para has a much greater effect on the acidity of a phenol
than a benzoic acid.
Ans. Charge delocalization in the nitrophenolate ion is much more effective because of the direct interaction between
O-and NO2, which interaction is not possible in the p-nitrobenzoate anion.
O
O +
O +
N O N C O
O O
direct extended π bonding no direct extended π bonding
52. Place the following groups of compounds in decreasing order of acidity and justify your answers.
(a) Phenol (A), o-nitrophenol (B), m-nitrophenol (C), p-nitrophenol (D);
(b) Phenol (A), o-chlorophenol (E), m-chlorophenol (F), p-chloroophenol (G); and
(c) (A), o-cresol (H), m-cresol, (I), p-cresol (J).
Ans. (a) NO2 is electron – withdrawing and acid –strengthening by both induction and resonance. Its resonance effect
is effective from only the ortho and para positions to about an equal extent. It predominates over the inductive
effect which operates from all positions but at decreasing effectiveness with increasing separation of NO2 and
OH. Hence all the nitrophenols are more acidic than phenol with m-nitrophenol being the weakest of the three.
Since the inductive effective from the closer o positions is the strongest, one might expect o-nitrophenol to
be stronger than p-nitrophenol. However, the intramolecular H-bond in o-nitrophenol must be broken and this
requires some energy. The decreasing order is D > B > C > A.
(b) Although Cl is electron – donating by resonance, its electron – withdrawing inductive effect that decreases
with increasing separation of Cl and OH predominates, making all the chlorophenols more acidic than phenol.
The decreasing order is E > F > G > A.
(c) Me is electron – donating inductive from all positions and hyperconjugatively from the ortho and para
positions. The three isomers are weaker acids than phenol. m-Cresol is the strongest because its acidity is not
weakened by hyperconjugation. The decreasing order is A > I > J > H.
53. Acidic nature is more for
(a) o-amino phenol (b) m-amino phenol
(c) p-amino phenol (d) All have equal Ka’s
Ans. –NH2 is electron donating group, at meta position the donation of electron will be least.
\ (b)
54. Phenol is less acidic than
(a) ethanol (b) methanol
(c) o-nitrophenol (d) p-cresol.
Ans. Nitro is electron withdrawing group
\ (c)
Acidic Strength of Carboxylic Acid

Acidity is relative case with which it loses a proton leaving behind the anion. Its acid strength depends upon the difference
in the stability of the acid and its anion.
O O O O
R R H+ R R
OH OH O O
non-equivalent structures of equivalent structures of
resonance hybrid resonance hybrid
both acid and its anion are stabilized by resonance, stabilization is far greater for the anion than for acid because anion
gives two identical resonating structure.
Effect of Substituents on Acidity

Any factor that stabilizes the anion more than it stabilizes the acid should increase the acidity and any factor that makes
the anion less stable should decrease the acidity of the carboxylic acid.
(a) An electron withdrawing substituent stabilizes the anion by dispersing the –ve charge and therefore increases the
acidity of carboxylic acid.
(b) Electron releasing substituetns intensify the –ve charge on the anion resulting in decrease of stability of the carboxylate
anion and therefore decreases the acidity of the acid.
Carboxylic acids are weak acids and their carboxylate ions are strong conjugate bases, slightly alkaline due to the
hydrolysis of carboxylate anion compared to other species. The orders of acidity and basicity of corresponding conjugate
bases are as follow.
Acidity — RCOOH > HOH > ROH > CH ≡ CH > NH 3 > RH
Basicity — RCOO − < OH − < HC ≡ C− < NH 2− < R −
The effect of various, numberous and their distance from the carboxylic group has been illustrated with the help of
following examples.
(i) The effect of number of the substituent is shown by the chloro substituted acetic acids. The acid strength increases in
the order given below.
ClCH — COOH < Cl CHCOOH < Cl COOH
2 2 3
The increase in the number of chloro substituent on α-carbon atom of acetic acid make the electron withdrawing
effect more pronounced and hence make carboxylate ion more stable.
When electron releasing substituent is attached to the carboxylic group, then acid strength decreases as the
electron releasing power increases.
(ii) The effect of nature of the substituent is illustrated by the various halo acetic acids.
Their acid strength follows the order
ICH 2 — COOH < BrCH 2 COOH < ClCH 2 COOH < F CH 2 COOH
CH 3 − CH 2 — CH 2 — COOH < CH 2 = CH − CH 2 − COOH < N ≡ C — CH 2 — COOH

↑ ↑
2
(sp ) (sp)
O O
C – EDG C –
EWG
O O
Electron withdrawing group (EWG) Electron doneting group (EDG)
stabilises the carboxylate anion and destabilises the carboxylate anion
strengthens the acid and weakens the acid
The effect of the following groups in increasing acidity order is

⊕
Ph < l CCl3COOH > CHCl2COOH > NO2CH2COOH > NC – H2CCOOH > FCH2COOH >

ClCH2COOH > BrCH2COOH > HCOOH > ClCH2CH2COOH > C6H5COOH > C6H5CH2COOH2COOH >
CH3CH2COOH (continue)
Illustration
HOOC H HOOC COOH

55. is less acidic than ; why is this so?
H COOH H H
Ans. The cis dicarboxylic acid after first ionization produces anion which is stabilized through intra molecular
H-bonding by second COOH group which is present on the same side of anioic group COO– . But anion formed
from trans compound can not stabilized by intra molecular H-bonding because COOH group is present on
opposite side of COO– group.
OH O
O C
O
C C
H H
(iii) Effect of the position of the substituent: The effect of the substituent decreases as its distance from —COOH group
increases.
Cl Cl
CH 3 — CH — COOH > CH 2 — CH 2 — COOH

α-chloro propanioic acid electron β -chloro propanioic acid electron
withdrawing effect more withdrawing effect less
(a) Increase in the number of halogen atoms on α–position increases the acidity, e.g.,
CCl3COOH > CHCl2COOH > ClCH2COOH > CH3COOH
(b) Increase in the distance of halogen from COOH decreases the acidity e.g.,
CH3–CH2–CH–COOH > CH3–CH–CH2–COOH > CH2–CH2–CH2–COOH
Cl Cl Cl
This is due to the fact that inductive effect decreases with distance.
(c) Increase in the electro negativity of halogen increases the acidity.
FCH2COOH > ClCH2COOH > BrCH2COOH > | CH2COOH
(d) HCOOH > C6H5COOH > RCOOH
Table 2.5 Inductive effect of substituent Groups of Some substituted Acetic acids
Acid pKa I effect of substitutent

H CH2 CO2H 4.75 H = reference point
CH3 CH2 CO2H 4.90 +I
CH3 O CH2 CO2H 4.30 –I
l CH2 CO2H 3. 0 –I
Br CH2 CO2H 2.9 –I
Cl CH2 CO2H 2.8 –I
⊕
(CH3)3N CH2 CO2H 1.8 –I
Here, –I x Acidic strength.

α 2.84 –I
CH3 CH2 CH CO2H
Cl
β α
CH3 CH CH2 CO2H 4. 06 –I
Cl
γ β α
CH2 CH2 CH2 CO2H 4.52 –I
Cl
Inductive effect is maximum from a position

HO2C CO2H 1.23 –I
HO2C CH2 CO2H 2.28 –I
HO2C CH2 CH2 CO2H 4.19 –I
Inductive effect is distance dependant; as distance increases, inductive effect decreases.

H CH2 CO2H 4.75 H = reference point
Cl CH2 CO2H 2.86 +I
Cond.
Cl CH CO2H 1.25 –I
Cl
Cl
Cl CH CO2H 0.65 Two (–I) effect
Cl
Inductive effect is an additive effect

O
H C OH 4.2 H = reference point
O
⊕
(CH3)3N C OH 3.9 –I
O
CH3 C OH 4.75 +I
O
CD3 C OH 4.6 +I
+I effect of deuteriu, is stronger than +I of hydrogen. +I (–CD3) > – CH3).

CH3 OH 15.5 +I
F 2C CH3 OH 12.4 –I
F 3C CH OH 9.3 –I
CF3
CF3
CF3 C OH 5.4 –I
CF3
Electron withdrawing groups lower the pKa of alcohols.
ORTHO EFFECT
The ortho substituted benzoic acid (whether the substituent is electron withdrawing or releasing) is comparatively stronger
acid than the para and meta isomers. This effect is called ortho effect. It occurs due to the joint operation of steric and
intra molecular H-bonding where ever it takes chance to stabilize the carboxylate anion due to nearness of the substituent.
Groups like —OH, —Cl, NO2 will cause more stabilization to anion due to direct interaction through intra molecular
H-bonding.
OH O
H
intra molecular
+
H
O
OH H-bonding
stabilization
O O
o-hydroxy benzoic acid Carboxylate anion
(Salicylic acid)
COOH COOH COOH

OH
> >
OH
OH
Order of acidic character
Most of the orthosubstituted aromatic acids are the strongest, which may be due to steric hindrance called ortho effect.
Some time it may be due to stabilization of conjugate base by intramolecular hydrogen bonding. Intramolecular hydrogen
bonding can,of course, operate in the undissociated acid as well as in the anion. But it is more effective in anion because
the negative charge on oxygen in the anion will lead to stronger hydrogen bonding. For example, 2,6-Dihydroxy benzoic
acid is found to have pKa = 1.3.
Both electron releasing and e– withdrawing substituent tend to increase acidic strength of benzoic acid when these are
present at ortho position.
–
O O O O O O
H H H
C C C
O O O
OH OH OH
p-Hydroxybenzoate ion, I o-Hydroxybenzoate ion II 2, 6-Dihydroxybenzoate ion, III
(more stable than I) (more stable than II)
The presence of groups such as – OCH3, –OH or halogens which are electron withdrawing inductively but electron
donating mesomerically when present in o– and p– position may even cause the p– substituted acids to be weaker than
m– substituted acids.
The behaviour of some ortho substituted benzoic acids is anomalous and the acid strength is considerably higher than
expected. This may be due to interaction of the group with the adjacent carboxylic group, i.e., intermolecular H–bonding.
COOH COOH COOH COOH
CH3
> > >
CH3 (PKa = 4.28)
(PKa = 3.9) (PKa = 4.2) (PKa = 4.27) (+1 and
(Ortho effect) (+1 effect) CH3 hyperconjugation)
COOH COOH
COOH COOH
OCH3
> > >
OCH3 (-1 and + M effect)
(Ortho effect) (-1 effect) (PKa = 4.7)
(PKa = 4.09) (PKa = 4.09) (PKa = 4.2)
OCH3
COOH COOH COOH COOH

NO2
> > >
NO2
(-1,- M and Ortho effect) (-1 effect)
(Pka = 2.2) NO2 (PKa = 3.49)
(-1- M effect)
(PKa = 3.42)
COOH COOH
< But CH2COOH > CH2COOH

F Cl
Cl - I effect - I effect
F is more is less
+ M effect + M effect
is more is less
COOH COOH COOH
> >
NO2 COOH
Decreasing order of acidic strength:

a-Nitro acid > a-Keto acid > a-hydroxy acid > formic acid > acetic acid.
Second ionization constant K2 for furmaric acid is greater than for maleic acid.
H-bonding involving acidic H has an acid weakening effect and H-bonding in conjugate base has an acid strengthening
effect.
Since the second ionisable H of the Maleate participates in H-bonding, more energy is needed to remove this H because
the H-bond must broken. The maleate mono anion is, therefore, the weaker acid.
pKa
C6H5CO2H 4.20
m-MeC6H4CO2H 4.24
p-MeC6H4CO2H 4.34
pKa O O
C
C6H5CO2H 4.20
⊕
o-O2NC6H4CO2H 2.17
m-O2NC6H4CO2H 3.45
p-O2NC6H4CO2H 3.43 N
O ⊕ O
3,5-(O2N)2C6H3CO2H 2.83
pKa of XC6H4CO2H
2 2 2 2 + &O %U 20H 2+
& &
R
P
S
; ;
Acidity of Dicarboxylic Acids

As the carboxyl group itself has an electron withdrawing inductive effect, the presence of a second such group in an acid
might be expected to make it stronger.
A dicarboxylic acid contains two carboxyl groups, it is apparently more acidic than monocarboxylic acid. Also a
dicarboxylic acid possesses two ionization constant (K1 and K2). The ionization of the second carboxyl group occurs rather
less readily than ionization of the first. It is rationalized on the basis that more energy is required to separate a proton from
the charged anion than from neutral molecule. This is evident from the KI and Ka values of oxalic acid.
– –
COOH K1
+
COO K2
+
COO
H + H + –
COOH COOH COO
K1 = 5.4 × 10–2
K2 = 5.2 × 10–5
HCO2H HO2CCO2H
3.77 1.23
CH3CH2CO2H HO2CCH2CO2H
4.76 2.83
CH3CO2H HO2CCH2CH2CO2H
4.88 4.19
C6H5CO2H HO2CC6H4CO2H
4.17 O-2.98
m-3.46
p-3.51
The effect is very pronounced, but falls off sharply as soon as the carboxyl groups are separated by more than one
Saturated carbon atom. Cis-butenedioic (maleic) acid (5, pKa1 = 1.92) is a much stronger acid than trans-butenedioic(fumaric)
acid (6, pKa1 = 3. 02), due to the intramolecular hydrogen bonding that can take place with the former, but not with the
latter, leading to relative stabilisation of the cis (maleate, 7) mono-anion (cf. o-hydroxybenzoic acid above):
O O O
H C H C
C O C O H C C OH
–H⊕
C HO
H H H C H
C
C
H
C=O C O
O H O O
(5) (7) (6)
The second dissociation of trans-butenedioic acid (pKa2 = 4.38) occurs more readily than that of the cis-acid (pKa2
= 6.23), however because of the greater difficulty in removing a proton from the negativity charged cyclic system in the
anion (7) derived from the latter. Ethane-dioic(oxalic), propane-1, 3-dioic(malonic) and butane-1,4-dioic(succinic) acids
are each weaker in their second dissociations than methanoic ethanoic and propenoic acids, respectively. This is because
the second proton has to be removed from a negatively charged species containing an electron-donating substituent, i.e.,
COΘ2 which might be expected to destabilise the anion with respect to the undissociated acids, as compared with the
unsubstituted system:
O O
O2C CH2 C CH3 C
O O
&2+
Table 2.6 List of Ka (pKa) values for ;
Value of X Ortho Meta Para

H 6.3 × 10–5 (4.2) 6.3 × 10–5 (4.2) 6.3 × 10–5 (4.2)
CH3 1.2 × 10–4 (3.9) 5.3 × 10–5 (4.3) 4.2 × 10–5 (4.4)
F 5.4 × 10–4 (3.3) 1.4 × 10–4 (3.9) 7.2 × 10–5 (4.1)
Cl 1.2 × 10–3 (2.9) 1.5 × 10–4 (3.8) 1.2 × 10–4 (3.99)
Br 1.4 × 10–3 (2.85) 1.5 × 10–4 (3.81) 1. 0 × 10–4 (4. 0)
I 1.4 × 10–3 (2.9) 1.4 × 10–4 (3.9) 9.2 × 10–5 (4. 0)
CH3O 8.1 × 10–5 (4.1) 8.2 × 10–5 (4.1) 3.4 × 10–5 (4.4)
O2N 6.7 × 10–3 (2.2) 3.2 × 10–4 (3.5) 3.8 × 10–4 (3.4)
OH 2.98 4. 08 4.58
Comparison of the Acidic Strength

Case I
When the phenyl ring has substituent groups, which show +H (hyperconjugation. ) and +I (inductive) effects.
(A) (B) (C) (D)
CH3 CH3 CH3 CH3
CH3
CH3
CH3
CH2 CH2 CH2 CH2

CH3
CH3
CH3
Destabilized Destabilized by Destabilized Stabilized
by hyperconjugation +1 by hyperconjugation
and +1 effects. and +1 effects.
+1 is maximum +1 is minimum
D >B >C >A
Acidic
strength
The more stable is the conjugate, the more will be the acidic strength.
For example, compare acidic strength of the following:
OH OH OH OH
CH3
CH3
CH3
(A) (B) (C) (D)
A>C>D>B
Acidic strength
Case II
When the phenyl ring has substituent groups with –M and –I effects,
(A) (B) (C)
CH3 CH3 CH3
NO2
NO2
NO2
CH2 CH2 CH2

NO2
NO2
NO2
Stabilized Stabilized by Stabilized by
-R of NO2 (-1) effect - R of NO2
-1 of NO2 of NO2 only - 1 of NO2
-1 is maximum - 1 is minimum
A>C>B
Acidic strength
For example, compare the acidic strength of the following:
CH OH OH
NO2
NO2
(A) (B) (C)
OH OH OH
NO2 O2N NO2
NO2 NO2 NO2

(D) (E) (F)
F>E>D>B>C>A
Acidic strength
Due to intramolecular hydrogen bonding the ortho isomer (B) is less acidic than the para isomer(D).
Case III
When the phenyl ring has substituent groups which show +R and –I effects.
For example, specify which group has (+R) and (–I) effect and compare the acidic strength of the following:
(A) (B) (C)
CH3 CH3 CH3
CH3
OCH3
OCH3
CH2 CH2 CH2

OCH3
OCH3
OCH3
Destabilized by
Destabilized
+ R effect of OCH3
+ R effect of Stabilized by and stabilized by
OCH3 and stabilized –1 of OCH3 –1 effect of OCH3
by –1 of OCH3
and –1 effect is
–1 is maximum
minimum
B>A>C
Acidic strength
Example:
OH OH OH
OCH3
OCH3
OCH3
B>A>C
Acidic strength
Illustrations
56. Account for the fact that (a) p-NO2C6H4COOH is more acidic than the meta isomer and (b) the reverse is true for
the Cl acids.
Ans. (a) Through resonance, wt-NO2 can induce a + charge at the C’s ortho to the C bearing the COO-. This process
is less effective because the induced charge is once removed from the C bonded to COO‑. m-Nitrobenzoic acid
is thus less acidic. (b) By resonance interaction p-Cl places a-charge, not a + charge, on the p-C of the ring, an
effect that is of minimal significance. Cl is an EWG by induction, and its effect is stronger from the nearer meta
position.
57. (a) Why are both p-Me and m-Me substituted acids weaker than PhCOOH, with the p-acid being the weaker one?
(b) Why is the p-OH acid weaker than PhCOOH while the m-OH acid is stronger?
Ans. (a) Both p-and m-Me are electron-donating and acid-weakening. Hyperconjugation permits a p-Me to put a little
extra S-on the ring C bearing the —COO-, resulting in more effective electron-donation and acid-weakening,
(b) Through resonance interaction, p-OH places an additional-charge on the carboxyate group (see C), an acid-
weakening effect that predominates over its electron-withdrawing, acid-strengthening inductive effect. A m-OH
cannot do this and behaves only inductively as an EWG to increase acidity.
O
+
HO C
O
C
58. Account for the differences in acidities: (a) PhCH2COOH or H2C = CHCH2COOH> CH3CH2COOH, and (b) N =
CCH2COOH or CH3COCH2COOH > CH3CH2COOH.
Ans. (a) The sp2 hybridized C’s of Ph and —C=C— attract the bonded electrons more than do the sp3 hybridized C’s.
Consequently Ph— and —C = C— are acid-strengthening EWG’s. (b) Because of S + on C, the polarized [d+C=O
d–
] and [d+C ≡ Nd–] are acid-strengthening EWG’s. The C of C=O uses sp2 HO’s and the C of C=N uses sp HO’s,
further enhancing the electron-withdrawal properties of these groups.
59. Would you expect 3-butenoic acid or 3-butynoic acid to be stronger?
Ans. The —C ≡ C —, whose C’s use sp HO’s, is a better EWG than is C=C whose C’s use sp2 HO’s. HC ≡
CCH2COOH (pKa = 3.32) is a stronger acid than H2C = CHCH2COOH (pKa = 4.35).
60. o-Nitrobenzoic acid (pKa = 2.21) is stronger than 3,5-dinitrobenzoic acid (pKa = 2.80) in water, whereas in
ethanolic solutions the opposite is true (their respective pKa’s in EtOH are 8.62 and 8. 09). Suggest a possible
reason for (a) the weaker acidities in ethanol and (b) the inversion of acidities in water.
Ans. (a) EtOH is a weaker base and a poorer ion-solvater than is H2O. Thus, the ionization equilibrium lies more to
the left in EtOH where the acids are weaker, (b) The DS of ionization has a greater influence on pKa in water
which is the better solvating medium. o-Nitrobenzoic acid is probably a stronger acid in water because of a more
favourable DS. In ethanol, where the entropy term is less significant, 3,5-dinitobenzoic acid may be stronger because
of a more favourable DH that can arise from the inductive effect of two nitro groups even though they are meta.
Me
61. Explain why highly-branched acids such as Me3CCH2CCOOH are less acidic than unbranched acids.
CMe3
Ans. The —COO-of the branched acid is shielded from solvent molecules and cannot be stabilized as effectively as can
an unhindered anion.
62. Use conformational theory to explain why (a) trans-4-Nbutylcyclohexanecarboxylic acid is stronger than the
cis-isomer, and (b) exo-2-norbornanecarboxylic acid is more acidic than the endo-isomer.
Ans. In both cases the less sterically-hindered is — COO-toward solvation, the stronger is the acid, (a) The COO-in the
trans-isomer is equatorial, less hindered and better solvated. Thus the trans acid is stronger. (b) Exo-COO-is more
exposed to solvent and the exo acid is stronger.
63. (a) Write the chemical equations for the complete dissociation of a typical dicarboxylic acid, HOOC(CH2)
n
COOH. (b) Give a relative comparison of pKa1 and pKa2 and justify your answer.

HOOC(CH2)nCOOH + H2O ← 
→ HOOC(CH ) COO– + H O+ pK
 2 n 3 a1

HOOC(CH2)nCOO– + H2O ← 
→ –OOC(CH ) COO– + H O+ pK
 2 n 3 a2
monoanion dianion
(b) Since it takes more free energy to remove an H+ from an anion than from a molecule, pKal is smaller pKa2 (Ka1
> Ka2).
64. What factor influences the acidity of the monoanions of malonic and succinic acids but not those of oxalic,
glutaric, or adipic acids?
Ans. In general, the acidity of an H is weakened if it participates in H-bonding because its ionization requires more
free energy to break the H-bond. This occurs between COOH and COO– of the acid monoanions of malonic, that
forms a five-membered ring (not counting the very small H), and succinic, that forms a six-membered ring as
shown:
H H
– O – O
O O
O=C C=O O=C C=O

CH2 CH2 CH2
Malonate monoanion Succinate monoanion
In the oxalate monoanion, the OH and O are less able to form an H-bond because they are spacially more
separated than in the malonate and succinate monoanions. In the glutarate and adipate monoanions, the rings
formed as the result of intramolecular H-bonding are seven-and eight-membered respectively. Formation
of these rings is unfavourable because of an appreciable loss in entropy. Consequently, H-bonding is less
significant.
65. Account for the fact that (a) maleic acid is a stronger acid than fumaric acid but maleate monoanion is a weaker
acid than fumarate monanion and (b) phthalic acid is stronger than either isophthalic or terphthalic acids but
phthalate monoanion is weaker than isophthalate and terphthalate monoanions.
Ans. In both cases H-bonding and the field effect in the monoanion are the key factors, (a) Maleic acid is stronger
because the H-bonding between the COOH and COO-stabilizes its monanion. However, this same H-bonding
weakens the acidity of the monoanion. The acidity is also attenuated because of the field effect generated by —
COO-on the nearby —COOH. In general, the closer are the COOH’s, the larger is DpKa. The trans COOH and
COO-in fumaric acid are too far apart for H-bonding or any significant field effect.
O
H H H H
HOOC H C H C=C
C=C HO C=C C=C O=C C O
H COOH H C HOOC COOH
O O O O
– H
Fumaric acid (weaker) Fumarate monoanion Maleic acid (stronger) Maleate monoanion
(no H-bonding and (H-bonding and
meager field effect) strong field effect)
(b) In phthalic acid the ortho groups are close enough to participate in H-bonding and to exert a field effect as
is the case in maleic acid. The meta groups in isophthalic acid and the para groups cannot exert a field-effect
because they are too far apart as is the case in fumaric acid. Hence, phthalic acid is the strongest of the three
acids because H-bonding stabilizes its conjugate base, the monoanion. However, this same H-bonding makes the
monoanion the weakest acid.
66. Account for the fact that salicylic acid, o-HOC6H4COOH, is a stronger acid than o-CH3OC6H4COOH.
Ans. We might expect the electronic effects of —OH and —OCH3 to be about the same. If anything, the —OCH3
might be more acid-strengthening because it is bulkier (ortho effect). The answer lies in the ability of salicylate
ion to undergo intermolecular H-bonding (the dominant factor) as shown, thereby stabilizing the conjugate base
and enhancing acidity.
O O H O O
C C H
O H + O
–H
67. R elative acidities have been determined in the gas phase by instrumental techniques, (a) Give the most important
advantage of these methods over studies in solvent for determining relative acidities. (b) Explain the following
gas phase observations that are contrary to findings in solution: Propanoic acid > acetic acid; chloroethanoic acid
> fluoroethanoic acid; t-butanol > n-butanol.
Ans. (a) In the gas phase one obtains the intrinsic acidities, free of the role of base and solvent. (b) Since each result
is opposite to what is expected from inductive effects, it appears that electronic effects are not pertinent. In
each case the larger anion is more stable. Apparently the stability of the anion is directly related to the ease of
polarization, which in turn is directly related to size.
BASES
pKb, pKBH⊕ and pKa

The strength of a base, B:, in water, may be determined by considering the equilibrium:
B : + HOH BH ⊕ + Θ OH
The equilibrium constant in water, Kb, is then given by:

[BH ⊕ ][Θ OH]
Kb ≈
[B :]
The [H2O] term is incorporated into Kb, because water is present in such excess that its concentration does not change
significantly; here again, concentrations can commonly be used instead of the more correct activities provided the solution
is reasonably dilute.
It is, however, now more usual to describe the strength of bases also in terms of Ka and pKa, thereby establishing a
single continuous scale for both acids and bases. To make this possible we use, as our reference reaction for bases, the
equilibrium
BH ⊕ + H 2 O : B : + H 3 O ⊕
for which we can then write,
[B :][H 3 O⊕ ]
Ka ≈
[BH ⊕ ]
where Ka (and pKa) is a measure of the acid strength of the conjugate acid, BH⊕, of the base, B:. This measure of the readiness
with which BH⊕ will part with a proton is, conversely, a measure of the lack of readiness with which the base, B:, will
accept one: the stronger BH⊕ is as an acid, the weaker B; will be as a base. Thus the smaller the numerical value of pKa for
BH⊕, the weaker B: is as a base. When using pK to quote the strength of a base, B:, pKBH⊕ should actually be specified but
it has become common—though incorrect—to write it simply as pKa.
BASICITY
Aliphatic Bases
(a) Inductive effect and solvation
As increasing strength in nitrogenous bases is related to the readiness with which they are prepared to take up protons, and
therefore, to the availability of the unshared electron pair on nitrogen, we might expect to see an increase in basic strength
on going: NH3 → RNH2 → R2NH→ R3N, due to the increasing inductive effect of successive alkyl groups making the
nitrogen atom more negative. An actual series of amines was found to have related pKa values as follows, however:
Me Me
Me NH 2 NH Me N
Me Me
10.64 10.77 9.80
NH3
9.25 Et Et
Et NH 2 NH Et N
Et Et
10.67 10.93 10.88
It will be seen that the introduction of an alkyl group into ammonia increases the basic strength markedly as expected.
The introduction of a second alkyl group further increases the basic strength, but the net effect of introducing the second
alkyl group is very much less marked than with the first. The introduction of a third alkyl group to yield a tertiary amine,
however, actually decreases the basic strength in both the series quoted. This is due to the fact that the basic strength of
an amine in water is determined not only by electron-availability on the nitrogen atom, but also by the extent to which the
cation, formed by uptake of a proton, can undergo solvation, and so become stabilized. The more hydrogen atoms attached
to nitrogen in the cation, the greater the possibilities of powerful solvation via hydrogen bonding between these and
water.
H2 O: H
• •• H 2 O: H
• •• H2 O: H • ••
| | |
R N⊕ H• • • • OH 2 > R N⊕ R > R N⊕ R
| | |
H2 O: • •• H H2 O: • •• H R
Decreasing stabilisation by solvation
Thus, on going along the series, NH3 → RNH2 → R2NH → R3N, the inductive effect will tend to increase the basicity,
but progressively less stabilisation of the cation by hydration will occur which will tend to decrease the basicity. The net
replacing effect of introducing successive alkyl groups thus becomes progressively smaller, and an actual changeover takes
place on going from a secondary to a tertiary amine. If this is the real explanation, no such changeover should be observed
if measurements of basicity are made in a solvent in which hydrogen-bonding cannot take place; it has, indeed, been found
that in chlorobenzene the order of basicity of the butylamines is
BuNH2 < Bu2NH < Bu3N
Tetralkylammonium salts, e.g., R4N⊕ I-, are known, on treatment with moist silver oxide, AgOH, to yield basic solution
comparable in strength with the mineral alkalis. This is readily understandable for the base so obtained, R4N⊕ –OH, is
bound to be completely ionised as there is no possibility, as with tertiary amines etc.
⊕
R 3 NH + − OH → R 3 N : + H 2 O
of reverting to an unionised form. The effect of introducing electron withdrawing groups, e.g., Cl, NO2, close to a basic
center is to decrease the basicity, due to their electron withdrawing inductive effect. Thus the amine
F3C
F3C N:
F 3C
is found to be virtually non-basic, due to the three powerfully electron withdrawing CF3 groups.
(b) Hybridization
Though pyridine is a base, it is much weaker than the aliphatic amines. This has been explained on the basis of the state of
hybridization of nitrogen atom in these compounds. In aliphatic amines, the unshared pair of electrons is in an sp2 orbital
while in pyridine, it is in the sp2 orbital. Obviously, the nitrogen atom in the sp2 state retains a greater hold on the unshared
pair of electrons than a nitrogen atom in the sp3 state, and is, therefore, less readily available for bonding with protons.
(c) Resonance effect
In general, aromatic amines are far less basic than aliphatic amines. This can be ascribed to relative resonance stabilization
of the free bases and the corresponding conjugate acids (anilinium ions). In aniline, for instance, the unshared electron pair
on nitrogen gets delocalized over the aromatic ring and is less readily available for co-ordination with a proton (aniline
becomes more stable). Further, the anilinium ion formed after protonation lacks this stabilization as the lone pair of
electrons on nitrogen becomes localized when nitrogen-proton bond is formed.
⊕ ⊕ ⊕
NH2 NH2 NH2 NH2
⊕
NH3
Base strength of amino nitrogen is further reduced in nitroanilines. This can be explained by the fact that these substituted
anilines are still more stabilized than substituted anilinium ions. Comparison of the base strengths of p-and m-nitroanilines
provides another interesting example of resonance effect. m-Nitroaniline is somewhat stronger than p-nitroaniline as
the lone pair on nitrogen in p-nitroaniline is stabilized due to extended resonance and in m-nitro-aniline only a weak
electron-withdrawing inductive effect operates which makes lone pair a little more readily available for protonation in the
latter compound.
⊕
NH2 NH2
etc
⊕ ⊕
N N
O O O O
In contrast, if an electron-releasing substituent (OH, OCH3) is present in o-and p-position, it makes the lone pair of
nitrogen more easily available due to mesomeric electron-release.
Base strength can considerably increase on account of resonance stabilization of the cation as compared to free base.
Guanidine, which is stabilized by resonance is a very strong base because protonation of the imino nitrogen leads to the
formation of guanidinium ion which has more resonance stabilization than the free base, as all its contributing forms are
equivalent.
NH NH NH
C ⊕ C C ⊕
H 2N NH2 H2N NH2 H2N NH2
⊕
H
⊕
NH2 NH2 NH2
C ⊕ C C ⊕
H 2N NH2 H2N NH2 H2N NH2
(d) Steric effects

Since a proton occupies a very small volume, steric effects are not of much significance in proton transfer reactions.
However, steric effects may indirectly influence base strength by interfering in resonance stabilization. Since all the atoms
of a delocalized system must He in one plane, any steric factor that prevents atoms from assuming coplanarity reduces
resonance and, therefore, destabilizes the whole system. For example, steric inhibition of resonance increases the base
strength of N,N,2,6-tetramethylaniIine relative to N, N-dimethylaniline, The ortho methyl groups in the former compress
the N-methyl groups in the conformation needed for maximum delocalization of the unshared electron pair on nitro
gen with the aromatic ring. Thus, coplanarity of the ring and the dimethylamino substituent is prevented. No such steric
factor operates in the latter as there is enough space to accommodate methyl groups attached to the nitrogen and the ortho
hydrogen atoms.
H3C CH3 H3C ⊕ CH3

N N
H H
H 3C ⊕ CH3
H3C CH3 N
N
H 3C CH3 H 3C CH3
On similar lines, we can explain with N, N-dimethylpicarmide is a stronger base than picramide.
H H H ⊕ H
N N
O 2N NO2 O2N NO2
NO2 N
Picromide O ⊕ O
H 3C CH3 H3C CH3

N ⊕
O 2N NO2 N
O2N NO2
NO2
N
O ⊕ O
A dramatic example of steric effects is provided by a study of relative stability of complexes formed by the reaction
of triethylamine and quinuclidine trimethylborane. Towards proton acids, both the amines have comparable base strength
but the trimethylborane complex of triethylamine is unstable in contrast to the very stable complex corresponding to
quinuclidine. The difference in behaviour can be rationalized on the consideration that the substituents in the latter amine
are held back by the ring system, while freely rotating ethyl group of the former block the approach of the Lewis acid to
the nitrogen.
CH3 CH3
H 2C H2C
Me
H 3C ⊕
N + B Me3 H3C N B Me
H2C H2C Me
H2C
CH2 CH3
CH3
Triethylamine
+ B Me3 ⊕
N N
B
Me Me
Me
Thus, amides are found to be only very weakly basic in water [pKa for ethanamide(acetamide) is ≈ 0.5], and if two C =
O groups are present the resultant imides, far from being basic, are often sufficiently acidic to form alkali metal salts, e.g.,
benzene-1,2-dicarboximide (phthalimide, 8):
O Oδ−
OH
N H Nδ−
O Oδ−
The effect of delocalization in increasing the basic strength of an amine is seen in guanidine, HN = C(NH2)2 (9), which,
with the exception of the tetraalkylammonium hydroxides above, is among the strongest organic nitrogenous bases known
⊕
with a related pKa of ≈ 13.6. Both the neutral molecule, and the cation, H 2 N = C(NH2)2 (10), resulting from its protonation,
are stabilised by delocalization;
⊕
NH2 NH2 NH2
Neutral
C C C ⊕
HN NH2 HN NH2 HN NH2 molecule
(9a) (9b) (9c)
⊕
⊕ H
NH2 NH2 NH2
C C C ⊕
NH2 Cation
⊕
H2N NH2 H2N NH2 H 2N
(10a) (10b) (10c)
but in the cation the positive charge is spread symmetrically by contribution to the hybrid of three exactly equivalent
structures of equal energy. No comparably effective delocalization occurs in the neutral molecule (in which
two of the contributing structures involve separation of charge), with the result that the cation is greatly
stabilized with respect to it, thus making protonation ‘energetically profitable’ and guanidine an extremely strong
base.
A somewhat analogous situation occurs with the amidines, RC(=NH)NH2(11):
R R
C C ⊕
HN NH2 HN NH2 Neutral
molecule
(11a) (11b)
⊕
H
R R
⊕ C C ⊕
H 2N NH2 H 2N NH2 Cation
(12a) (12b)
While stabilization by delocalization in the cation (12) would not be expected to be as effective as that in the guanidine
cation (10) above, ethanamidine, CH3C(=NH)NH2 (pKa = 12.4), is found to be a much stronger base than ethylamine,
MeCH2NH2 (pKa = 10.67).
Ortho and Para Effects

Basic concepts of resonance, steric effect and steric inhibition of resonance have been widely used when interpreting
reactivities of crowded conjugated molecules. Ortho effect is used in following cases:
1. Benzoic acid: Ortho-substituted benzoic acid is stronger than benzoic acid.

CO2H CO2H
CH3
>
2. Aniline: Ortho-substituted aniline is a weaker base than aniline.
NH2 NH2
CH3
>
3. Para-substituted aniline is a strong base because of effects known as para effects.

NH2 NH2
OCH3
>
OCH3
Compare basic strengths of the following compounds:
NH2 NH2 NH2
CH3
36.
CH3
CH3
(A) (B) (C)
NH2 NH2 NH2 NH2
NO2
37.
NO2
NO2
(A) (B) (C) (D)
SOLUTIONS
C > B > A
36. + H effect + 1 effect Ortho effect

D > B > C > A
37. Lone –1 effect –R effect Ortho

pair is not of NO2 of – NO2 effect
involved in
resonance
Illustrations
68. Arrange ethylamine, 2-amino ethanol and 3-amino-1-propanol in the order of decreasing basicity and give your
reason.
Ans. CH 3CH 2 NH 2 > HO(CH 2 )3 NH 2 > HO(CH 2 ) 2 NH 2.
The electron withdrawing inductive effect of the OH group decreases the electron density on nitrogen, thus
lowering the amine’s basicity. this effect diminishes with distance from the amino group.
69. Account for the following order of increasing basicity:
RC ≡ N: < R'CH = NR < RNH2
nitrile imine amine
Ans. The more s character in the hybrid orbital of the N with the unshared pair of e–s, the less basic is the molecule.
The nitrile N using sp HO’s has the most s character, the imine N using sp2 HO’s has the intermediate s character,
and the amine N using sp3 HO’s has the least s character.
70. Compare the basicities of
(a) H2C = CHCH2NH2, CH3CH2CH2NH2 and HC ≡ CCH2NH2, and
(b) C6H5CH2NH2, cyclohexyl – CH2NH2 and p-NO2C6H4CH2NH2.
Ans. (a) The significant difference among these three bases is the kind of hybrid orbital used by Cb — the more s character
it has, the more electron-withdrawing (by induction) and base weakening it will be. The HO conditions are
H2C = CbHCH2NH2(sp2), CH3CbH2CH2NH2(sp3), and HC ≡ CbCH2NH2(sp). The increasing order of electron –
attraction is propargyl > allyl > propyl >, and the decreasing order of basicity is
CH3CH2CH2NH2> H2C = CHCH2NH2 > HC ≡ CCH2NH2
(b) The decreasing order is
β
CH2NH2 > C6H5CH2NH2 > P-NO2C6H4CH2NH2
The Cb is cyclohexyl – CH2NH2 uses sp3 HO’s while Cb in the benzylamines uses sp2 HO’s. The electron
withdrawing p-NO2 makes the phenyl ring even more electron–withdrawing and base weakening.
71. Account for the fact that although N,N—dimethylaniline is only slightly more basic than aniline, 2,6-dimethyl
N,N-dimethylaniline is much more basic than2,6 – dimethylaniline.
Ans. Extended p bonding between the amino N and the ring requires that the s bonds on N become coplanar with the
ring and its ortho bonds. Bulky substituents in the ortho 2,6 – positions sterically hinder the attainment of this
geometry and interfere with the base – weakening extended p bonding. This effect is called steric inhibition of
resonance.
CH 3
H CH 3 CH 3
N+ N
CH 3 CH 3
H CH 3
72. The amino group in ethyl amine is basic whereas that in acetamide is not basic. Explain.
Ans. In amides the lone pair of electrons on nitrogen atom is delocalized and hence less available for protonation than in
amines where no resonance is possible and thus acetamide is a weaker base than ethylamine.
O O–
C C
+
H3 C NH2 H3 C NH2
73. Account for the fact that 2-aminoethanoic acid (glycine) exists as a dipolar ion, as does p-aminobenzenesulfonic
acid (sulfanilic acid) but p-aminobenzoic acid does not.
Ans. The aliphatic NH2 is sufficiently basic to accept an H+ from COOH. the COOH is not strong enough to donate H+
to the weakly basic ArNH2, but SO3H is a sufficiently strong acid to do so.
H3N+ – CH2COO– P – H2N – C6H4 – COOH P – H3N+ – C6H4 – SO3–
74. Account for the following order of decreasing basicities:

C6H5NH2 (A) > m-NO2C6H4NH2 (B) > p-NO2C6H4NH2 (C) > o-NO2C6H4NH2 (D)
Ans. NO2 is electron-withdrawing, by induction from all positions but mainly by extended p bonding from the ortho
and para positions. Therefore all the nitroanilines are less basic than aniline, and so C is less basic than B. D
is less basic than C because its NO2 is closer and exerts a stronger inductive effect. Figure below shows the
resonance hybrid of the para-NO2 compound.
O– + + H
N N
O– H
75. Account for the following order of decreasing basicities:

(a) p-CH3OC6H4NH2 (E) > C6H5NH2 (A) > o-CH3OC6H4NH2 (F) > m-CH3OC6H4NH2 (G)
(b) p-CH3C6H4NH2 (H) > m-CH3C6H4NH2 (I) > C6H5NH2 (A) o-CH3C6H4NH2(J)
Ans. (a) CH3O is strongly electron-donating from the ortho and para positions by extended p bonding.
This effect completely submerges the electron-withdrawing inductive effect from these positions
leaving only the meta position where inductive withdrawal dominates. This discussion is consistent with the
declining basicity order E > A > G. But why is F weaker than A? This is an example of the ‘ortho effect’ first noted
with substituted benzoic acids. All o-substituted anilines are less basic than p-substituted anilines regardless of
the electronic effect of the substituent. This effect is attributed to steric hindrance by the o-substituent to solvation
of the cation. This steric effect destabilizes the cation making the amine a weaker base.
(b) CH3, A typical alkyl group, is inductively electron-donating and base-strengthening from all positions.
Moreover, if the R group has a benzylic H, as does CH3, it is electron-donating by hyperconjugation from the
ortho and para positions. Hence the decreasing order of basicity is H (hyperconjugation and induction) > I
(induction) > A > J (ortho effect).
76. Account for the fact that (a) 4-cyanoaniline is slightly more basic than 4-nitroaniline, and (b) 3,4,5-trinitroaniline
is more basic than 4-cyano-3,5-dinitroaniline.
Ans. (a) The NO2 that ends up with the-charge on the more electronegative O more effectively participates in base-
weakening electron delocalization with the amino N than does CN that ends up with the-charge on the less
electronegative N. (b) In order for NO2 to be base-weakening, its O’s must become coplanar with the ring. Bulky
substituents on the adjacent 3,5-positions sterically hinder the attainment of this coplanarity, thereby inhibiting
the base-weakening ability of NO2 [Fig. (a)]. CN is a linear group and does not encounter this steric inhibition of
resonance as shown in Fig. (b). Note that this steric inhibition of resonance occurs at the substituent, not at the
amino group.
O 2N O2N
– +
steric O + NH2
NH2 N C
–
hindrance N
O O2N
O 2N
(a) (b)
77. Explain why Me3NCH2CH2NH2 is a weaker base than Me3CCH2CH2NH2.

Ans. Inductively the N+ is strongly electron-attracting and base-weakening. However, the effect of the + charge
is also transmitted through space and not just through the chain of a bonds. This is an example of the field
effect.
ISOMERISM
Structural Isomerism
Compounds which possess the same molecular formula but differ in bonding arrangement of atoms (or) groups within the
molecule, i.e., differ in structure [A structural formula for a compound conveys which atom is directly linked to which
other atom. It, however, tells nothing about the shape of the molecule but indicates the groups of elements present which
provide clues to the properties of the substance], are structural isomers and this phenomenon is known as structural isom-
erism.
(i) Chain or nuclear isomerism
In this type the isomers differ in the variation of the carbon chain (or) skeleton of the molecule. The same molecular for-
mula may represent a straight chain of carbons as well as a branched chain. The molecular formula C4H10 stands for two
isomers namely n-butane and isobutane.
H3C CH3
CH
CH3 CH2 CH2 CH3 ≡ and ≡
n − Butane CH3
isobutane (2 methyl propane)
C5H12 stands for three chain isomers
(i) CH 3CH 2 CH 2 CH 3CH 3 ≡
(n-pentane)
CH3
CH CH3
(ii) H3C CH2 ≡
isopentane
CH3
(iii) H3C C CH3 ≡
CH3
neopentane (2,2-dimethyl propane)
Cyclohexane and methyl cyclopentane are nuclear isomers
CH3
CH2
H2C CH2 CH
H2C CH2
H2C CH2 H2C CH2
CH2
C4H10O
CH3
OH
H3C OH and H3C
butan-1-ol 2-methylpropan-1-ol
Note:
(1) Except alkynes, chain isomerism is observed when the number of carbon atoms is four or more than four.
(2) Chain isomers differ in the nature of carbon chain, i.e., in the length of the carbon chain.
(3) The isomers showing chain isomerism belong to the same homologous series, i.e., functional group, class of the com-
pound (cyclic or open) remains unchanged.
(4) Chain and position isomerism cannot be possible together between two isomeric compounds. If two compounds are
chain isomers then these two will not be positional isomers.
Illustrations
78. Give the possible chain isomers for propyl benzene.

H3C CH3
CH 2 CH 2 CH 3
Ans.
propylbenzene isopropylbenzene
79. Give the possible chain isomers for C5H13N

NH2
Ans. H3C
CH3
H3C NH2 H3C
CH3 NH2
CH3
(ii) Position isomerism

In it, the isomers differ in the attachment of the functional group (or) substituents to the carbon chain. This is illustrated
by the following examples.
(i) CH 3CH 2 CH = CH 2 ≡ and CH 3 − CH = CH − CH 3 ≡

But-1-ene But-2-ene
Cl
(ii) Cl and H3C
H3C
1-chloropropane CH3
2-chloropropane
CH3
(iii) H3C CH3 and H3C CH3
3-methylpentane
CH3
2-methylpentane
Illustration
80. Give the possible positional isomerism for di chlorobenzene.

Ans.
Cl Cl Cl
Cl
Cl
1,2-dichlorobenzene 1,3-dichlorobenzene
Cl
1,4-dichlorobenzene
Note: In the aromatic series, the disubstitution products of benzene also exhibit isomerism due to different
relative positions occupied by the two substituents on the benzene ring.
(iii) Functional isomerism

If the molecules have the same molecular formula but differ in the type of the functional group, then it is known as func-
tional group isomerism. A few examples of functional isomers are:
(a)
Molecular formula p-alcohol s-alcohol t-alcohol Ethers
C2H6O H3C –– –– H3C O
OH CH3
ethanol dimethyl ether
C3H8O OH H3C –– H3C O

H3C
OH CH3
H3C
OH CH3 H3C O CH3
C4H10O H3C OH CH3 H3C CH3 O

H3C H3C CH3
OH
CH3 H3C O
OH CH3
H3C
H3C
(b) Monocarboxylic acids and esters are functional isomers.

H3C O
OH and H3C
O O
propanoic acid H3C
methyl acetate
(c) Aldehydes, ketones, unsaturated alcohols and alkene oxides are functional isomers.
H3C H2C O
(i)
C 2H4O OH
O Ethylene oxide
Ethanal Vinyl alcohol
O
(ii)
H3C H2C
H3C OH
C 3H6O
O CH3 Allyl alcohol
Propanal Propanone
(iii) Cyanides are isomeric with isocyanides

RCN (Alkyl cyanide) RNC (alkyl isocyanide)
(iv) Nitroalkanes are isomeric with alkyl nitrites.

O
R O
R N
N O
O
Nitroalkane Alkyl Nitrite
(v) Aromatic alcohols may be isomeric with phenols.

OH
CH3
OH
phenylmethanol o-cresol

(vi) Sometimes a double bond containing compound may be isomeric with a triple bond containing compound. This
is also called as functional isomerism. Thus butyne is isomeric with butadiene (Molecular formula C4H6).
H3C H2C
CH CH2
but-1-yne buta-1,3-diene

(vii) Primary, secondary and tertiary amines of some molecular formula are also the functional isomers.
CH3
H3C H3C NH
H3C N
NH2 C 2H5
CH3
propan-1-amine N-ethyl-N-methylamine N,N,N-trimethylamine

38.
I II III
Among these, positional isomers are
(a) I and II (b) I and III
(c) II and III (d) All of these
39.

I II III
Among these, positional isomers are
(a) I and II (b) I and III
(c) II and III (d) none of these
SOLUTIONS
38. (a) 39. (d)
Illustrations
81. C4H8 can have so many isomers. Write their structures.

Ans. C4H8 can have following structures:
(a) CH3—CH2—Ch=CH2 1-butene (b) CH3—CH=CH—CH3 2-butene, (cis and trans)
(c) CH3—C=CH2 2-methyl-1-propene (d) Cyclobutane
|
CH3
(e) methyl cyclopropane
82. Give the functional isomer for acetic acid

2 2
Ans. +& +
2+ 2 &+
DFHWLFDFLG PHWK\OIRUPDWH
Monocarboxylic acids and Ester’s are functional isomers.
83. Give the functional isomer for acetaldoxime.

O
Ans. H3C
H3C
N OH
NH2
(1E)-acetaldehyde oxime
acetamide
Oximes and amides are functional isomers.

84. Give the functional isomer for ethyl thioalcohol.
Ans. H3C H3C S
S H CH3
ethanethiol (methylthio)methane
Thioalcohols and thio ethers are functional isomers.
Metamerism
It arises when different alkyl radicals are joined with the same divalent functional group present in the molecule, e.g.,
ethers, thioethers, secondary amines, ketones, esters etc.
O H3C O
(a) H3C O CH3 H3C CH3
CH3
diethyl ether 1-methoxypropane
H3C
2-methoxypropane
S H3C S
(b) H3C S CH3 H3C CH3
CH3
(ethylthio)ethane 1-(methylthio)propane
H3C
2-(methylthio)propane
Illustration
85 Give the metamer for ethyl propionate.

O
O CH3 CH3
Ans. H3C H3C O
propyl acetate
O
ethyl propionate
Ring chain isomerism

This type of isomerism is due to difference in way of linking of carbon atoms and the isomers may have either open chain
(or) closed chain structure e.g., alkenes and cycloalkanes.
(a) C3H6
+ &
&+ F\FORSURSDQH
SURSHQH
(b) C4H8
&+
+& +&
+ & &+
&+ &+ &+
EXWHQH F\FOREXWDQH PHWK\OF\FORSURSDQH
EXWHQH
PHWK\OSURSHQH
(c) C6H12
+& &+
&+
KH[HQH
F\FORKH[DQH PHWK\OF\FORSHQWDQH
Note: Ring chain isomers are always functional isomers.
Number of Structural Isomers

Number of structural isomers corresponding to any molecular formula (say C7H16) can be written by the following
methods:
(1) Start with the longest possible straight chain. In case of C7H16, this will give n-heptane.
CH3— CH2— CH2— CH2— CH2— CH2— CH3
n-heptane
(2) Shorten the chain by one carbon, and add ‘extra’ carbon as a methyl group at all possible positions, starting with the
left hand side carbon and moves to the right. This generates the methyl hexanes.
OR
Shorten the chain by one carbon and write all possible positional isomers of methylcyclohexane. You must check each
isomers you make to be sure it is not a repeat by IUPAC nomenclature.
CH3–CH–CH2–CH2–CH2–CH3 CH3–CH2–CH–CH2–CH2–CH3
CH3 CH3
2-Methylhexane (2) 3-Methylhexane (3)
CH3–CH2–CH2–CH–CH2–CH3 CH3–CH2–CH2–CH2–CH–CH3
CH3 CH3
3-Methylhexane (repeat) 2-Methylhexane (repeat)
(3) Shorten the chain by one more carbon (i.e., five carbon straight chain). Two carbons to be added as two methyl groups
or a single ethyl group. Two methyl groups can be placed either on the same carbon or different carbons. Again start
at the left most carbon and move to the right, checking each isomers to be sure it is not a repeat.
CH3
CH3–C–CH2–CH2–CH3
CH3
2, 2-Dimethylpentane (4)
CH3
CH3–CH2–C –CH2–CH3
CH3 Two methyl groupe on
the same carbon
CH3
CH3–CH2–CH2 –C –CH3
CH3
2, 2-Dimethylpentane (repeat)
CH3–CH–CH –CH2 –CH3
CH3 CH3
CH3–CH–CH2 –CH –CH3
Two methyl groupe on
CH3 CH3 different carbon
CH3–CH2–CH –CH –CH3
CH3 CH3
2, 3-Dimethylpentane (repeat)
WriteWrite
all possible isomers
all possible of ethyl
isomers pentane
of ethyl pentane
CH
CH33–CH–CH
–CH–CH22–CH
–CH22–CH
–CH33 CHCH–CH
3 3
–CH –CH–CH
–CH–CH
2 2
–CH
2 2
–CH
3 3
CH32–CH33 CHCH–CH3 3
2 3–CH
3-Methylhexane(repeat)
3-Methylhexane (repeat) 3-Ethylpentane (8)(8)
3-Ethylpentane
(4) Shorten the chain again and try to fit the three extra carbons on a butane chain. This will give only one structure.
CH3
CH3 C CH CH3
CH3 CH3
2,2,3-Trimethylbutane (9)
Thus, C7H16 has 9 isomers.
Number of Structural Isomers

Table 2.7 Number of structural isomers
Molecular formula Number of isomers

Alkanes:
C4H10 Two
C5H12 Three
C6H14 Five
C7H16 Nine
C8H18 Eighteen
C9H20 Thirty five
C10H22 Seventy Five
Molecular formula Number of isomers

Alkenes and cycloalkanes:
C3H6 Two (One alkene + one cycloalkane)
C4H8 Six (Four alkenes + 2-cycloalkane)
C5H10 Nine (Five alkenes + 4-cycloalkane)
Alkynes:
C3H4 Two
C4H6 Six
Monohalides:
C3H7X Two
C4H9X Four
C5H11X Eight
Dihalides:
C2H4X2 Two
C3H6X2 Four
C4H8X2 Nine
C5H10X2 Twenty one
Alcohols and ethers:

C2H6O Two (One alkene and one ether)
C3H8O Three (two alcohols and one ether)
C4H10O Seven (Four alcohols and three ethers)
C5H12O Fourteen (eight alcohols and six ethers)
Alkenes and ketones:

C3H6O Two (one aldehyde and one ketone)
C4H8O Three (two aldehydes and one ketone)
C5H10O Seven (four aldehydes and three ketones)
Monocarboxylic acids and esters:
C2H4O2 Two (one acid and one ester)
C3H6O2 Three (one acid and two esters)
C4H8O2 Six (two acids and four esters)
C5H10O2 Thirteen (four acids and nine esters)
Aliphatic amines:
C2H7N Two (one 1°-amine and one 2°-amine)
C3H9N Four (two 1°-amines, one 2°-amine and one 3°-amine)
C4H11N Eight (Four 1°-amines, three 2°-amines and one 3°-amine)
Aromatic compounds:
C8H10 Four
C9H12 Nine
C7H8O Five
TAUTOMERISM
It is a special type of functional isomerism, in which the isomers are readily interchangeable and maintain a dynamic
equilibrium with each other. Hence, the name dynamic isomerism. Both the isomers represent one and a single substance.
This isomerism is caused by the oscillation of a hydrogen atom between two polyvalent atoms with necessary rearrange-
ment of linkage.
This type of isomerism in which a substance behaves as if it has two different structures is known as tautomerism
and different forms are called as tautomers. Tautomerism is also known as desmotropism (Desmos = bond,
tropos = turn)
Structural requirements for tautomerism

(i) Compound should have electronegative atom bonded with multiple bond (i.e., N and O).
(ii) Compound should have at least one acidic hydrogen present on a-carbon of the molecule.
If these two conditions are fulfilled, then compound will show tautomerism. For example,
O O
α Electronegative atom α Electronegative atom
H3C H3C
H CH3
α Electronegative atom
H3C N Electronegative atom
α
N O H3C
CH3
O
These compounds fulfil both the conditions, hence these will show tautomerism.
CH3 O C 6H5 O C 6H5
H3C H3C N H5C 6
α CH3 H α C 6H5 O α CH3 N
In these compounds, electronegative atom is bonded with multiple bond, but the compound has no hydrogen on a-
carbon, hence these compounds will not show tautomerism.
If the compound has active methylene group (or) active methyne group, then a-carbon for tautomerism is always car-
bon of active methylene (or) methyne group. For example,
2
D
+& 2
D 2 &+ 2 D &1
&+ D
+&
1& &+
+&22& &+ &+ +& &+
&1
DFWLYHPHWK\OHQHJURXS DFWLYHPHWK\OHQHJURXS DFWLYHPHWK\OHQHJURXS
These compounds will also show tautomerism because these compounds fulfill both structural requirements.
Cause of tautomerism: Migration of acidic hydrogen from a-carbon to electronegative atom which is bonded with
multiple bond is the cause of tautomerism.
OH
CH3 H2C
H
CH3
O
(I) (II)
(i) Both (I) and (II) are isomers known as tautomers.

(ii) Tautomers are always in equilibrium state.
(iii) Number of sigma, pi and lone pair of electrons in both tautomers are always the same.
(iv) Tautomerism is a chemical phenomenon which takes place only in liquid state.
(v) Tautomersim is catalysed by acid as well as base.
(vi) Tautomers are always reversible functional groups, functional isomers.
Tautomerism is of several types; the two important types are dyad and triad systems.
(a) Dyad System: It involves the oscillation of H atom between two polyvalent atoms, e.g., hydrogen cyanide (I) and
hydrogen isocyanide (II).
H N H N C
(I) (II)
In the above example the H atom vibrates between carbon and nitrogen atoms. The alkyl derivatives of (I) are called
cyanides while those of (II) isocyanides.
(b) Triad System: In it, one H atom oscillates between three polyvalent atoms.
(i) Keto-enol tautomerim: In this case, the polyvalent atoms are one oxygen and two carbon atoms, e.g., aceto acetic
ester, acetyl acetone, benzoyl acetone, acetaldehyde, acetone, phenol etc.
The form containing keto (oxo) group is called keto while that having alkene and –ol functions is called an enol
form.
H
H3C O
O O
C 2H5
C 2H5
OH O
CH3 O
keto form enol form
H3C CH3 H3C CH3
O O OH O
keto form enol form
H5 C 6 CH3 H5C 6 CH3
O O OH O
keto form enol form
The conversion of a keto form into enol form is known as enolization. It is catalyzed by the presence of acid (or)
alkali. This dynamic isomerism is shown only by those aldehydes, ketones or esters which have at least one labile
a-hydrogen atom. For example, benzaldehyde and benzophenone do not have labile a-hydrogen, hence, these do
not show tautomerism.
O O
H5C 6 H5C 6 (absence of α-H atom)
H C 6H5
On other hand, acetophenone contains a-H atoms, hence, exhibits tautomerism.
O OH
H5C 6 H5C 6
α
CH3 CH2
Keto form
Keto form Enol
Enolform
form
Enolization is in the following order:

CH3COCH3 < CH3COCH2COOC2H5 < C6H5COCH2COOC2H5 < CH3COCH2CHO < CH3COCH2COCH3
In compounds whose molecules have two carbonyl groups separated by one –CH2 – group (called b-dicarbonyl
compounds), the amount of enol present at equilibrium is far higher, For example,
2+ 2
2 2
+& &+
+& &+

The greater stability of the enol form of b-dicarbonyl compounds can be attributed to stability gained through
resonance stabilization of the conjugated double bonds and (in a cyclic form) through hydrogen bonding.
H H
O O O O
H3C CH3 H3C CH3
H H
Percentage of enolic contents of some common compounds in decreasing order is given below:
O O O O O
H H CH3 CH3
O O
O O
H3C H H3C CH3

H3C O
C 2 H5
Percentage composition of tautomeric mixture:

O O OH
For the enol form is the more stable form as it is Caromatic enol form.
For the other compounds, we can say that quarter the acidic strength of ∝H, w.h.t., to casbonyl gp., the more is
the % of enol form.
■ Any reaction that simply involves the intramolecular transfer of a proton is called a tautomerism. Here are two
other examples.
H H
H⊕
O O O O
R R
Fot the tautomerism of a carboxylic acid, the mixture must be exactly 50:50 as the two forms (tautomers) are identical.
R R
NH
⊕
H N N N H

Fort the tautomerism of an imidazole, the mixture must not be axactiy 50:50 as the two forms are not identical.
In the first case the two tautomers are the same and so the equilibrium constant must be exactly 1 or. If you prefer,
the mixture must be exactly 50:50. In the second case the equilibrium will lie on one side or the other depending
on the nature of R.
Why do simple aldehydes and ketones not exist as enols?
Although any carbonyl compound with protons adjacent to the carbonyl group can enolize, simpler carbonyl
compounds like cyclohexanone or acetone have only a trace of enol present under ordinary conditions. The equi-
librium lies well over towards the keto form (the equilibrium constant K for acetone is about 10–6).
energy
H
O K O
enol
H
H keto
keto form of aoetone enol form of aoetone
This is because the combination of a C = C double bond and an O–H single bond is (slightly) less stable than the
combination of a C = O double bond and a C–H single bond. The balance between the bond energies is quite fine.
On the one hand, the O–H bond in the enol is a stronger bond than the C – H bond in the ketone, but, on the other
hand, the C = O bond of the ketone is much more stable than the C = C bond of the enol. Here are some average
values for these bonds.
Typical amounts of enols in solution are about one part in 105 for normal ketones. So why do we think they are
important? Because enolization is just a proton transfer, it is occurring all the time even though we cannot detect
the minute proportion of the enol. Let us look at the evidence for this statement.
Table 2.8 Typical Bond Strengths (kj mol–1) In Keto and Enol Forms
Bond to H π bond Sum

keto form (C–H) 440 (C=O) 720 11.60
enol form (O–H) 500 (C=C) 620 1120
Percentage of enol contents of some compounds is given below in the table.

Table 2.9 Enol Content of Some Compounds
Compound Enol Percentage Compound Enol Percentage

O 0. 00025 O O 31. 00
H3C
H3C O
CH3
CH3 CH3
O 0. 0056 O O 80.4
CH3
H3C H3C CH3
O O 4.8 O O 89. 0
H3C O H5C 6 CH3
CH3
O O 7.7 O 99.99
H3C O
C 2H5
The conversion of a keto form into an enol form is known as enolisation and the enolisation of a compound has
been found to depend upon various factors such as structural factor, temperature and nature of solvent. However,
the most important is the structural factor (resonance and hydrogen bonding).
(i) Ketonic form predominates in simple monocarbonyl compounds like acetaldehyde, acetone and cyclohexanone.
This is due to the greater bond strength of C = O (>C = O, 365 kJ/mole) present in keto form than the carbon-
carbon double bond (C = C, 250 kJ/mole) present in enolic form.
(ii) Enolic form predominates in b-di ketones due to intramolecular hydrogen bonding and resonance. Intramolecular
hydrogen bonding stabilizes enol form by 7 kcal/mole and resonance stabilizes enol form by 15 kcal/mole. Thus
enol form is more stable than keto form by 22 kcal/mole in 1,3-diketones.
O O
H H
O O O O
H3C CH3
H3C CH3 H3C CH3
H H H H
O O O O O O O O
H3C CH3 H3C CH3 H3C CH3 H3C CH3

(ii) Triad System containing Nitrogen

(a) Nitrous acid exists in two tautomeric forms:
O
H O
H N
N O
O Nitrite form
Nitro form
The alkyl derivatives of nitro form and nitrite form are called as nitro alkanes and alkyl nitrites, respectively.
(b) Primary and secondary nitroalkanes have liable a-H atom, hence exhibit nitro-aci nitro type of tautomerism.
α H3C
H3C
N O N OH
O O
Nitro form (I) Aci form (II)
(c) Nitroso-isonitro System: In this system one tautomer exits as nitroso while the other tautomer exists as an
isonitroso (oxime) form.
OH
O
H3C N
H3C N
Isonitroso form
Nitroso form
(d) Imine-Enamine System

H3C H3C
NH NH2
Imine Enamine
Mechanism of tautomerism
Reactions like this are given name tautomerism.
O OH
H H
H
keto form of enol form of
1-phenylpropan-1-one 1-phenylpropan-1-one
But, when the enol form reverts to the keto form, it picks up a deuteron instead of a proton because the solution
consists almost entirely of D2O and contains only a tiny amount of DOH (and no H2O at all).
■ Notice that the double bond in this enol could be either E of Z has been discursed. E – 2 Nomenclature.
' '
2 2 2
UHWXUQWR
HQROL]DWLRQ NHWRIRUP
' + '
+ + +
The process can now be repeated with the other hydrogen atome on the same carbon atom.
' + 2
'
+ &+
2 2 2
UHWXUQWR ''
HQROL]DWLRQ
+ +
NHWRIRUP
'
+ ' ' ' ' +
Enolization is Catalysed by Acids and Bases

Enolization is, in fact, quite a slow process in neutral solution, even in D2O, and we would catalyse it with acid or base if
we really wanted it to happen. In the acid-catalysed reaction, the molecule is first protonated on oxygen and then loses the
C–H proton in a second step. We shall use a different example here to show that aldehydes form enols too.

+ 2 + 2 + 2 +
SURWRQDWLRQ ORVVRISURWRQ 2
RQR[\JHQ IURPFDUERQ
+ + +
+ +
³NHWRÍRUPRIDOGHK\GH 2+ HQROIRUPRIDOGHK\GH
This is a better mechanism for enolization than those we have been drawing because it show that something (here
a water molecule) must actually be removing the proton form carbon. Though this reaction will occur faster than the
uncatalysed enolization, the equilibrium is not changed and we still cannot detect the enol spectroscopically.
In the base-catalysed reaction, the C–H proton is removed first by the base, say, a hydroxide ion, and the proton added
to the oxygen atom in a second step.
+
2 +2 + 2 SURWRQDWLRQ
2
ORVVRISURWRQ
IURPFDUERQ RQR[\JHQ
+ +
+ +
2+
³NHWRÍRUPRIDOGHK\GH HQROIRUPRIDOGHK\GH
This is a good mechanism too because it shows that something must remove the proton from carbon and something
(here a water molecule—we can not, of course, have protons in basic solution) must put the proton on the oxygen atom.
The concentration of free protons in water is vanishingly small.
Notice that both of these reactions are genuinely catalytic. You get the proton back again at the end of the
acid-catalysed mechanism.
H H
loss of proton O
O⊕
from carbon
⊕
H H + H2O – H
H
OH2
enol form of aldehyde
And you get the hydroxide ion back again at the end of the base-catalysed mechanism.
protonation H
O
Ο on oxygen
HO +
H
Η
enol form of aldehyde
With unsymmetrical ketones, enolization may occur in either of two directions.
OH O OH
α α
H2C C CH2 CH3 H3C C CH2 CH3 H3C C CH2 CH3
but-1-en-2-ol 2-Butanone but-2-en-2-ol
The ketone is by far the most abundant species present at equilibrium. Both enols are also present, but in very small con-
centrations. The enol with the more highly substituted double bond is themore stable of the two enols and is present in
higher concentration than the other.
(i) Nitro-acinitro system: In this system one tautomer exists as nitroalkane (nitroform) while the other tautomer exists
as an acinitro.
O OH
CH3 N CH2 N
O O
Nitro form Acintro form
1, 3-Nitro-acinitro tautomerism
(ii) Nitroso-isonitroso system: In this system one tautomer exists as nitroso while the other tautomer exists as an
isonitroso (oxime) form.
CH3 – CH2 – N = O CH3CH=N – OH
Nitroso form Isonitroso form
(iii) Imine-enamine system:
CH3CH2CH=NH CH3CH=CHNH2
Imine Enamine
40. x%
O OH
O O
EtO – C – CH2 – C – OEt
OH O
EtO – C = CH – C – OEt y%
O O
CH3 – C – CH2 – C – OEt
OH O
CH3 – C – CH – C – OEt z%
The relation between the enol contents x, y, z should be

(a) x > y < z (b) z < x < y
(c) y > x > z (d) y < z > x
O O
41. Base Enolate

(Major)
The major enolate ion should be
O O O O
(a) (b)
(c) both (a) and (b) in equal proportions (d) there is no reaction
42. H⊕ Enol
O (Major)
The major enol should be
(a) (b)
OH OH
(c) both (a) and (b) in equal proportions (d) there is no reaction
O
D2O (excess)
43. Product
OD
The product of this reaction should be
D D
O O
(a) (b) D
D
D
O
(c) (d) none of these
D
D
SOLUTIONS
40. (b) 41. (b) 42. (a) 43. (b)
Stereoisomerism: When isomers have the same structural formula but differ in relative arrangements of atoms or
groups in space within the molecule, these are known as stereosiomers and the phenomenon as stereoisomerism.
Stereo isomers can be configurational isomers or conformation isomers.
The fixed relative spatial arrangement of atoms in the molecule is known as configuration.
A particular orientation (or arrangement) of atoms in a molecule, differing from other possible orientations by rotation
around single bonds is known as conformation.
Configurational isomers can be geometrical isomers (or) optical isomers.
Geometrical Isomerism: Configurational stereo isomers arising due to different arrangements around carbon-carbon
double bond are known as geometrical isomers. Those stereo isomers having same structural formula but differing in
spatial arrangement of the group around the double bond are known as geometrical isomers and the phenomenon as geo-
metrical isomerism.
Since the presence of pi(π) bond above and below the plane of sigma (σ) bond locks the molecule in a fixed position,
alkene derivatives of the formula abc=cab can be written by two spatial arrangement.
a c b a c b
a c b b c a
I (cis) II (trans)
In spatial arrangement (I) similar groups are present on the same side of double bond, while in (II) the similar groups
are present on the opposite side of the double bond. Hence, spatial arrangement (I) is called cis, whereas (II) as the trans-
isomer. Such type of geometrical is called as cis-trans isomerism.
Reason of Occurrence of geometrical Isomerism: When the two atoms are joined together by a double bond
(>C=C<), one pi and one sigma, free rotation about the carbon-carbon double bond becomes restricted (hindered), hence
the spatial arrangements of atoms (or) groups attached with these carbon atoms becomes fixed in space and it represents
two different isomers. Thus, lack of free rotation about carbon-carbon double bond gives rise to geometrical isomersm.
In general, the necessary and sufficient conditions for the occurrence of geometrical isomerism are (i) restricted (hin-
dered) rotation of the carbon-carbon double bond and (ii) both the doubly bonded carbons should have different substituents.
Van’t Hoff explained the occurrence of cis-trans isomers on the basis of tetrahedral conception of carbon atom.
According to him, a double bond may be created by placing the two tetrahedrons edge-to-edge; such an arrangements
would be rigid and free rotation around the double bond would be restricted.
Thus, for a compound of the general formula abc=cab, two spatial models can be constructed where free rotation would
be impossible.
The simple examples showing geometrical isomerism are given below.
H3C CH3 H3C H
2-Butene
H H H CH3
cis-2-butene trans-2-butene

H H H CH2 CH3
3-Hexene
H3C CH2 CH2 CH3 H3C CH2 H
cis-3-Hexene trans-3-Hexene
H C COOH H C COOH
Maleic and
H C COOH HOOC C H
Fumaric acids
Maleic acid (cis) Fumaric acid (Trans)
Geometrical isomerism in the compounds containing C=N: Oximes of aldelydes and unsymmerical ketones,
i.e., aldoxines and unsymmetrical ketoximes are the best examples of the occurrence of such geometrical isomerism.
Benzaldoxime (C6H5 — CH = NOH) has the following two geometrical isomers.
H 5 C6 C H H 5 C6 C H
N OH HO N
syn anti
Geometrical isomerism in the compounds containing N=N: The simplest example is that of azobenzene.
N N
It has following two

geometrical isomers.
C6H 5 C6H 5
N N
N N
C6H 5 H 5C6
syn anti
Geometrical Isomerism in Cyclic Compounds: In cyclic compounds, there can be no free rotation about carbon-
carbon single bonds because rotation would break the bonds and break the ring system. For example, 1,2-dimethyl
cyclopropane exists in two isomeric forms.
H H H3C H
CH3 CH3 H CH3

cis-1,2-dimethylcyclopropane trans-1,2-dimethylcyclopropane
Stability of cis, Trans (or) Geometrical isomers: The trans isomers of alkenes are usually more stable than their
corresponding cis isomers.
A B
A C B C
A C B C
B A
cis-isomer
The reason for this becomes clear if we consider the cis and trans-isomers of the alkene ABC=CAB in which À’ is a
bulky group as compared to `B’ (e.g., CH3 — HC = CH — CH3. In the cis isomer, the two bulky À’ groups are very close
to each other. The repulsion due to the overlapping of the electron clouds of the two bulky À’ groups will make this isomer
less stable than trans isomer in which the bulky À’ groups are far apart [being on the opposite sides of the double bond].
Number of Geometrical Isomers

(a) In compounds containing more than one double bond, the number of geometrical isomers (N) is given by the formula
N = 2n
where n = number of double bonds with different substituents at each end.
For example, R—CH=CH—CH=CHR has 4 isomers.
(b) When the ends of an alkene are the same and n is the number of double bonds, then the number of geometrical isomers
is given as:
N = 2n –1 + 2p–1
where p = n when n is even

2
and p = n + 1 when n is odd.

2
For example: CH 3 — CH = CH — CH = CH — CH = CH — CH 3 , has the number of geometrical isomers.
N = 23–1 + 22–1 = 22 + 2 = 4 + 2 = 6
E and Z nomenclature of geometrical isomers: If all the four groups/atoms attached to C=C double bond are
different, then cis and trans nomenclature fails in such cases and a new nomenclature called E and Z system of nomenclature
replaces it.
H I higher H I higher
priority C priority
C
C C
higher Br Cl Cl Br higher
priority priority
E Z
I II
The group/atom attached to carbon-carbon double bond is given to higher rank, whose atomic weight is higher. If two
higher ranked group are across, it is called E form (E stands for the German word entgegen meaning there by opposite) and
the two higher ranked groups are on the same side, they are called Z-form (Z stands for German word zusummen meaning
there by on the same side. )
If the first atom is common in the groups, then the priority is given to the second atom in the group.
44. CH2 = CH-CH=CH-CH=CH2
How many geometrical isomers of this compound are possible?
(a) 2 (b) 3 (c) 4 (d) 8
45. CH2=CH–CH=CH–CH=CH–CH3
(a) 2 (b) 3 (c) 4 (d) 8
46. CH3–CH2–CH=CH–CH=CH–CH3
(a) 2 (b) 3 (c) 4 (d) 8
47. CH3–CH=CH–CH=CH–CH3
(a) 2 (b) 3 (c) 4 (d) 8
48. CH3–CH=CH–CH=CH–CH=CH–C2H5
How many geometrical isomers of this olefine are possible?
(a) 4 (b) 5 (c) 6 (d) 8
49. CH3–CH=CH–CH=CH–CH=CH–CH3
How many geometrical isomers of this olefine are possible?
(a) 4 (b) 5 (c) 6 (d) 8
50. CH3–CH= C − C = CH–CH3
| |
Br Cl
(a) 2 (b) 3 (c) 4 (d) 6
51. CH3–CH= C − C = CH − CH3

| |
Br Br
(a) 2 (b) 3 (c) 4 (d) 6
CH3
52.
CH3
(a) 2 (b) 3 (c) 4 (d) 6
CH3
53.
C2H5
(a) 0 (b) 2 (c) 3 (d) 4
CH3
54. CH3
CH3
(a) 0 (b) 2 (c) 3 (d) 4
CH3
55. C2H5
CH3
(a) 0 (b) 2 (c) 3 (d) 4
56.
How many geometrical isomers of this cyclodecene are possible?

(a) 0 (b) 2 (c) 3 (d) 4
CH3
57.
CH3
How many geometrical isomers of this compound are possible which can be isolated at room
temperature?
(a) 0 (b) 2 (c) 3 (d) 4
CH3
58. C=N–OH
C2H5
How many geometrical isomers in this compound are possible?
(a) 0 (b) 2 (c) 3 (d) 4
SOLUTIONS
44. (b) 45. (c) 46. (c) 47. (b) 48. (d) 49. (c) 50. (c) 51. (b)
52. (b) 53. (b) 54. (a) 55. (b) 56. (b) 57. (a) 68. (b)
OPTICAL ISOMERISM
Before dealing with optical isomerism in detail, it is useful to discuss some terms which will be used in optical
isomerism.
(1) Chiral Carbon Atom or Asymmetric Carbon Atom

A carbon bonded to four different groups is called a chiral carbon or a chirality centre. The chirality centre is indicated by
asterisk.
CH3—C*HOH—CHO CH2OH—C*HBr—COOH
Notice that the only carbons that can be charality centres are sp3-hybridised carbons; sp2 and sp-hybridised carbons
cannot be chiral carbons because they cannot have four groups attached to them.
Note: Isotopes of an atom behave as different groups in stereoisomerism.
D H1
H *C T 35
Cl *C Cl37
Br H2
Note: Carbon of the following groups will not be a chiral carbon.
–CH3 – CH2OH – CHX2 – CHO – C – Z
(2) Optical Activity and Optically Active Compounds

Compound which rotates the plane of plane polarised light is known as optically active compound and the phenomenon is
known as optical activity.
Whether compound is optically active or not can be known by the configuration of the compound as well as by
polarimeter.
If a substance rotates the plane polarised light in clockwise direction then it is dextrorotatory, (+) form or (d) form. If a
substance rotates the plane polarised light in anticlockwise direction then it is laevorotatory, (-) form or (l) form. Whether
the compound is (d) form or (l) form can only be known by the use of polarimeter and not by the configuration of the
compound.
(3) Specific Rotation

Optical rotation
Enantiomers share many of the same properties; they have the same boiling points, the same melting points, and the
same solubilities. In fact, all of the physical properties of enantiomers are the same except those properties that depend
on how groups bonded to the chirality center are arranged in space. One of the properties that enantiomers do not share
is the way an enantiomer interacts with polarized light. What is polarized light? Normal light consists of electromagnetic
waves that oscillate in all planes perpendicular to the direction the light travels. Plane-polarized light oscillates only in
a single plane. Plane-polarized light is produced by passing normal light through a polarizer such as a polarized lens or a
Nicol prism.
direction of light propagation
normal polarizer plane-polarized

light light
You have experienced the effect of a polarized lens if you own polarized sunglasses. Because polarized sunglasses allow
only light oscillating in a single plane to pass through them, they block reflections more effectively than do nonpolarized
sunglasses.
In 1815, the physicist Jean-Baptiste Biot discovered that certain natural organic substances such as camphor and oil of
turpentine are able to rotate the plane of polarized light. He noted that some compounds rotated the plane of polarized light
in a clockwise direction and some in a counterclockwise direction, while others had no effect on the light. He predicted
that the ability to rotate the plane of polarized light was attributable to some asymmetry that existed in the molecule. Van’t
Hoff and Le Bel later determined that the molecular asymmetry was the result of having four different groups attached to
a carbon (a chirality center).
When plane-polarized light passes through a solution of achiral molecules, the light emerges from the solution with its
direction of polarization unchanged, because there is no asymmetry in the molecules. An achiral compound does not rotate
the plane of polarized light. It is optically inactive.
normal polarizer plane-polarized sample tube plane-polarized

light light containing an light
achiral compound
However, when plane-polarized light passes through a solution of a chiral compound, the light emerges with its direction
of polarization changed, because the molecules are asymmetric. Thus, a chiral compound rotates the plane of polarized
light. A chiral compound will rotate the plane of polarized light in either a clockwise or a counterclockwise direction. If one
enantiomer rotates the plane of polarized light in a clockwise direction, its mirror image will rotate the plane of polarized
light exactly the same amount in a counterclockwise direction.
normal polarizer plane-polarized sample tube plane-polarized

light light containing a light;
chiral compound its plane has
been rotated
A compound that rotates the plane of polarized light is said to be optically active. In other words, chiral compounds
are optically active and achiral compounds are optically inactive.
If an optically active compound rotates the plane of polarized light in a clockwise direction, it is called dextrorotatory,
indicated by (+); if an optically active compound rotates the plane of polarized light in a counterclockwise direction, it is
called levorotatory, indicated by (—). Dextro and levo are Latin prefixes for ‘to the right’ and ‘to the left,’ respectively.
Do not confuse (+) and (—) with R and S. The (+) and (—) symbols indicate the direction in which an optically active
compound rotates polarized light, whereas R and S indicate the arrangement of the groups about the chirality center. Some
compounds with the R configuration are (+) and some are (—).
The amount that an optically active compound rotates the plane of polarized light can be measured with an instru-
ment called a polarimeter. Because the amount of rotation depends on the wavelength of the light used, the light source
for a polarimeter must produce light with a single wavelength (monochromatic light). Most polarimeters use light from
a sodium arc (called the sodium D-line; wavelength = 589 nm). In a polarimeter, monochromatic light passes through
a polarizer and emerges as plane-polarized light. The polarized light then passes through an empty sample tube (or one
filled with an optically inactive solvent) and emerges with its direction of polarization unchanged. The light finally passes
through an analyzer.
light
source
polarizer Schematic of a polarimeter.
sample
tube
analyzer
viewer
The analyzer is a second polarizer mounted on an eyepiece with a dial marked in degrees. The user rotates the analyzer
until he or she sees total darkness. At this point the analyzer is at a right angle to the first polarizer, so no light passes
through. This setting of the analyzer corresponds to zero rotation. The sample to be measured is then placed in the sample
tube. If the sample is optically active, it will rotate the plane of polarized light. The analyzer will no longer block all the
light, and light reaches the user’s eye. The user then rotates the analyzer again until no light passes through. The amount
the analyzer is rotated can be read from the dial and represents the difference between an inactive sample and the active
sample. This is called the observed rotation (a), and it is measured in degrees. The amount of rotation caused by the
sample depends on the number of optically active molecules the light encounters in the sample. This, in turn, depends on
the concentration of the sample and the length of the sample tube. The observed rotation also depends on the temperature
and the wavelength of the light source.
Each optically active compound has a characteristic specific rotation. The specific rotation is the number of degrees of
rotation caused by a solution of 1. 0 g of the compound per mL of solution in a sample tube 1. 0 dm long at a specified tem
perature and wavelength. The specific rotation can be calculated from the observed rotation using the following formula:
α
[α]Tλ =
l×c
When polarized lenses are at a 90° angle to each other, there is no transmission of light through them.
Where [a] is the specific rotation; T is temperature in °C; X is the wavelength of the incident light (when the sodium
D-line is used, X is indicated as D); a is the observed rotation; l is the length of the sample tube in decimeters; and c is the
concentration of the sample in grams per milliliter of solution.
For example, one enantiomer of 2-methyl-1-butanol has been found to have a specific rotation of +5.75°. Because its
mirror image rotates the plane of polarized light the same amount but in the opposite direction, the specific rotation of the
other enantiomer must be—5.75°.
CH2OH
CH2OH
C
C H CH3
H
CH3 CH2CH3
CH2CH3
(R)-2-methyl-1-butanol (S)-2-methyl-1-butanol
[α]20°C
D = + 5.75° [α]20°C
D = + 5.75°
(4) Symmetric, Asymmetric and Dissymmetric Molecules

(A) Dissymmetric Molecule: Molecule will be a dissymmetric molecule if it has
(i) no plane of symmetry
(ii) no centre of symmetry and
(iii) no alternating axis of symmetry.
Note: Presence or absence of symmetries in the molecule can be known by the configuration of the molecule and not by
its structure.
A centre of symmetry: A centre of symmetry in a molecule is said to exist if a line is drawn from any atom or group to
this point and then extended to an equal distance beyond this point, meets the identical atom or group.
A centre of symmetry is usually present only in an even numbered ring. For example, the molecule of trans-2, 4-dimethy
1-cyclobutane-trans-1, 3-dicarboxylic acid has a centre of symmetry.
CH3 COOH
H H
H H
COOH CH3
All lines are passing through this point,
hence it is the centre point of the molecule.
Another interesting compound is dimethyl ketopiperizine. This has two isomers, cis and trans. The cis form has no
plane of symmetry or centre of symmetry. The trans form on the other hand has a centre of symmetry.
CH3
NH – NH }
CH3 CO – CO are symmetrical but
CO NH
C C
NH CO CH3 and H are not mirror images or not
H H symmetrical with respect to centre point.
}
CH3 H NH – NH
CO – CO they are symmetrical
CO NH CH3 – CH3 with respect ot centre
C C the molecule.
NH CO H–H
H CH3
center point
Alternating axis of symmetry: A molecule possesses an alternating axis of symmetry if, when rotated through an
angle of 360°/n about this axis and then followed by reflection in a plane perpendicular to the axis, the molecule is
indistinguishable from the original molecule. Alternating axis of symmetry is rare and it can be present in cyclic as well
as open chain compounds.
An open chain compound will be dissymmetric if it has no plane of symmetry.
COOH
H C OH
H C OH
COOH
No plane of symmetry, hence molecule is a dissymmetric molecule.
(B) Asymmetric Molecule: Dissymmetric molecule having at least one asymmetric carbon is known as asym-
metric molecule. All asymmetric molecules are also dissymmetric molecules but the reverse is not necessarily
true.
COOH
H *C OH
H C OH
*
C6H5
No plane of symmetry
⇓
Dissymmertric molecule
⇓
Asymmetric molecule
CHO
*
H C OH
CH3
no plane of symmetry
⇓
Dissymmetric molecule
⇓
Asymmetric molecule
(C) Symmetric Molecule: If any symmetry is present in the molecule then molecule will be symmetric molecule.
COOH
H C OH
plane of symmetry
H C OH
COOH
Symmetrical molecule.
Note: Mirror images of dis-symmetric compounds are always nonsuperimposable. Thus mirror images of asymmetric
compounds are also nonsuperimposable.
OR
If mirror images are nonsuperimposable, then the compound will be a dis-symmetric compound.
CHO CHO
H C OH HO C H
CH3 CH3
(I) (II)
= (I) is dissymmetric and (II) is also dissymmetric

= (I) and (II) are mirror images
= (I) and (II) are nonsuperimposable.
Note: Non-super imposable mirror image of any configuration can only be made if compound is dissymmetric or
asymmetric.
(5) Condition for Optical Activity

The necessary and sufficient condition for optical activity is that the molecule should be dis-symmetric, i.e., should have
no element of symmetry.
Note: For open chain compounds, Molecule will be optically active if it has no plane of symmetry.
OR
If mirror images will not be superimposable, then the compound will be an optically active compound.
(6) Optical activity of Compounds Having Asymmetric Carbons

(A) Calculation of number of optical isomers
(1) If molecule is not divisible into two identical halves and molecule has an n asymmetric carbon atom, then
Number of optically active forms = 2n = a
Number of enantiomeric pair = a/2
Number of racemic mixture = a/2
Number of meso form = 0
Examples:
C6H5— C*HOH— C*HOH— C*HOH— CH3
This molecule cannot be divided into two identical halves and it has three asymmetric carbons. Hence, number of
optical active isomers = a = 2n = 23 = 8.
* * * *
CH2OH – CHOH – CHOH– –CHOH — CHOH —CHO
n=4
Number of optically active forms = a = 24 = 16
* *
CH3 – CHOH– –CHCl — CH3
n=2
Number of optically active forms = 22 = 4

(2) If molecule is divisible into two identical halves, then the number of conflgurational isomers depends on the number
of asymmetric carbon atoms.
Case I: When compound has even number of carbon atoms, i.e., n = 2, 4, 6, 8, 10, 12,. . . :
(i) Number of optically by active forms = a = 2n-1
(ii) Number of enantiomeric pairs = a/2
(iii) Number of racemic mixture = a/2
(iv) Number of meso forms = m = 2(n/2-1)
(v) Total number of conflgurational isomers =a +m
Example:
* *
COOH – CHOH – –CHOH — COOH
(I) (II)
Two identical halves (I) and (II) having n = 2.

Thus number of optical isomers = a = 22-1 = 2
Number of meso form = m = 2(n/2)-1 = 2(2/2)-1 = 2° = 1
Total number of conflgurational isomers = 2 + 1 = 3
C6H5— CHCl— CHCl-|-CHCl— CHCl— C6H5
n = 4, even
Total number of conflgurational isomers = 8 + 2 = 10
Case II: When compound has odd number of carbon atoms, i.e.,
n = 3,5,7,9, 11,. . . :
(i) Number of optically active forms = a = 2n-1 – 2(n-1)/2
(ii) Number of enantiomeric pairs = a/2
(iii) Number of racemic mixture = a/2
(iv) Number of meso forms = m = 2(n-1)/2
(v) Total number of conflgurational isomers = a + m
Example:
* * *
CH2OH–CHOH–CHOH–CHBr–CH2OH
(I) (II)
Compound has two identical halves and has three asymmetric carbons.
Thus,
a = 2n-1 – 2(n-1)/2 = 22 – 21 = 4 – 2 = 2
m = 2(n-1)/2 = 21 = 2
Hence, total number of conflgurational isomers = 2 + 2 = 4
* * * * *
COOH–CHCl–CHOH–CHBr–CHOH–CHCl–COOH
(I) (II)
n=5
Compound is divisible in two identical halves. Therefore,

a = 2n-1 – 2(n-1)/2 = 24 – 22
= 16 – 4 = 12
m = 2(n-1)/2 = 22 = 4
Therefore, total number of configurational isomers = 12 + 4 = 16.
59. If n is the number of active double bonds in a molecule along which geometrical isomerism is
possible, the number of geometrical isomers must be
(a) 2n (b) 2n2 (c) 2n–1 (d) 2n+1
60. In open chain compounds, if numbering of the parent chains is not possible from either side of the
chain and if n (no. of active double bonds) is more than one, then number of geometrical isomers
will be
(a) 2n (b) 2n2 (c) less than 2n (d) less than 2n2
61. In open chain compounds, if numbering of the parent chains is possible from either side of the
chain and if n is more than one then number of geometrical isomers will be
(a) 2n (b) 2n2 (c) less than 2n (d) less than 2n2
Br
62.
Br
How many stereoisomers are possible in this compound?
(a) 2 (b) 3 (c) 4 (d) 5
Br
63.
Cl
(a) 2 (b) 3 (c) 4 (d) 5
Br
64.
Br
(a) 2 (b) 3 (c) 4 (d) 5
SOLUTIONS
59. (a) 60. (a) 61. (c) 62. (b) 63. (c) 64. (b)
(B) Conversion of structural formula into configurational isomers:

Consider the following compound which has one chiral carbon
CH3—CHOH—COOH
Step I: Draw a chiral carbon. Draw four bonds at right angles to one another on it.
Out of the four bonds, one bond is above, one bond is below, one is on the left hand side and other is on the right hand side
on asymmetric carbon.
Step II: The group which is on the right hand side of asymmetric carbon in the structure of the compound (i.e., COOH)
will be placed above on chiral carbon and the group which is on the left hand side of asymmetric carbon in the structure
(i.e., CH3) will be placed below on chiral carbon.
COOH –COOH is above
and
–C– –CH3 is below on
CH3 asymmetric carbon
Step III: The remaining two groups present on the asymmetric carbon in the structure of the compound (i.e., H and OH)
will be placed on the left and right sides on asymmetric carbon in the configuration.
Which group will be on the left hand side or which group will be on the right hand side on asymmetric carbon in
the configuration, depends on you. If H is on the left hand side then OH will be on the right hand side. Thus one of the
configuration of the lactic acid will be
COOH
H – C – OH
CH3
(I)
Other configuration of lactic acid will be the mirror image of (I)
COOH COOH
H – C – OH HO – C – H
CH3 CH3
(I) (II)
(7) Optical Activity of Compounds Containing one Asymmetric Carbon

Examples:
*
CH3– CHOH – COOH
*
CH3– CHOH – CHO
*
CH2OH – CHOH – CHO
* – CH
C H – CHCl
6 5 3
Any molecule having one asymmetric carbon atom exists in two configurational isomers which are nonsuperimposable
mirror images.
COOH COOH
H – C – OH HO – C – H
CH3 CH3
(I) (II)
(I) and (II) have the same molecular formula, the same structure but different configurations; hence, (I) and (II) are
known as configurational isomers. (I) and (II) are nonsuperimposable mirror images, hence (I) and (II) are optical isomers.
Configurational isomers, which are nonsuperimposable mirror images, are known as enantiomers. Thus (I) and (II) are
enantiomers. Pair of (I) and (II) is known as enantiomeric pair.
(A) Properties of Enantiomers: All chemical and physical properties of enantiomers are same except two physical
properties.
(i) Mode of rotation: One enantiomer rotates light to the right and the other by an equal magnitude to the left direction.
For example
Enantiomer [a] bp d
(+) 2-methyl-l-butanol +5.78 128.9 1.41
(-) 2-methyl-l-butanol -5.78 128.9 1.41
(ii) Rate of chemical reaction with an optically active compound: Both the enantiomers of 2-methyl-l-butanol
are converted to 2-methyl butene when treated with cone. H2SO4. The rate of the reactions is the same.
When both these compounds are treated with lactic acid, the rate of the reaction is different.
(+)-2-methyl-1-butanol
K3 (–)lactic acid
Ester
(–)-2-methyl-1-butanol
K4 (–)lactic acid
Ester
K3 ≠ K4
Thus, rate of reactions of enantiomers with optically active compound is different.
(B) Racemic Mixture: An equimolar mixture of two enantiomers is called a racemic mixture (or racemate, ± form,
(dt) form or racemic modification). Such a mixture is optically inactive because the two enantiomers rotate the plane
polarised light equally in opposite directions and cancel each other’s rotation. This phenomenon is called external
compensation.
⇒ Racemic mixture can be separated into (+) and (–) forms. The separation is known as resolution.
⇒ The conversion of (+) or (–) form of the compound into a racemic mixture is called racemisation. It can be caused by
heat, light or by chemical reagents.
⇒ Racemic mixture is designated as being (±) or (dl).
Conversion of Flying wedge to Fischer:

In the below the plane
plane CH3 (vertical line)
Cl Br CH3 CH3 horizontal
of chiral
Br ‘e’ line
Cl Br Cl Br
Cl above
H H
H CH3 the plane
H of chiral rertical
w.r. to viewer
down up (horizontal line) line
Br ‘c’
Cl
C2H5
C2H5 Cl Br (viewer sees it one the
CH3 page from the perpendicular
Cl Br
direction – the vertical line
Br is behind the plane of the page
Cl • CH3
our horizonal lines are above the
down up plane of the page and chiral
with respect to riewer centre is in the plane of the page)
(horizontaline above the plane)
up C2H5 up
Vertical
Br (* =) chiral carbons
line below
the plane are in the plane.
•
Cl Cl
*
•
Br
CH3
down down
w.r. to horizonal plane w.r. to viewer
viewer above theplane
(closer to viewer)
Illustration
86. The observed rotation of 2. 0 g of a compound in 10 mL of solution in a polarimeter tube 10 cm long is +134°. What
is the specific rotation of the compound?
Ans. Knowing whether a chiral molecule has the R configuration or the S configuration does not tell us the direction
in which the molecule rotates polarized light Some compounds with the R configuration rotate light to the right
(+), and some rotate light to the left (—). We can tell by looking at the structure of a compound whether it has the
R configuration or the S configuration. But the only way we can tell whether a compound is dextrorotatory (+)
or levorotatory (-) is to put the compound in a polarimeter. For example, (S)-lactic acid and (S)-sodium lactate
have very similar structures, but one is dextrorotatory and the other is levorotatory When we know the direction
in which an optically active compound rotates the plane of polarized light, we can incorporate (+) or (—) into its name.
CH2CH3 CH2CH3
C C
H H
HO HO – +
COOH COO Na
(S)-(+)-lactic acid (S)-(–)-sodium lactate
A mixture of equal amounts of a pair of enantiomers is called a racemic mixture, a racemic modification, or a
racemate. Racemic mixtures do not rotate polarized light; they are optically inactive. For every molecule in a racemic
mixture that rotates the plane of polarized light in one direction, there is a mirror-image molecule that rotates the plane in
the opposite direction. As a result, the plane o polarized light emerges from a racemic mixture with its direction unchanged.
The symbol (±) is used to specify a racemic mixture. Thus, (±)-2-bromobutane indicates a mixture of (+)-2-bromobutane
and an equal amount of (—)-2-bromobutane
65. Which of the following compounds has asymmetric centre?
O O O
(a) (b) (c) Br (d)
O
Br
OH OH
66. Which of the following compounds has two dissimilar asymmetric centres?
CH3
O O O O
(a) (b) (c) (d) both (b) and (c)

CH3
C2H5 C2H5
CH3 OH
67. H OH HO H
H C2H5 CH3
CH3
I II III
Which of these structures represent configurationally identical molecules?
(a) I and II (b) I and III (c) II and III (d) none of these
H O H CH3 O CH3 CH3 CH3
68.
O
CH3 CH3 H H H H
I II III
Which of these structures represent configurationally identical molecules?
(a) I and II (b) I and III (c) II and III (d) all of these
(C) Optical Purity

Whether a particular compound consists of a single enantiomer or a mixture of enantiomers can be determined by its
observed specific rotation. For example, an enantiomerically pure sample of (S)-(+)-2-bromobutane will have an
observed specific rotation of +23.1° because the specific rotation of (S)-(+)-2-bromobutane is +23.1°. If, however, the
sample of 2-bromobutane has an observed specific rotation of 0°, we will know that the compound is a racemic mixture. If
the observed specific rotation is positive but less than +23.1°, we will know that we have a mixture of enantiomers and the
mixture contains more of the enantiomer with the S configuration than the enantiomer with the R configuration.
From the observed specific rotation, we can calculate the amount of each enantiomer present in the mixture. First we must
calculate the optical purity using the following formula.
observed specific rotation
optical purity =
specific rotation of the pure enantimoer
For example, if a sample of 2-bromobutane has an observed specific rotation of +9.2°, its optical purity is 0.40. In other
words, it is 40% optically pure.
+9.2°
optical purity = = 0.40 or 40%
+23.1°
Because the observed specific rotation is positive, we know that the solution contains excess (S)-(+)-2-bromobutane.
The optical purity tells us how much excess (5)-(+)-2-bromobutane is in the mixture. The mixture is 40% optically pure,
which means that 40% of the mixture is excess S enantiomer and 60% is a racemic mixture. Half of the racemic mixture
plus the amount of excess S enantiomer equals the amount of the S enantiomer present in the mixture. Thus, 70% of the
mixture is the S enantiomer (1/2 × 60 + 40) and 30% is the R enantiomer.
Illustrations
87. (+)-Mandelic acid has a specific rotation of +158°. What would be the observed specific rotation of each of the
following mixtures?
(a) 25% (—)-mandelic acid and 75% (+)-mandelic acid (b) 50% (—)-mandelic acid and 50% (+)-mandelic acid
(c) 75% (-)-mandelic acid and 25% (+)-mandelic acid
88. The specific rotation of (R)-(+)-glyceraldehyde is +8.7°. If the observed specific rotation of a mixture of (R)-
glyceraldehyde and (S)-glyceraldehyde is +1.4°, what percentage of the glyceraldehyde is present as the R
enantiomer?
89. A solution prepared by mixing 10 mL of a 0.10 M solution of the R enantiomer and 30 mL of a 0.10 M solution of
the S enantiomer was found to have an observed specific rotation of +4.8°. What is the specific rotation of each
of the enantiomers?
Ans. One millimole (mmol; 10 mL x 0.10 M) of the R enantiomer is mixed with 3 mmol of the S enantiomer; 1 mmol
of the R enantiomer plus 1 mmol of the S enantiomer will form 2 mmol of a racemic mixture. There will be
2 mmol of S enantiomer left over. Therefore, 2 mmol out of 4 mmol is excess S enantiomer (2/4 = 0.50). The
solution is 50% optically pure.
observed specific rotation

optical purity = 0.50 =
specific rotation of the pure enantiomer
+4.8°
0.50 =
x
x = +9.6°
The S enantiomer has a specific rotation of +9.6°; the R enantiomer has a specific rotation of-9.6°.
(8) Optical Activity of Compound Containing Two Chiral Carbon Atoms

Case I: When the molecule is not divisible into two identical halves.
The number of optical isomers possible in this case is four (a = 22 = 4). Further there will be two pairs of enantiomers and
two racemic modifications. In practice also it is found to be so. For example, dibromocinnamica acid exists in the follow-
ing four optically active forms.
COOH COOH COOH COOH
H C Br Br C H H C Br Br C H
H C Br Br C H Br C H H C Br
C6H5 C6H5 C6H5 C6H5

(I) (II) (III) (IV)
First pair of enantiomers Second pair of enantiomers
Thus, there are two pairs (I), (II) and (III), (IV) of enantiomers. Further, more equimolar mixture of (I) and (II) will give
one racemic mixture. Similarly, equimolar mixture of (III) and (IV) will give other racemic mixture.
Now let us examine the relationship between the structures (I) and (III), (I) and (IV), (II) and (III) and (II) and (IV).
These are configurational isomers but these are not mirror images. Configurational isomers which are not mirror images
are known as diastereomers.
Thus, (I) and (III) are diastereomers
(I) and (IV) are diastereomers
(II) and (III) are diastereomers
(II) and (IV) are diastereomers
(A) Properties of Diastereomers: Diastereomers have different physical properties, e.g., melting and boiling points,
refractive indices, solubilities in different solvents, crystalline structures and specific rotations. Because of differences
in solubility they often can be separated from each other by fraction crystallisation; because of slight differences in
molecular shape and polarity, they often can be separated by chromatography.
Diastereomers have different chemical properties toward both chiral and achiral reagents. Neither any two
diastereomers nor their transition states are mirror images of each other and so will not neccessarily have the same
energies. However, since the diastereomers have the same functional groups, their chemical properties are not too
dissimilar.
Case II : When molecule is divisible into two identical halves.

Number of optical isomers = a = 22-1 = 2
Number of meso forms = m = 2° = 1
Total number of configurational isomers = 3
For example, tartaric acid exists in the following three forms:
COOH COOH COOH
H C OH HO C H H C OH
HO C H H C OH H C OH
COOH COOH COOH

(I) (II) (III) No non-super imposible
mirror image because it
has a plane of symmetry.
(I) and (II) are enantiomers.

(I) and (III) are diastereomers.
(II) and (III) are diastereomers.
(III) is optically inactive due to symmetry of the molecule. It is known as meso form.
(B) Mesoform: Symmetrical molecule having two or more than two chiral carbons is known as meso form.
CH2OH
COOH CH2OH H C OH
H C OH H C OH H C OH
plane of symmetry plane of symmetry plane of symmetry
H C OH H C OH H C OH
COOH CH2OH H C OH
Meso form Meso form
CH2OH
Meso form
Meso compounds are optically inactive due to the symmetry of the molecule.
(9) Name of Optical Isomers

The following three nomenclatures are used for optically active compounds:
(A) D/L System of Nomenclature: This nomenclature is mainly used in sugar chemistry or optically active
polyhydroxy carbonyl compounds. This nomenclature was given by Emil Fischer to designate the configurations of
various sugars relative to the enantiomeric (+) and (-) glucose as reference.
All sugars whose Fischer projection formula shows the OH group on the chiral carbon atom adjacent to the terminal
CH2OH group on the right hand side belong to the D-series.
H C OH
CH2OH
D-series
Similarly if OH is on the left hand side, then the sugars belong to the L-series.
HO C H
CH2OH
L-series
Examples:
CHO CHO
H C OH HO C H
CH2OH CH2OH
D(d)-glyceraldehyde L(l)-glyceraldehyde
or or
D(+) glyceraldehyde L(–) glyceraldehyde
⇒ It must be noted that there is no relation between the sign of rotation (+, – or d, l) and the configuration (D and L) of
an enantiomer.
⇒ Any compound that can be prepared from, or converted into D(+) glyceraldehyde will belong to D-series and
similarly any compound that can be prepared from, or converted into L(–) glyceraldehyde will belong to the L-series.
⇒ This nomenclature is also used in L-amino acids.
COOH COOH
H C NH2 NH2 C H
R R
D–Amino acid L–Amino acid
(B) Erythro and Threo System of Nomenclature: This nomenclature is used only in those compounds which have
(i) only two chiral carbons and
(ii) the following structure
R’_Cab—Cbc—R’
i.e., out of six substituents on two asymmetric carbons, at least two should be same.
When two like groups (in the given example, group is b) in Fischer projection formula are drawn on the same side of
the vertical line, the isomer is called erythro form; if these are placed on the opposite sides, the isomer is said to be threo
form.
R′ CH3 CH3
a C b H C Cl H C Cl
c C b H C Br Br C H
R′′ C6H5 C6H5

Erythro form Erythro form Threo form
CH3 CH3
H C OH H C OH
H C Cl Cl C H
CH3 CH3
Erythro form Threo form
CH3 CH3
H C OH HO C H
H C Cl Cl C H
CH3 CH3
(I) (II)
(I) and (II) are enantiomers, also known as erythro enantiomers.

CH3 CH3
H C OH HO C H
Cl C H H C Cl
CH3 CH3
(III) (IV)
(III) and (IV) are threo enantiomers.

(C) R, S Nomenelature (Absolute Configuration)

The order of arrangement of four groups around a chiral carbon (stereocentre) atom is called the absolute configuration
around that atom. System which indicates the absolute configuration was given by three chemists R. S. Cahn, C. K. Ingold
and V. Prelog. This system is known as (R) and (S) system or the Cahn-Ingold Prelog system. The letter (R) comes from
the latin rectus (means right) while (S) comes from the latin sinister (means left). Any chiral carbon atom has either an
(R) configuration or an (S) configuration. Therefore, one enantiomer is (R) and other is (S). A racemic mixture may be
designated (R) (S), meaning a mixture of the two.
(R) (S) nomenclature is assigned as follows:
Step-I: By a set of sequence rules given below the atoms or groups connected to the chiral carbon are assigned a priority
sequence.
Sequence Rules for Order of Priority
Rule 1: If all four atoms directly attached to the chiral carbon are different, priority depends on their atomic number. The
atom having highest atomic number gets the highest priority, i.e., (1). The atom with the lowest atomic number is given
the lowest priority, i.e., (4), the group with next higher atomic number is given the next higher priority (3) and so on. Thus,
Cl 2
F C I 4 C 1
Br 3
F Cl Br I
Increasing atomic number
4 3 2 1
Increasing priority
COOH 4
H 2N C Br 3 C 1
OH 2
C N O Br
Increasing priority
Rule 2: If two or more than two isotopes of the same element are present, the isotope of higher mass receives the higher
priority.
1 2 3
1H 1H 1H
Increasing priority
3 2 1
Rule 3: If two or more of the atoms directly bonded to the chiral carbon are identical, the atomic numbers of the next atoms
are used for priority assignment. If these atoms also have identical atoms attached to them, priority is determined at the
first point of difference along the chain. The atom that has attached to it an atom of higher priority has the higher priority.
I 2H and Br
↑
I H2C H2C C CH2 Br
↑
2H and C CH2 CH2 CH3
↑
2H and C
In this example, the atoms connected directly to the chiral carbon are iodine and three carbons. Iodine has the
highest priority. Connected, to the three carbons are 2H and Br, 2H and C and 2H and C. Bromine has the highest atomic
number amongst C, H and Br and thus CH2Br has highest priority among these three groups (i.e., priority number 2). The
remaining two carbons are still identical (C and 2H) connected to the second carbons of these groups are 2H and I and 2H
and C. Iodine has highest priority amongst these atoms, so that — CH2 — CH2 — I is next in the priority list and CH2—
CH2 — CH3 has the last priority.
1
I
I – CH2 – CH2 – C – CH2 – Br = 3 2
CH2 – CH2 – CH3
4
Rule 4: If a double or a triple bond is linked to chiral centre the involved atoms are duplicated or triplicated respectively.
O
C == O = C O
C ≡≡ N ≡ C N
N
O O
Step 1: By this rule, we obtain the following priority sequence:
CH = CR2 CN, CH2OH, CHO, CO, COOH

Increasing priority
Step 2: The molecule is then visualised so that the group of lowest priority (4) is directed away from the observes (at this
position the lowest priority is at the bottom of the plane). The remaining three groups are in a plane facing the observer.
If the eye travels clockwise as we look from the group of highest priority to the groups of second and third priority (i.e., 1
→ 2 → 3 with respect to 4) the configuration is designated R. If arrangement of groups is in anticlockwise direction, the
configuration designated S. For example,
2 2
1 C 3 3 C 1
4 4
Clockwise arrangement of Anticlockwise arrangement of
1 , 2 and 3 ⇒ R 1 , 2 and 3 ⇒ S
Let us apply the whole sequence to bromochlorofluoro methane.

F 1
Br C H = 1 C 4
Cl 2
In this Fischer projection the least priority number is not at the bottom of the plane.
In such cases the Fischer projection formula of the compound is converted into another equivalent projection formula
in such a manner that atom or group having the lowest priority is placed vertically downward. This may be down by two
interchanges between four priority numbers. The first interchange involves the two priority numbers, one is the least
priority number and other is the priority number which is present at the bottom of the plane. In the above case first inter-
changes will takes place between 2 and 4,
3 3
First interchange
1 C 4 between 2 and 4
1 C 2
2 4
(A) (B)
First interchange of two groups at the chiral centre inverts the configuration and this gives enantiomer of the original
compound. Thus (A) and (B) are enantiomer. The second interchange involves the remaining two groups.
A second interchange creates the original molecule (i.e., A)
3 1
Second interchange
1 C 2 between remaining
3 C 2
4 groups, i.e., 4
(B) 1 and 3 (A)
⇓
Arrangement of
1 , 2 and 3 are
clockwise, hence
configuration is R
Examples:
H O
CHO C 2
O First interchange
H C OH H C OH 4 C 1 between 3 and 4
CH2OH CH2OH 3
1 2
Second interchange
3 2 3 C 1
between 1 and 2
4 4
⇓
Clockwise
R configuration
CHO 2
(i) First interchange between 3 and 4
H C OH ≡ 1 C 4
(ii) Second interchange between 1 and 2
CH2OH 3
1
2 C 3
4
Anticlockwise
⇓
S–configuration
Glyceraldehyde (for example) has one asymmetric carbon, hence it has two configurational isomers (I) and (II).
CHO CHO
H C OH HO C H
CH2OH CH2OH
(R) glyceral dehyde (S) glyceral dehyde
(I) (II)
One can draw a number of other configurations for glyceraldehyde but each of them will be a repetition of either (I) or
(II). In this connection it is important to note that if two projection formulae of a molecule differ by an odd number of
interchanges (1, 3, 5, 7,. . . ) of positions of groups on the chiral carbon, they are different, but if the two differ by an even
number of interchanges (2, 4, 6,. . . ) they are identical. For example,
CHO CHO OH
H1 CH2OH Second interchange
H C OH First interchange CH 2
OH C H between OH, CHO CH 2
OH C CHO
CH2OH H H
(I) (II) (III)
Third interchange CH2OH, OH
CH2OH CH2OH
Fourth interchange
HO C H H, CHO
HO C CHO
CHO H
(V) (IV)
Thus, (I), (III) and (V) are identical. Similarly (II) and (IV) are identical.
69. If an open chain molecule has two or more similar asymmetric centres, number of optical isomers
will be
(a) 2n (b) more than 2n (c) less than 2n (d) n2
70. CH 3– CH –CH=CH2
|
OH
How many geometrical and optical isomers are possible in this compound?
(a) 0, 2 (b) 0, 3 (c) 2, 0 (d) 2, 2
71. CH3– CH − CH –CH2–CH3

| |
OH OH
How many optical isomers are possible in this compound?
(a) 2 (b) 3 (c) 4 (d) 5
72. CH3– CH − CH –CH3

| |
OH OH
(a) 2 (b) 3 (c) 4 (d) 5
73. CH3– CH − CH – CH –CH3
| | |
OH OH OH

(a) 2 (b) 3 (c) 4 (d) 5
SOLUTIONS
69. (c) 70. (a) 71. (c) 72. (b) 73. (c)
(10) Optical Isomerism in Compounds Containing No Chiral Carbon Atom

As mentioned earlier, the presence of chiral carbon in an organic compound is neither a necessary nor a sufficient condition
for showing optical activity. The chirality, i.e., dissymmetry of a molecule as a whole is the necessary condition for optical
activity. Various types of organic compounds are known which have no chiral carbon but the molecule as a whole is
dissymmetric. Due to this they are optically active. Compounds belonging to this group are allenes alkylidenes, spiranes
and biphenyls.
1. Allenes
Allenes are the compound with the general formula
>C=C=C<
Allenes are found to be optically active when the two groups attached to each terminal carbon atom are different, i.e.,
a a a x
C C C or C C C
b b b y
(I) (II)
Examples:
C6H5 C6H 5 H H H C2H5

C C C C C C C C C
C10H7 C10H7 CH3 CH3 CH3 H
2. Alkylidenes
When one of the double bonds in allenes is replaced by one cyclohexyl ring, compound is known as alkylidene cyclo-
alkane. Such compound will be optical active if two groups attached to each terminal carbon atom are different.
a a a x
C C
b b b y
Example:
H3C H
1 C
H 4 COOH
2 3
1-Methylcyclohexylidene-4-acetic acid
3. Spiranes
When both double bonds in allenes are replaced by two cycloalkane rings (same or different), resulting system is
known as spiranes. The resulting compound is represented below:
a a a x
b b b y
Examples:
H H H H
H 2N NH2 HOOC COOH
Cl OMe
Br H
4. Biphenyls
Biphenyls show optical isomerism when the following two conditions are satisfied: (i) Each ring should be
unsymmetrically substituted, i.e., neither ring should have a plane of symmetry.
A B B A A B B A B
B B B B A B
Both rings have no plane of symmetry Both rings have no plane of symmety
(ii) Both rings should be substituted at o-positions (minimum number of substituents should be two, one substituent
in each ring). The two substituents must have a large size.
A A A A A C
B B D
74. Mixture of enantiomers of N-methylethanamine cannot be resolved due to
(a) pyramidal inversion which leads to rapid inter-conversion between the enantiomers of this
compound as
CH3 CH3
H N N H
C2H5 C2H5
(b) self deprotonation-protonation as

CH3
H N +H N CH3
C2H5 C2H5
CH3
⊕
H N H+N
C2H5 CH3 C2H5

(c) both (a) and (b)

(d) none of these
75. CH3–CH=C=CH–CH3
If this compound is optically active then it should be due to
(a) non-planar geometry as
CH3 CH3
C= C=C
H H
(b) planar geometry as
CH3 CH3
C= C=C
H H
This geometry makes it dissymmetric
(c) non-planar geometry as
CH3 CH3
C= C=C
H H
This geometry makes it dissymmetric
(d) none of these
76. CH3–CH=C=C=C=CH-CH3
This structure leads to how many optical isomers
(a) 0 (b) 1 (c) 2 (d) 3
77. A biphenyl will be optically active if
(a) both phenyl rings are not coplanar to each other and either ring is not symmetrically substituted
(b) both phenyl rings are coplanar to each other and either ring is not symmetrically substituted
(c) both (a) and (b)
(d) none of these
78. Which of the following biphenyls is optically active?
I
NO2
I I
Br I I I Br Br
Br I Br Br
I Br
(a) (b) (c) (d)
SOLUTIONS
74. (a) 75. (a) 76. (c) 77. (a) 78. (b)
(11) Resolutioin of Racemic Modifications

The separation of a racemic mixture into its enantiomers is known as resolution. The following methods are used for
resolution.
(A) Resolution by Mechanical Separation: Since (+) and (-) forms have opposite crystalline shapes, this property
can be used in the separation of the two forms from a racemic mixture.
(B) Biochemical Separation: When a living organism is added to or developed to a racemic mixture, they eat up
one of the enantiomers preferentially leaving the other behind. Thus, resolution of racemic forms can be done using
this specific property of living organisms. For example, Penicillium glaucum can be used to remove (d)-ammonium
tartrate from the racemic mixture to leave back only the (l)-ammonium tartrate after a suitable time interval.
(C) Separation by Conversions into Diastereomers: Enantiomers have identical physical properties while
diastereomers have different physical properties. This fact is utilised in separation of enantiomers from racemic
mixture. The racemic mixture to be resolved is allowed to react with an opticallv active compound. This leads to the
formation of two diastereomers. These have different physical properties, so both diastereomers can be separated by
physical methods. Each of the enantiomers may then be regenerated and isolated from the diastereomers. Resolution
of enantiomers through the use of diastereomers is given below:
Pair of diastereomers, Top of
the molecules are mirror
1 : 1 enantiomers images but bottoms
are not.
B B B B
A C D+ D C A A C D D C A
X X Chemical W + W
(R) (S)
reaction
O U C W U C W
U C W V V
(R, R) (R, R)
V
(R)
Single optically active
enantiomer Physical
separation
R, R R, S
Chemical Chemical
reconvession reconvession
B B
A C D D C A
X X
(R) (S)
Separated enantiomers
Note: Group X reacts with group O to give new group W.
CONFORMATIONS OF ALKANES: ROTATION ABOUT CARBON-CARBON SINGLE BONDS

A carbon-carbon single bond is formed as the result of the overlap of an sp3 orbital of one carbon with an sp3 orbital
of a second carbon. Because sp3 orbitals are cylindrically symmetrical (they are symmetrical about an imaginary line
connecting the centers of the two atoms joined by the sigma bond), rotation about a carbon-carbon single bond is possible
without any change in the amount of orbital overlap (Figure 2.4). The different spatial arrangements of the atoms that result
from rotation about a single bond are called conformations. Different conformations are also called conformational
isomers or conformers.
C C
Figure 2.4 A carbon–carbon = is formed by the overlap of cylindrically symmetrical sp3 orbitals.
Therefore, the bond can rotate without changing the amount of orbital overlap.
When an ethane molecule rotates about its carbon-carbon bond, two extreme conformations can result: the staggered
conformation and the eclipsed conformation. An infinite number of conformations between these two extreme confor
mations is also possible. Compounds are three-dimensional, but we are limited to a two-dimensional sheet of paper when
showing their structures. There are several ways to represent on paper the three-dimensional spatial arrangements of the
atoms that occur as a result of rotation about a sigma (s) bond. Wedge-and-dash structures, sawhorse projections, and
Newman projections are all commonly used methods. In a wedge-and-dash structure, bonds protruding out from the plane
of the paper are drawn as solid wedges, those protruding into the paper are drawn as dashed lines, and solid lines are used
for bonds that lie in the plane of the paper. In a sawhorse projection, you are looking at the carbon-carbon bond from an
oblique angle. In a Newman projection, you are looking down the length of a particular carbon-carbon bond. The carbon
that is in front is represented by the point at which three bonds intersect, and the carbon that is in back is represented by a
circle. The three lines emanating from each of the carbons represent the carbon’s other three bonds. We will use Newman
projections because they do the best job of representing the conformational isomers.
staggered conformation eclipsed conformation

for rotation about the carbon- carbon for rotation about the carbon-carbon
bond in ethane bond in ethane
H H H H
wedge-and-dash C H 60°
C–C C–C
structures H H H
H H H H
H H H
sawhorse 60°
projections
H H H H
H
H H H H
H HH
Newman H H 60°
H H
projections H H H
H H
The electrons in a carbon-hydrogen bond will repel the electrons in another carbon-hydrogen bond if the bonds get too
close to each other. The staggered conformation, therefore, is the most stable conformation because the carbon-hydrogen
bonds are as far away from each other as possible. The eclipsed conformation is the least stable conformation, because in
no other conformation are the carbon-hydrogen bonds that close to one another. The extra energy of the eclipsed confor-
mation is called torsional strain. Torsional strain is the name given to the repulsion felt by the bonding electrons of one
substituent as they pass close to the bonding electrons of another substituent. In the staggered conformation, the distance
between the hydrogen nuclei is 2.55 Å, but they are only 2.29 Å apart in the eclipsed conformation.
Rotation about a carbon-carbon single bond is not completely free because of the energy difference between the
staggered and eclipsed conformations. The eclipsed conformation is of higher energy, so an energy barrier must
be overcome when rotation about the carbon-carbon bond occurs (Figure 2.5). This energy barrier is only 2.9kcal/mol
(12kJ/mol), which means that at room temperature there is enough thermal energy in the surroundings to allow an easy
transition over the barrier. So even though there is an energy barrier to rotation, the barrier is small enough to allow the
conformational isomers to interconvert millions of times per second at room temperature.
Butane has three carbon-carbon single bonds, and the molecule can rotate about each of them.
the C-2–C-3 bond

1 2 3 4
CH3–CH2–CH2–CH3
butane
the C-1 –C-1 bond the C-3 –C-4 bond
For example, a staggered and an eclipsed conformer can be drawn for rotation about the C-3—C-4 bond. The carbon
in the foreground in a Newman projection has the lower number.
eclipsed conformers
HH HH
3’ 2’
HH
1’
H3’ H H2’ H H1’

H
potential energy
H H1’ H H3’ H
H2’
2.9 kcal/mol
H H H H
H1’ H3’ H3’ H2’ H2’ H1’ H1’ H3’
H H H H
H H H H
H2’ H2’ staggered conformers H3’ H2’
0° 60° 120° 180° 240° 300° 360°
Degrees of rotation
Figure 2.5 Potential energy of ethane as a function of the angle of rotation about the carbon-carbon bond
CH2CH3 H CH2CH3
H H
H C-4 H H
H H H
H C-3
staggered conformation for rotation eclipsed conformation for rotation
about the C-3–C-4 bond in butane about the C-3–C-4 bond in butane
Although the staggered conformers resulting from rotation about the C-3—C-4 bond in butane all have the same
energy, the staggered conformers resulting from rotation about the C-2—C-3 bond do not have the same energy. The
staggered conformers for rotation about the C-2—C-3 bond in butane are shown below. Conformer C, in which the two
methyl groups are as far apart as possible, is more stable than the other two staggered conformers (A and E). The most
stable of the staggered conformers is called the anti conformer, and the other two staggered conformers are called gauche
conformers (anti is Greek for ‘opposite of’; gauche is French for ‘left’). In the anti conformer, the largest substituents are
opposite each other; in the gauche conformer, they are adjacent. The two gauche conformers have the same energy, but
each is 0.9 kcal/mol (3.8 kJ/mol) less stable than the anti conformer.
CH3 H CH3 CH3 H CH3 CH3 H3C CH3
H CH3 H H H 3C H
H H H CH3 H H H H H H H H
H H H 3C H H H
H CH3 H
staggered eclipsed staggered eclipsed staggered eclipsed
gauche anti gauche
A B C D E F
Anti and gauche conformers do not have the same energy because of steric strain. Steric strain (or steric hindrance) is
the strain put on a molecule when atoms or groups are too close to each other, which causes repulsion between the electron
clouds of the atoms or groups. The van der Waals radius is defined as half the distance between the nuclei of two equiva-
lent atoms or groups when they are at an energy minimum. The van der Waals radius of a methyl group is 2. 0 Å, whereas
the van der Waals radius of a hydrogen atom is 1.2 Å, Two methyl groups, therefore, must be at least 4. 0 Å apart (the sum
of their van der Waals radii), and a methyl and a hydrogen must be at least 3.2 Å apart, to avoid steric strain. There is more
steric strain in the gauche conformer than in the anti conformer, because the two methyl groups are closer together in the
gauche conformer. This is called a gauche interaction.
The eclipsed conformers resulting from rotation about the C-2—C-3 bond in butane also have different energies. The
eclipsed conformer in which the two methyl groups are closest to each other (F) is less stable than the other eclipsed
conformers (B and D). The energy diagram for rotation about the C-2—C-3 bond of butane is shown in Figure 2.6. All of
the eclipsed conformers have both torsional and steric strain—torsional strain because of bond-bond repulsion, and steric
strain because of the closeness of the eclipsing groups. In general, steric strain in molecules increases as the size of the
eclipsing groups increases.
Because there is continuous rotation about all of the carbon-carbon single bonds in a molecule, organic molecules with
carbon-carbon single bonds are not static balls and sticks. Molecules with carbon-carbon single bonds have many intercon
vertible conformers. Conformers cannot be separated because they rapidly inter-convert.
The number of molecules in a particular conformation at any one time depends on the stability of the conformation; the
more stable the conformation, the greater the number of molecules that will be in that conformation. So most molecules are
in staggered conformations, and more molecules are in an anti conformation than in a gauche conformation. Calculations
reveal that at room temperature about 72% of the molecules of butane are in the anti conformation and about 28% are in a
gauche conformation. The preference for a staggered conformation causes carbon chains to orient themselves in a zigzag
fashion, as shown by the structure of decane.
potential energy
B D F
4.5 kcal/mol
3.8 kcal/mol E
A 0.9 kcal/mol A
C
0° 60° 120° 180° 240° 300° 360°

Degrees of rotation
Figure 2.6 Potential energy of butane as a function of the degree of rotation about the C-2—C-3 bond. Green letters
refer to the conformers (A-F) shown on page 86.
a computer generated picture of decane
79. a. Draw all the staggered and eclipsed conformers for rotation about the C-2—C-3 bond of pentane.
b. Draw a potential energy diagram for rotation of the C-2—C-3 bond of pentane through 360°.
80. Which of the following conformers of 2-fluoroethanol is most stable?
OH O H
H H H F
(a) (b)
H F H H H H
(Anti form) (Gauche form)
OH F H OH
(c) (d)
H H F
H H H H H
(Fully eclipsed form) (Partially eclipsed form)
81. Which of the following statements I true about these two structures?
Cl Cl
CH3 D H Br
H CH3 D CH3
Br CH3
I II
(a) I and II are a pair of enantiomers (b) I and II are a pair of diastereomers
(c) I and II are a pair of conformers (d) I and II are a pair of structural isomers
CYCLOALKANES: RING STRAIN

Early chemists noted that cyclic compounds found in nature generally had five-or six-membered rings. Compounds with
three–and–four–membered rings were found much less frequently. This finding indicated that compounds with three-and
four-membered rings are not as stable as compounds with five or six-membered rings.
The German chemist Baeyer was the first to suggest that the instability of these small rings was due to angle strain.
We know that an sp3 hybridized carbon has bond angles of 109.5°. In 1885, Baeyer suggested that the stability of a cyclic
compound could be predicted by determining how close the bond angle of a planar cyclic compound is to the desired
tetrahedral bond angle of 109.5°. The angles in a regular triangle are 60°. The bond angles in cyclopropane, therefore, are
Compressed from the desired tetrahedral angle of 109.5°_to 6. 0°. The deviation of the bond angle from the desired bond
angle causes the strain known as angle strain.
banana bonds
The angle strain in a three-membered ring can be appreciated by looking at the orbitals that overlap to form the sigma
(s) bonds in cyclopropane (Figure 2.7). Normal s bonds are formed by the overlap of two sp3 orbitals that point directly
toward each other. In cyclopropane, overlapping orbitals cannot point directly toward each other. Therefore, orbital overlap
is less effective than in a normal carbon-carbon bond. The less effective orbital overlap causes the carbon-carbon bond to
be weaker than a normal carbon-carbon bond. Because the bonds in cyclopropane have shapes that resemble bananas, they
are sometimes called banana bonds.
In addition to angle strain, three-membered rings also have torsional strain, because all of the adjacent carbon-hydrogen
bonds are eclipsed.
good overlap poor overlap

strong bond weak bond
(a) (b)
Figure 2.7 (a) Overlap of sp3 orbitals in a normal σ bond. (b) Overlap of sp3 orbitals in cyclopropane.
The bond angles in planar cyclobutane would have to be compressed from 109.5° to 90°, the bond angle associated
with a planar four-membered ring. Planar cyclobutane would be expected to have less angle strain than cyclopropane
because the bond angles in cyclobutane are only 19.5° away from the normal tetrahedral bond angle.
cyclopropane
Baeyer predicted that a five-membered ring compound would be the most stable of the cyclic compounds because its
bond angles (108°) are the closest to the tetrahedral bond angle. He predicted that six-membered ring compounds with
bond angles of 120° would be less stable, and as cyclic compounds became larger than six-membered rings they would be
less and less stable.
‘planar’cyclopentane ‘planar’cyclohexane ‘planar’cycloheptane

bond angles = 108° bond angles = 120° bond angles = 128.6°
Contrary to what Baeyer predicted, however, cyclohexane is more stable than cyclopentane. Furthermore, cyclic
compounds do not become less and less stable as die number of sides increases. The mistake that Baeyer made was to
assume that all cyclic compounds are planar. Because three points define a plane, the carbons of cyclopropane must lie in
a plane. But the other cycloalkanes are not planar. Cyclic compounds twist and bend in order to achieve a final structure
that minimizes the three different kinds of strain that can destabilize a cyclic compound.
1. Angle strain is the strain that results when the bond angles are different from the desired tetrahedral bond angle of
109.5°.
2. Torsional strain is caused by repulsion of the bonding electrons of one substituent with the bonding electrons of a
nearby substituent.
3. Steric strain is caused by atoms or groups of atoms approaching each other too closely.
Although planar cyclobutane has less angle strain than cyclopropane, it has more torsional strain because it has eight
pairs of eclipsed hydrogens compared with six pairs in cyclopropane, In addition, the hydrogens in cyclobutane are closer
together. So cyclobutane is not planar—it is bent. One of its methylene groups is bent at an angle of about 25° from the
plane of the other three methylene groups. This increases the ring strain, but the increase is more than compensated for by
the decreased torsional strain that results from the adjacent hydrogens not being as eclipsed as they would be in a planar
structure.

cyclopentane
Unlike what Baeyer predicted, cyclopentane has some angle strain. If cyclopeantane were flat, there would be essentially
no angle strain but there would be ten pairs of adjacent hydrogens that would experience considerable torsional strain.
Cyclopentane puckers so that the hydrogens become nearly staggered. In the process, cyclopentane acquires some angle
strain. This puckered form of cyclopentane is called the envelope conformation, because the shape resembles a squarish
envelope with the flap up.
CONFORMATIONS OF CYCLOHEXANE
Despite Baeyer’s prediction that five-membered ring compounds would be the most stable, the cyclic compounds most
commonly found in nature contain six-membered rings. Six-membered ring compounds are so prevalent because they
can exist in a conformation that is almost completely free of strain. This conformation is called the chair conformation
(Figure 2.8). In the chair conformation of cyclohexane, for example, all the bond angles are 111°, which is very close to
the tetrahedral bond angle (109.5°), and all the adjacent carbon-hydrogen bonds are staggered. The chair conformation is
such an important conformation that you should learn how to draw it.
1. Draw two parallel lines of the same length, slanted upward. Both lines should start at the same height.
2. Connect the tops of the lines with a V. The left-hand side of the V should be slightly longer than the right-hand side.
Connect the bottoms of the line with an inverted V. The lines of the V and the inverted V are parallel. This completes
the framework of the six membered ring.
H H H H
6
4 H H 6 H CH2 H
H 5 H 2
1 1
4
H 2 H
3
H H1 H CH2 H
3
H H H H
chair conformation of Newman projection of ball-and-stick model of the
cyclohexane the chair conformation chair conformer of cyclohexane
Figure 2.8 The strain-free chair conformation of cyclohexane and the Newman projection of the chair conformation,
showing that all of the carbon-hydrogen bonds are staggered.
3. Each carbon has an axial and an equatorial bond. The axial bonds are parallel to the edge of the page and alternate
their directions. The one on the uppermost carbon is up, the next is down, the next is up, and so on.
4. The equatorial bonds (blue circles) point outward from the ring. If the axial bond is up, the equatorial bond on the
carbon is below the plane perpendicular to the bottom of the axial bond. If the axial bond is down, the equatorial bond
is above the plane perpendicular to the top of the axial bond.
equatorial bond
5. Notice that each equatorial bond is parallel to a ring bond ‘two carbons over. ’
6. Remember that cyclohexane is viewed on edge. The lower bonds of the ring are in front, and the upper bonds of the
ring are in back.
= axial bond
= equatorial bond
lf we assume that cyclohexane is completely free of strain, we can calculate the amount of total strain energy (angle
strain plus torsinal strain plus steric strain) that each of the other cycloalkanes experiences. Taking the heat of formation of
cyclohexane (Table 2.10) and dividing by 6 for the six CH2 groups in cyclohexane gives us a value of —4.92 kcal/mol ( —
20.6 kJ/mol) for a ‘strainless’ CH2 group ( — 29.5/6 = —4.92). We can now calculate the heat of formation of a ‘strainless’
cycloalkane by multiplying the number of CH2 groups in the ring by —4.92 kcal/mol. The total strain in the compound is
the difference between the ‘strainless’ heat of formation and the actual heat of formation (Table 2.8). For example, cyclo-
pentane has a ‘strainless’ heat of formation of 5 X —4.9 = — 24.6 kcal/mol. Because its actual heat of formation is —18.4
kcal/mol, it has a strain energy of 6.2 kcal/mol [-18.4 – (-24.6) = 6.2].
As a result of rotation about its carbon-carbon single bonds, cyclohexane rapidly interconverts between two stable
chair conformations. This interconversion is known as ring-flip (Figure 2.9). When the two chair conformers interconvert,
bonds that lire equatorial in one chair conformer become axial in the other chair conformer.
Cyclohexane can also exist in a boat conformation (Figure 2.10). Like the chair conformation, the boat conformation
is free of angle strain. However, the boat
Table 2.10 Heats of Formation and Total Strain Energies of Cycloalkenes

"Strainless"
Heat of formation Heat of formation Total strain energy
(kcal/mol) (kJ/mol) (kJ/mol) (kJ/mol) (kcal/mol) (kJ/mol)
cyclopropane +12.7 53.1 –14.6 –61.1 27.3 114.
cyclobutane +6.8 24.5 –19.7 –82.4 26.5 110
cyclopentane –18.4 –77. 0 –24.6 –102.9 6.2 25
cyclohexane –29.5 –123.4 –29.5 –123.4 0 0
cycloheptane –28.2 –118. 0 –34.4 –143.9 6.2 25
cyclooctane –29.7 –124.3 –39.4 –164.8 9.7 40
cyclononane –31.7 –132.6 –44.3 –185.4 12.6 5.
cyclodecane –36.9 –154.4 –49.2 –205.9 12.3 5.
cycloundecane –42.9 –179.5 –54.1 –226.4 11.2 40
pull this
carbon down
3 1 4 2
2 3 6
5 ring-flip
4 6 5 1
push this
carbon up
Figure 2.9 The bonds that are axial in one chair conformation are equatorial in the other chair conformation. The
bonds that are equatorial in one chair conformation are axial in the other chair conformation.
conformation is not as stable as the chair conformation because some of the carbon-hydrogen bonds in the boat conformation
are eclipsed. The boat conformation is further destabilized by the close proximity of the flagpole hydrogens. These
hydrogens (at the ‘bow’ and ‘stern’ of the boat) are 1.8 Å apart, but the sum of their van der Waals radii is 2.4 Å. The
flagpole hydrogens are also called transannular hydrogens because they are across the ring from each other.
The conformations that cyclohexane assumes when interconverting from one chair conformer to the other are shown
in Figure 2.11. To convert from the boat conformation to one of the chair conformations, one of the uppermost carbons of
the boat conformation must be pulled down so it becomes the bottommost carbon. When the uppermost carbon is pulled
down just a little, the twist-boat (or skew-boat) conformation is obtained. The twist-boat conformation is more stable
than the boat conformation because the flagpole hydrogens have moved away from each other. When the uppermost carbon
is pulled down to the point where it is in the same plane as the sides of the boat, the very unstable half-chair conformation
is obtained. Pulling the uppermost carbon down farther produces the chair conformation. Figure 2.11 shows the energy of
a cyclohexane molecule as it interconverts from one chair conformer to the other. The energy barrier for interconversion
from one chair conformer to the other is 10.8 kcal/mol (45.2 kJ/mol). From this value, it can be calculated that cyclohex-
ane undergoes 10 flips per second at room temperature. In other words, the two chair conformers are in rapid equilibrium.
flagpole hydrogens
H H
H H
H CH2 H
H H CH2 H
H
H H
H H
HH HH
H H
boat conformer of Newman projection of ball-and-stick model of the boat
cyclohexane the boat conformer conformer of cyclohexane
Figure 2.10 The boat conformation of cyclohexane and the Newman projection of the boat conformation, showing
that some of the carbon-hydrogen bonds are eclipsed.
half-chair half-chair
boat
free energy
twist-boat twist-boat
chair chair
Firure 2.11 Diagram showing the conformations of cyclohexane (and their relative energies) as one chair
conformation interconverts to the other chair conformation.
Because the chair conformers are the most stable of the conformers, at any instant more molecules of cyclohexane
are in chair conformations than in any other conformation. It has been calculated that, for every thousand molecules of
cyclohexane in the chair conformation, no more than two molecules are in the next most stable conformation—the twist-boat.
CONFORMATIONS OF MONOSUBSTITUTED CYCLOHEXANES

Unlike cyclohexane, which has two identical chair conformers, the two chair conformers of a monosubstituted cyclohexane
such as methylcyclohexane are not identical. Because the methyl substituent is in an equatorial position in one conformer
and in an axial position in the other conformer (Figure 2.12), the two chair conformers do not have the same stability.
The chair conformer with the substituent in the equatorial position is more stable than the chair conformer with the
substituent in the axial position. The reason is the same as the reason that an anti conformer is more stable than a gauche
conformer. We saw that an anti conformer is more stable than a gauche conformer because the gauche interaction causes
steric strain. Gauche interaction also make a cyclohexane with a substituent in the axial position less stable than a cyclo-
hexane with a substituent in the equatorial position. When the methyl group is in the equatorial position, it is anti to the
C-3 and C-5 carbons, and it extends into space away from the rest of the molecule.
When the methyl group is in the axial position, however, it is gauche to both the C-3 and the C-5 carbons (Figure 2.12).
If you take a few minutes to build models, you can easily see that a substituent has more room if it is in an equatorial
position.
the methyl group is in
an equatorial position
CH3
ring-flip the methyl group
in an axial posit
more stable
less stable CH3
chair conformer
chair conformer
Firgure 2.12 A substituent is in the equatorial position in chair conformation and in the exial position in the other
chair canformation. The conformation with the substituent in the equartorial position is more stable.
In addition to the steric strain resulting from the gauche relationship of the axial substituent and the C-3 and C-5 carbons,
the axial substituent also has unfavourable steric interactions with the two other axial substituents (in this case, hydrogens)
that are on the same side of the ring. Notice that the three axial bonds on the same side of the ring are parallel to each other.
The unfavourable steric interaction between an axial substituent and a substituent on one of these parallel bonds results
from the distance between them being less than the sum of their van der Waals radii. Because the interacting substituents
are on 1,3-positions relative to each other, these unfavourable steric interactions are called 1,3-diaxial interactions.
Since a substituent has more freedom from repulsive interactions with other atoms if it is in an equatorial position, at
any instant more monosubstituted cyclohexane molecules are in the chair conformer with the substituent in the equatorial
position than in the chair conformer with the substituent in the axial position. The relative amounts of the conformers with
the substituent in the equatorial and axial positions depend on the substituent. For example, the equilibrium constant (Keq)
for the conformers of methylcyclohexane indicates that 95% of methyl-cyclohexane molecules have the methyl group in
the equatorial position at 25 °C (see the calculation below). In the case of tert-butylcyclohexane, where the steric interac-
tions are even more destabilizing because a tert-butyl group is larger than a methyl group, more than 99.9% of the mol-
ecules have the tert-butyl group in the equatorial position. The investigation of the various conformations of a compound
and their relative stabilities is called conformational analysis.
15 NITROGEN AND PHOSPHOURS CHIRALITY CENTRES

Atoms other than carbon can be chirality centres. When an atom such as nitrogen or phosphorus has four different groups
or atoms attached to it, it is a chirality centre. Such compounds can exist as a pair of enantiomers, and the enantiomers can
be separated.
CH3 CH3 O O
+
H N Br P
+
Br– H N –
H H P
CH3CH2O
CH3CH2CH2CH2CH3 CH3CH2 CH2CH2CH3 OCH3 CH3O OCH2CH3
a pair of enantiomers a pair of enantiomers
If one of the four ‘groups’ attached to nitrogen is a pair of nonbonding electrons, the enantiomers cannot be separated
because rapid inversion between the two enantiomers takes place at room temperature.
Nitrogen is sp hybridized in the transition state for amine inversion. If, in a particular compound, the nitrogen atom
cannot achieve the 120° bond angles required for sp2 hybridization, inversion will not take place and the enantiomers can
be separated. For example, 1,2-dimethylaziridine cannot undergo inversion at room temperature because the nitrogen is
in a three-membered ring. A nitrogen in a three-membered ring cannot achieve a 120° bond angle. The two enantiomers,
therefore, can be separated.
CH3 CH3
H N N H
CH3 CH3
enantiomers of 1,2-dimethylaziridine
82. Compound I has two stereoisomers. But compounds II and III exist as single compounds. Explain.
CH = CH2 CH = CH2 CH = CH2
CH3 N H CH3 N H CH3 N H
+ +
CH2CH3 Cl– CH3 Cl–
I II III
CONFORMATIONS OF DISUBSTITUTED CYCLOHEXANES

Two things that we have already learned about monosubstituted cyclohexanes ai important to our understanding of the
conformations of disubstituted cycle hexanes:
1. The two chair conformations rapidly interconvert, and bonds that are equtorial in one conformation are axial in the
other conformation
2. There is more room for a substituent in an equatorial position than in an axial position.
Conformations of 1, 4-Disubstituted Cyclohexanes

1,4-Disubstituted cyclohexanes do not have any chirality centers; therefore, they d not have enantiomers. A 1,4-disubsti-
tuted cyclohexane has only one cis isomer an one trans isomer.
H H H C(CH3)3
H3C C(CH3)3 H 3C H
cis-1-tert-butyl- trans-1-tert-butyl-
4-methylcyclohexane 4-methylcyclohexane
Each of the isomers has two chair conformations. In drawing the conformation for a particular disubstituted cyclohexane,
do you place the substituents in the axia or in the equatorial positions? If you are working with three-dimensional
molecula models, it is easy to determine where the substituents for a given conformatioi should be placed. If, however,
you are working on a two-dimensional paper surface, it is a little more difficult unless you can easily visualize objects
in thre< dimensions. A way around this difficulty is to look first at the axial bonds. It readily apparent that substituents
in the 1,2-diaxial positions and in the 1,4-diaxia positions are trans to each other, while substituents in the 1,3-diaxial
positions art cis to each other. For example, we can easily see that one of the chair conformations of? Trans-1-terf-butyl-
4-methylcyclohexane has both substituents in axial positions It is harder to see that the other chair conformation has both
substituents in equatorial positions, but we know that it does because substituents that are axial in one conformation are
equatorial in the other conformation. the more stable conformation is the one with both substituents in equatorial positions,
where there is less chance of unfavourable steric interactions.
Table 2.11 Locations of Substituents in Disubstituted Cyclohexanes
cis trans
1,2-disubstituted one axial and one equatorial both equatorial or both axial
1,3-disubstituted both equatorial or both axial one axial and one equatorial
1,4-disubstituted one axial and one equatorial both equatorial or both axial
H
CH3
C(CH3)3
H3C H
H
more stable
H less stable C(CH3)3
trans-1-tert-butyl-4-methylcyclohexane
Because trans-1-tert-butyl-4-methylcyclohexane either has both substituents in equatorial positions or both substitu-
ents in axial positions, the cis isomer must have one substituent in the equatorial position and one substituent in the axial
position (Table 2.11). One of the chair conformations of cis-1-tert-butyl-4-methylcyclo-hexane has the tert-butyl group
in the equatorial position and the methyl group in the axial position, while the other chair conformation has the tert-butyl
group in the axial position and the methyl group in the equatorial position. A tert-butyl group is larger than a methyl group,
so the more stable conformation is the one with the tert-butyl group in the equatorial position, where there is more room
for the larger substituent.
H H
C(CH3)3 H3C
H
H
CH3 more stable less stable C(CH3)3

cis-1-tert-butyl-4-methylcyclohexane
CONFORMATIONS OF 1,3-DISUBSTITUTED CYCLOHEXANES

1,3-Disubstituted Cyclohexanes have two chirality centers. Therefore, a compound such as 1-tert-butyl-3-methylcyclohexane
has four stereoisomers. The cis isomer exists as a pair of enantiomers, and the trans isomer exists as a pair of enantiomers.
H H H H
H H CH3 CH3
(CH3)3C C(CH3)3 (CH3)3C C(CH3)3

CH3 CH3 H H
We know that the 1,3-diaxial positions are cis to each other. So each cis enantiomer has a chair conformation in which
both substituents are in axial positions and a chair conformation in which both substituents are in equatorial positions. The
most stable conformation for each cis isomer is the one in which both substituents are in equatorial positions. Because
the two enantiomers of cw-1-ferf-butyl-4-methylcy-clohexane are mirror images, the more stable conformation of one
enantiomer is the mirror image of the more stable conformation of the other enantiomer.
H H
H C(CH3)3
(CH3)3C H
CH3 CH3
the more stable chair conformation for each of the two enantiomers
of cis-1-tert-butyl-3-methylcyclohexane
Each enantiomer of trans-1-ferr-butyl-3-methylcyclohexane has two chair conformations. In each conformation, one
of the substituents is in the equatorial position and one is in the axial position. The more stable conformation is the one in
which the larger substituent is in the equatorial position.
H H
H3C C(CH3)3
(CH3)3C CH3
H H
the more stable chair conformation for each of the two enantiomers
of trans-1-tert-butyl-3-methylcyclohexane
CONFORMATIONS OF 1,2-DISUBSTITUTED CYCLOHEXANES

1,2-Disubstituted cyclohexanes, like 1,3-disubstituted cyclohexanes, have two chirality centers and four stereoisomers.
H H H H
H H C(CH3)3 (CH3)3C
H 3C CH3 H3C CH3

C(CH3)3 C(CH3)3 H H
In cis-1-terf-butyl-2-methylcyclohexane, one substituent is in the equatorial position and the other is in the axial
position. For each of the enantiomers, the conformation with the larger tert-butyl group in the equatorial position is the
more stable conformation.
H H
C(CH3)3 (CH ) C
3 3
H H
CH3 CH3
the more stable chair conformation for each of the two enantiomers of
cis-1-tert-butyl-2-methylcyclohexane
H H
C(CH3)3 (CH3)3C
CH3 H3C
H H
the more stable chair conformation for each of the two enantiomers of
trans-1-tert-butyl-2-methylcyclohexane
Because the 1,2-diaxial positions are trans to one another, the substituents in trans-1-ferf-butyl-2-methylcyclohexane
are both in axial positions in one conformation and both in equatorial positions in the other conformation. The conforma
tion with both substituents in equatorial positions is the more stable conformation.
Meso compound
If the two substituents in a 1,3-disubstituted cyclohexane are identical, the cis isomer will be a meso compound (because
it has a plane of symmetry) and the trans isomer will exist as a pair of enantiomers.
H CH3 CH3
H H H
CH3 H H
CH3 CH3 CH3
meso compound pair of enantiomers
Similarly, if the two substituents in a 1,2-disubstituted cyclohexane are identical, the cis compound will be a meso
compound and the trans compound will exist as a pair of enantiomers.
H H H Br Br H
Br Br Br H H Br
meso compound pair of enantiomers
So both 1,2-dibromocyclohexane and 1,3-dimethylcyclohexane have three non-interconvertible isomers. The cis
isomers are meso compounds; the trans isomers exist as a pair of enantiomers.
It is apparent from looking at the above structure for cis-1,2-dibromocyclohexane that the compound has a plane
of symmetry. Cyclohexane, however, is not a flat hexagon; it exists preferentially in a chair conformer, and the chair
con-former of cis-1, 2-dibromocyclohexane does not have a plane of symmetry. Only the much less stable boat conformer
of cis-1,2-dibromocyclohexane has a plane of symmetry. So is cis-1,2-dibromocyclohexane a meso compound? The
answer is yes. As longas any one conformer of a compound has a plane of symmetry the compound is achiral, and if the
compound has two chirality centers it can be considered to be a meso compound.
no plane of symmetry CH3 no plane of

CH3
H plane of
symmetry
Br
symmetry
H Br H Br
plane of
symmetry
H H Br Br H
Br Br Br CH3
chair conformer boat conformer CH3 staggered conformer
eclipsed conformer
This holds for acyclic compounds as well. We have seen that 2,3-dibromobutane is an achiral meso compound because
it has a plane of symmetry. But when we made that determipation, we were looking at a relatively unstable eclipsed
conformer. The more stablfe staggered conformer does not have a plane of symmetry. But 2,3-dibromobutaine is a meso
compound because it has a conformer that has a plane of symmetry.
CONFORMATIONS OF FUSED RINGS

When two cyclohexane rings are fused together, the second ring can be considered to be a pair of substituents bonded to the
first ring. The two substituents can be either cis or trans. If the cyclohexane rings are drawn in their chair conformations,
the trans isomer will have both substituents in the equatorial position. The cis isomer will have one substituent in the equa-
torial position and one substituent in the axial position. Trans fused rings, therefore, are more stable than cis fused rings.
H H
H
trans-decalin cis-decalin
trans-fused rings
cis-fused rings
more stable
less stable
Trans fused rings cannot undergo chair-chair interconversion. Cis fused rings are much more flexible and undergo
chair-chair interconversion almost as fast as cyclohexane.
STEREOCHEMISTRY OF REACTIONS: REGIOSELECTIVE, STEREOSELECTIVE, AND

STEREOSPECIFIC REACTIONS
Stereochemistry is the field of chemistry that deals with the structure of molecules in three dimensions. When we
study the stereochemistry of a reaction, we are concerned with the following questions:
1. If stereoisomers are possible for a reaction product, does the reaction produce a single stereoisomer, a set of particular
stereoisomers, or all possible stereoisomers?
2. If stereoisomers are possible for the reactant, do all stereoisomers react to form the same stereoisomeric product, or
does each reactant form a different stereoisomer or a different set of stereoisomers?
Before we examine the stereochemistry of addition reactions, let us become familiar with some terms used in describ-
ing the stereochemistry of a reaction.
We learned in that a regioselective reaction is one in which two constitutional isomers can be obtained as products but
more of one is obtained than of the other. A regioselective reaction selects for a particular constitutional isomer. Recall that
a reaction can be moderately regioselective, highly regioselective, or completely regioselective depending on the relative
amounts of the constitutional isomers formed in the reaction.
Stereoselective is a similar term, but it refers to the preferential formation of a stereoisomer rather than a constitutional
isomer. If a reaction that generates a carbon-carbon double bond or a chirality center in a product leads to the preferen
tial formation of one stereoisomer over another, it is a stereoselective reaction. In other words, it selects for a particular
stereoisomer. Depending on the degree of preference for a particular stereoisomer, a reaction can be described as being
moderately stereoselective, highly stereoselective, or completely stereoselective.
A regioselective reaction forms more of one constitutional isomer than of another.
A→B+C
more B is formed than C where B and C are constitutional isomers
A stereoselective reaction forms more of one stereoisomer than of another.
A→B+C
more B is formed than C where B and C are stereoisomers
In a stereospecific reaction, each stereoisomeric reactant forms a different stereoisomeric product.
A stereospecific reaction
A→B
C→D
A and C are stereoisomers
B and D are stereoisomers
All stereospecific reactions are also stereoselective. All stereoselective reactions are not necessarily stereospecific.
Notice that, in the preceding reaction, because stereoisomer A forms stereoisomer B but does not form D, the reaction
is stereoselective in addition to being stereospecific. All stereospecific reactions, therefore, are also stereoselective. All
stereoselective reactions are not stereospecific, however, because there are stereoselective reactions in which the reactant
does not have a carbon-carbon double bond or a chirality center, so it cannot exist as stereoisomers.
1. How many isomers are there corresponding to the CH 2 Cl2 , CH 2 Cl — CH 2 Cl, CHBr = CHCl ,
formula C4H10O?
CH 2 Cl — CH 2 Br .
Sol. There are 7—1-butanol, 2-butanol, 2-methyl-1-
Sol. Only CHBr = CHCl can exist as geometric iso-
propanol, 2-methyl-2-propanol, diethyl ether, methyl
mers:
propyl ether, and methylisopropyl ether.
Br Cl Br H
2. Compare the acidic strength of propenoic acid, C C and C C
propanoic acid and propynoic acid.
H H H Cl
Sol.
In CH 2 Cl — CH 2 Cl and CH 2 Cl — CH 2 Br ,
HC ≡ C — CO 2 H > CH 2 = CH — CO 2 H >
the carbon atoms are connected by a single bond
CH 3 — CH 2 — CO 2 H about which the groups can rotate relatively freely.
Thus any conformation of the halogen atoms may
3. Give reason why acetate ion is more stable than acetic be converted into any other simply by rotation about
acid.
the single bond. In CH 2 Cl2 , the configuration of the
Sol.
molecule is tetrahedral, and all interchanges of atoms
O O yield exactly equivalent configurations.
H3C C O ←→ H3C C O 6. Show why the phenolate ion, C6 H 5O – , has a greater

Both resonating structure of equal energy. resonance stabilization than phenol, C6 H 5OH .
O O Sol.
H3C C O H ←→ H3C C O H
O O O
(high energy so unstable)
Positive charge on
electronegative atom. O O
Phenol doesnot have low energy forms such as the

4. If the bonds in dichloro benzene, C6 H 4 Cl2 , were
three at the right, because the oxygen atom would
localized between specific carbon atoms, how many
have a partial positive charge.
isomer’s of this compound would exist? How many
isomer’s actually exists?
7. If the OH– has the Possibility of reaction with either a
Sol. If the bonds were localized, there would be 4 proton (or) a carbonium ion what will happen.
isomers; actually there are only 3. Of the following,
the first two are identical, because the bonds are not Sol. Generally hard nucleophiles react with hard elec-
localized. trophiles. OH– is a hard nucleophile and so reacts with
H+ more readily. Similarly soft nucleophiles react
with soft electrophiles.
Cl Cl Cl Cl
Cl Cl → adduct .
CH 2 = CH 2 + Br2 
nucleophile
Br2 reacts with ethylene because a soft nucleophile

Cl
reaction with soft electrophile. (In Br2, Br+ is a soft
Cl electrophile due to large size of Br atom).
5. Which of the following compounds can exist as 8. Calssify the following as Electrophiles (or)
geometric isomers? Nucleophiles.
C2 H 5 O – , BF3 , Cl+ , CCl2 , SiF4 , CH 4 , I – , NH 3 , NO 2+ , O O

H 2 , CH 3 CN, HCHO, HCl H3C C H3C C + H+
OH O
Sol. CH 4 and H 2 are neither nucleophilic nor elec-
trophilic. Because they are stable and all the electrons O O
are involved in bonding.
Ph C Ph C + H+
CH 3 — C ≡ N : CH 2 = O have electrophilic C. The O
OH
EN N (or) O is nucleophilic. These are both electro-
[Combine effect of –I + (+R) of phenyl group]
philic and nucleophilic.
11. Identify the stable carbocation in each pair
C2 H 5 — O – and I – are anions, NH3 has a lone pair. +
These are nucleophiles. (a) CH3 – CH2 – CH2+ and CH3 – CH – CH3
+
(b) CH 3 – CH – CH – CH3 and
BF3 Cl , CCl2 have only six valence electron – elec-
–
|
trophiles. CH3
+
NO +2 is a strong electrophile. CH3 – CH2 – C H – CH3
(c) CH3 –CH2+ and CH3 – O – CH2+
HCl provides H + -electrophile.
Sol. +
In SiF4 , Si can expand the octet and accept electron (a) CH3 – CH – CH3 (because of + I effect and hyper-
conjugation)+
pairs; ex. SiF62– -electrophile.
(b) CH3 – CH2 CH – CH3 (because of hyperconjuga-
tion)
9. Identify the effects operating in each of the +
(c) CH3 – O – CH2 (because of resonance due to l.p.
molecule. on oxygen)
(a) CH3Cl 12. Identify the stable carbanion in each pair
(b) CH3 — CH = CH2 –
(a) CH3 – CH2 – CH2– and CH3 – CH – CH3
O O O
− || − ||
CH C (b) C H2 – C– CH3 and C H 2 – CH2 – C– H
(c) H3C CH H (c) Ph – CH2– and Ph – CH2 – CH2–
Sol.
(d) CH2 = CH — CH = CH2
(a) CH3 – CH2 – CH2– (because of inductive effect)
Sol.
– O
(a) Inductive effect (b) CH2 – || – CH3 (because of mesomeric effect)
(b) Inductive and hyperconjugative effects C
(c) Inductive, hyperconjugative and mesomeric (c) Ph – CH2– (because of resonance)
effects
(d) Mesomeric effect and inductive effect 13. Which of the following intermediates is stable?
+ –
10. Is benzoic acid a stronger acid than acetic acid.
Explain your answer with proper reasoning.
Sol. Yes. This is due to the fact that [–I and (+R)] effect
(a) (b)
of phenyl group is less electron releasing (combindly)
than the +I effect of methyl group. Consequently,
the benzoate ion will be more stabilized than acetate Sol.
ion, thus making benzoic acid stronger than acetic (b) is stable because carbocations can’t form in the
acid. bridge head position.
14. Benzylamine is a stronger base than aniline. Explain. 20. Identify the effects operating in each of the molecule.
Sol. In aniline the lone pair of electrons on N atom are (a) CH3Cl
delocalised in the benzene ring and hence the basicity (b) CH3 – CH = CH2
decreases. O
||
15. Which of the following carbocations is most stable. (c) CH3 – CH = CH – C – H
+ (d) CH2 = CH – CH = CH2
Sol. (a) Inductive effect
(a) (b)
(b) Inductive and hyperconjugative effects
+
(c) Inductive, hyperconjugative and mesomeric
effects
Sol. (d) Mesomeric effect and inductive effect
(a) is most stable as it is a 3° carbocation as well as
allylic. 21. Can you think acidic nature of
(a) F—CH2COOH (b) Cl—CH2COOH
16. Why is always the resonance effect dominating over
(c) Br—CH2COOH (d) I —CH2COOH
the inductive effect?
Sol. As we have stated (–I) effect (electron-
Sol. Resonance effect operates thro’ the p-electrons withdrawing nature) is in order
and inductive effect operates thro’ the s-electrons. p- F > Cl > Br > I,
electrons can be easily perturbed and hence that effect hence (a) is strongest acid and (d) is weakest acid out
is dominating. of (a), (b), (c) and (d).
17. Write the isomeric structures of an alkene having m.f. F←←←←CH2COOH>Cl—←←← CH2COOH > Br
C4H8. Indicate which is more stable. — ←← CH2COOH > I —←CH2COOH
Sol. 22. Take the following isomeric a, b, g chlorobutyric acid
CH3 CH3 CH3 α β
CH3 CH2 C COOH CH3 C HCH2COOH
C = CH2; C = C; ↓ ↓
| |
H3C H Cl Cl
H
(I) (II) (i) (ii)
γ
CH3 H CH2CH2CH2COOH
↓
C=C; |
H CH3 Cl
(III) (iii)
The stability order is I > III > II Sol. As we have stated, as we go away from the
source, electron - withdrawing tendency decreases,
18. Which of the following C – Cl bond is weaker.
hence acidic nature also decrease. Thus
Cl
| 23. Compare the basic strength of the following
(a) Ph – CH– CH3 (b) Ph – CH2 – CH2 – Cl
NH3, CH3NH2 (CH3)2NH (CF3)3N
Sol.
(a) In this structure if we break C – Cl bond heterolyti- Sol. The increasing order of basic strength is as fol-
cally we end up with a C+ ion; a benzyl carbocation. lows
CF3 CH3 H
19. Which of the following carbonyl compound is more
acidic. H
O O N
|| || F3C N: < H — N < H — N < H 3 C
(a) CH3 – C – CH3 (b) CH3 – C – H
H H CH3
Sol. (b) The acidity of a-hydrogen depends on +ve
charge on the carbon atom to which it is attached. In CF3
an aldehyde the carbonyl carbon has more positive CF3 group being – I effect groups attracts the electron
charge and hence more –I effect. pair of nitrogen makes protonation difficult in primary
and secondary amine due to presence of +I effect Sol.

group (CH3) which make protonation easy. Hence the
increasing order of basic strength is as follows. H3 C Cl H Cl
C C
I > II > III
strongest weakest
24. C4H8 can have so many isomers. Write their structures.

Sol. C4H8 can have following structures: C C
(a) CH3—CH2—CH=CH2 1-butene H3 C Cl H Cl
I II
(b) CH3—CH=CH—CH3 2-butene, (cis and trans)
(c) CH3 — C=CH2 2-methyl-1-propene Resultant vector Resultant vector
| Br Cl Cl H
CH3
C C
(d) Cyclobutane
(e) Methyl cyclopropane
25. Write the following Alkenes in increasing order of
their stability with explanation C C
R2C=CR2, R2C=CHR, R2C=CH2, RCH=CH2, CH2=CH2 Br Cl
III H I Cl
Sol. Let R = CH3
Resultant vector Nonet resultant
(a) CH2 = CH2 (no. α-H. no. Hyperconjugation) vector
H3 C H
In I, there is addition of vector
(b) C=C (3α-H, 3-Hyperconjugative In II, there will neither be addition nor subtraction of
H structures) vector
H
H3C H In III, there is subtraction of vector
(c) C=C (6 α -H, 6H–structures) In IV, the vectors almost cancel each other. So the
CH3 increasing order of dipole moment is IV < III < II
H < I.
H3 C CH3
27. Why CCl3COOH is stronger acid than CH3COOH?
(d) C=C (9 α –H, 9H–structures)
Sol.
CH 3 H
Cl
+ & &+
(e) & & Į ±++VWUXFWXUHV Cl C C O
&+ &+ Cl O
From (a) to (e) number of hyperconjugative structures
Cl is the electron with drawing group which stabilize
increases, hence stability of alkene also increases,
the anion by distributing the charge where as in
hence the correct order is
case of CH3COOH, CH3 is electron releasing group
a < b < c < d < e
which destabilize the anion by increasing charge
26. Arrange the following species in increasing order of intensity. Therefore CCl3COOH is stronger acid than
dipole moment. CH3COOH.
Cis – 2,3–Dichloro–2–butene, O O
(i) || ||
Cis–1,2–dichloroethene, 28. Why CH3 – C– CH 2 – C – CH3 is known as active
(ii) methylene compound?
Cis–1,2–dibromo-1,2-dichloroethene, Sol. The – CH2 – group (methylene group) is acidic in
(iii) nature i.e. these hydrogen’s can be easily lost as H+,
trans–1,2–dichlorethene on action of a base because the resulting carbanion
(iv) can be resonance stabilized.
O O O– O H3C COOH
|| || ||
CH3 – C – CH – C– CH3 ←→ CH3 – C = CH –C – CH3 (c)
O F
O
|| COOH
←→CH3 – C – CH = C – CH3 ≡ (d) F
–
Oδ
–
Oδ Sol. As the inductive effect of fluorine decreases with
CH3 – C –––– CH –––– C – CH3 distance, (a) will be most acidic, because the carbox-
ylate ion which results after the loss of H+ can be
stabilized by electron withdrawing nature of fluorine
29. Why allylic free radical CH2 = CH – &+ is more (—I effect) which is strongest in which fluorine atom
stable than CH3– CH2 – &+ while both are primary is at α carbon.
free radicals.
33. Write all possible structural isomers of the compound
Sol. Allylic free radical is resonance stabilized while with molecular formula C4H10O.
propyl free radical is not resonance stabilized.
Sol. Total number of structural isomers = 7
&+ &+±&+ &+±&+ &+ {
G G
CH3 — CH2CH2CH2 — OH H3 C CH CH2OH

&+±&+±&+ (i)
CH3
(ii)
30. Give the order of stability of the following
carbocations. CH3
CH 3+ , CH 3 CH +2 , CH 3 CH 2 CH +2 ,
H3 C CH CH2CH3 H3 C C OH
CH 3 CH + CH 3 (CH 3 )3 C +
Sol. The decreasing order of stability OH CH3
(iii) (iv)
(CH 3 )3 C+ > CH 3 CH + CH 3 > CH 3 CH 2 CH +2 > CH 3 CH +2
CH3CH2 — O — CH2CH3
In
> CH +
3. CH 3 CH +2 , CH 3 group donates electron’s (v)
by +I effect. As the no. of CH 3 group increases dis-
tribution of charge and hence the reduction of charge CH3 — O — CH2 — CH2 — CH3
density on C bearing +ve charge is more effective. So (vi)
(CH 3 )3 C+ is most stable-most no. of alkyl groups- H3C O CH CH3
most stable.
CH3
31. Give the relative order of solubility of carbanions. (vii)
CH 3– , CH 3 CH 2– , CH 3 CH – CH 3 , (CH 3 )3 C –
Sol. The decreasing order is 34. In phenol, almost 100% enol form exists. Why?
CH 3– > CH 3 CH 2– > CH 3 CH – CH 3 > (CH 3 )3 C – .
Sol.
The order is opposite to that proposed for cations +I
effect of alkyl group increases the –ve charge on C.
OH
Electron releasing groups destabilize anions. O
32. Which among the following most acidic H
H3C COOH H
(a)
enol
F keto
F
In phenol, there is almost 100% enol form, because it
(b) H3C retains the aromaticity of the ring but in keto form the
CH2COOH aromaticity of the ring gets ruptured.
35. Sol. (a) P is larger than N. Electron delocalization and

H base weakening is more in PH3 due to larger size of
4 central atom
O O In PH3 bond angle is 90° lone pair left in s orbital
P uses p orbital for bonding, more strongly held.
H H In NH3 lone pair in sp3 hybrid orbital less s character
1 2 for orbital.
This lone pair is more available for bonding with H+,
H therefore NH3 > PH3.
OH (b) In SH–, S is larger and charge is more dispered and
3 more stabilized. So SH– weaker base.
Arrange all these numbered H in order of their OH– > SH–
decreasing acidic strength. OH– is conjugate acid which is weaker acid that is
Sol. The order is 4 > 3 > 2 > 1. why it is a stronger base than SH–.
36. How will you distinguish between Maleic acid and 40.
Fumaric acid. OC2H5
H3C CH2
Sol. Maleic acid forms an anhydride where as fumaric C C
acid does not.
O O O
I
CO2H H
C CH3
CH +
H3C CH2
H O C C
CH Δ
CO2H C O O
H
II
O
H CO2H When I and II are heated with base separately carban-
+
ion result which carbanion will be more stable.
H
Δ
no anhydride Sol. Carbanion from (II) will formed because of more
thermodynamic stability.
CO2H H
41. Why does cyclopentene not exhibit geometric isomer-
37. Arrange the following alcohols in increasing order of ism though it has a double bond.
acidity. Sol.
(a) CH 2 = CH — OH H H
(b) CH 3 — CH 2 — OH
Sol. a >b
CH 2 = CH — O –
This is cis form. Two H atoms on the same side.
the negative charge on 'O’ atom is delocalized to a To get trans, ring must be twisted.
lager extent. CH3 — CH2 — O–, the negative charge Double bond becomes severely twisted-destabilized.
on Ò’ atom is increased by +I effect. Effective overlap of P orbitals is missing, so does not
exist.
38. Write the basicity order of NH3, CH3NH2, (CH3)2NH,
(CH3)3N in aqueous medium. 42. Draw the structure of allyl cation. Compare its
Sol. stability with that of n-propyl cation.
(CH 3 ) 2 NH > CH 3 NH 2 > (CH 3 )3 N > NH 3 Sol. The Pz orbitals forming π-bonds and the empty
Pz orbital of the carbon with +ve charge are paral-
39. Explain the difference in base strengths of the lel. So the electrons may be delocalized. The +ve
following. charge is effectively spread out over two carbons;
(a) PH 3 & NH 3 (b) OH – & SH – delocalized.
H π − orbital Sol. CHCl3 is a stronger acid. Cl3CH —→ Cl3C– + H+

empty orbital In this case the negative charge on C is delocalised in
C C the vacant orbitals of Cl, which is absent in F3C–.
C H
H 47. HC ≡ C– is a weaker base than CH2 = CH–. Why?
H
Sol. HC ≡ C–, in this the negative charge is on a sp
+ +
hybridised carbon atom which has less tendency to
CH 2 = CH — C H 2 ←
→ C H 2 — CH = CH 2
give electrons.
In n propyl cation, +I effect of R increases the stabil-
ity. 48. Why does 2-butene exhibit cis-trans isomerism but
In allyl +M effect increases the stability. But +M ef- but-2-yne does not?
fect in allyl cation is more effective. So allyl > propyl. Sol. Alkynes are all linear molecules and hence there
A group with +M effect stabilizes cation; destabilizes is no chance of exhibiting geometrical isomerism.
anion.
49. Arrange the following in increasing order of reactivity
43. Between C C F and C C Cl which lone pair-π towards H+ addition.
conjugation will be more preffered.
(a) CH = CH2
Sol. Lone pair-pπ conjugation between fluorine and
carbon will be more effective than between chlorine CH = CH2
and carbon.
(b)
44. Suggest the order of stability of the following
+ + + + O 2N
(a) C H 3 , C H 2 Cl , C HCl2 , C Cl3
CH = CH2
(b) CH 3– , CH 2 Cl – ,CHCl2– , CCl3–
(c)
Sol. In both series, charge rests on C. In (a) –I effect
of Cl destabilizes cation. The order is Me
+ + + + CH = CH2
C H 3 > C H 2 Cl > C HCl2 > C Cl3 .
In (b) –I effect of Cl stabilizes anion. The order is
(d)
CCl3– > CHCl2– > CH 2 Cl – > CH 3– MeO
Electron with drawing group increases +ve charge Sol. d > c > a > b
of C in a cation; stability decreases. This group The order depends on the carbocation stability.
decreases the –ve charge of C by drawing electrons +
away; stabilized. CH – CH3 is a stable carbocation. It
is stabilized both by + I
Charge concentration is destabilizing.
effect and resonance.
Charge dispersal is stabilizing.
MeO
45. CH3CO2H is a stronger acid than CH3CH2 – OH.
Explain 50. Arrange the following in the increasing order of C –
O Br bond energy.
|| Br
Sol. CH3 – CO2H CH3 – C – O– + H+ |
CH3 – CH2 – OH —→CH3 – CH2 – O– + H+ (a) CH3 – C − CH 2 – CH3
|
In EtO– the negative charge on O atom is increased CH3
by +I effect, whereas in CH3CO2–, the negative charge
Br
on O atom is decreased by delocalisation. Lesser the |
charge density on negatively charged atom, weaker is (b) CH3 – CH– CH2 – CH2 – CH3
the base. (c) CH3 – CH2 – CH2 – CH2 – CH2 – Br
46. Which of the following will be a stronger acid and (d) CH2 = CH – Br
why? Cl3CH and F3CH (e) Ph – CH2 – Br
Sol. e < a < b < c < d In I, II, how many geometrical and optical isomers
The order depends on carbocation stability will be obtained.
Sol. In (I), 2 geometrical, 0 optical isomers and in (II)
51. Identify the enantiomeric and diasterreomeric pairs
2 geometrical and 2 optical isomers will be obtained.
among following
Therefore, in total 3 stereoisomers will be obtained
CH3 CH3 CH3
for (II) (as 1 is common).
HO H H OH H OH O
H OH HO H H OH 55. Compare the acidity of R—OH and R C OH.
CH3 CH3 CH3 Sol. In R — O– there is localized charge; + I effect of
(I) (II) (III) R increases the charge intensity. In RCOO– there is
stabilization due to resonance. (–M effect of C=O).
Sol. I and II are enantiomeric pair I, III and II, III are
diastereomeric pairs R C O
R C O
52. Which of the following pairs show tautomerism.
+ O O
OCH3 OMe
RCOO– is more stable; weaker conjugate base.
(a) CH3 – C – NMe 2 and CH 3 – C – NMe 2 RCOO > — OH as acid.
O OH 56. Arrange the following compounds in order of increas-
ing basicity.
(b) and CH3
N N
| (a) Cl3C , H3 C N CH3 , CH 3 — O — CH 3
H + –
Sol. (b) In (a) there is simple shifting of charge and (b) N H 4 , N H 2 , NH 3
hence it is resonance and not tautomerism. Sol.
53. In each of the following sets explain which structure (a) CH 3 — O — CH 3 > CH 3 — N — CH 3 > Cl3C –
is likely to be more important contributing structure
towards resonance hybrid. CH 3
⊕ ⊝ the order follows’ the order of stabilities of the
(a) CH2 = CH2 CH2 — CH2 conjugate acids.
(b) R2 C C O R2 C C O H
+
R R H3C O CH3 > H3C N CH3 > CHCl
3
(I) (II)
H CH3
(c) R C OH R C OH
O O (b) NH 4 < NH 3 < NH 2

+
(I) (II) N H 4 cannot act as a base as there are no-bonding
Sol. (a) II has charge separation; fewer no. of bonds; electrons.
higher in energy; less important; (I) is important.
57. Which of the following C—I bond is weak and why?
(b) II has a higher energy; the more E.N atom O has
+ve charge; O has only 6 electrons; I is important. (a) CH3O — CH2 — I
(c) II has charge separation; I is important. CH3
54. (b) H3 C N CH2 I
CH3 CH3 CH3
Sol. In the first case the carbocation generated is
CH3 stabilized by resonance due to the lone pair of O.
The same happens in the second case, but now due
H H H to the lone pair of N. N beingless electronegative
H can provide electrons easily. Hence the C—I bond in
(I) (II) second case is weak.
H 61. Compare the bond dissociation energies of C—H

bonds in the following:
CH3 — NH — CH2 — I H3 C N CH2 (a) H — CH 2 — CH 2 — CH 2 — CH 3
+
H3C N CH2 H
H (b) CH3
H3C
58. Account for the following: (c) (CH3)3 C — H.
(a) CCl3– is less basic than CF3– . Sol. The dissociation of a C—H bond gives a radical
. .
(b) I– is weaker base than F–. R — H  →R +H
Sol. (a) F is more electro negative. Exerts a strong
C—H bond dissocaition energy reflects the stability
inductive effect. In CCl3– resonance stabilization of R. Alkyl groups stabilize alkyl radicals. The order
occurs with p-d π bonding. of stability is R 3C > R 2 CH > R CH 2. If the radical
Cl C Cl Cl C Cl Cl C Cl ThreeR TwoR OneR
is more stable, C—H bond is weaker. So the order of
Cl Cl Cl decreasing bond dissociation energy is 1 > 2 > 3 (i.e.,
The stabilization is more effective than that by 1° > 2° > 3°).
inductive effect in CF3– . so CCl3– is weaker.
62. Why is Guanidine a stronger base?
(b) I– is larger than F–. Charge is more spread out (or)
delocalized. I– is more stable and less basic. NH
||
59. Explain the following: NH2 – C − NH2 (Guanidine)
(a) NC — CH2 — CN is a stronger acid than CH3 — Sol. In Guanidine lone pair on any one of the nitrogen
CO — C2H5. atoms is always available for donation as a base.
(b) CH3 — CO — C2H5 is more acidic than CH3 — –
NH NH
CH = CH2.
(c) CH3 — CH = CH — OH is more acidic than CH2
= CH — CH2 — OH.
+
H2 N NH2 H2 N NH2
Sol. (a) The anion formed by loss of proton is reso-
If any of the nitrogen gets protonated, even then also
nance stabilized.
we have a lone pair available for donation as a base.
N ≡ C – CH – C ≡ N N = C = CH – CH
+
N ≡ C – CH = C = N NH2 NH2
O O
H2C C C2 H5 H2C C C2 H5 +
H2 N NH2 H2 N NH2
Greater degree of delolalization makes the former an- Hence Guanidine is a stronger base
ion more stable. Since the conjugate base is weaker
the acid is stronger. 63. Among parachlorophenol and parafluorophenol,
(b) CH 2 — CH = CH 2 ← which will be a stronger acid and why?
→ CH 2 = CH — CH 2
Charge is delocalized on weakly electronegative Sol. The one having a weaker conjugate base will be
C. In the other more E.N O is involved; conjugate a stronger acid. If the conjugate base has to be weak,
base is weaker. Ketone is more acidic the negative charge has to be delocalised to a larger
(c) sp2 hybrid C is more EN and stabilizes the anion extent.
better. CH3 — CH = CH — O– is the weaker con- In P-chlorophenol
jugate base. O O O
60. Why does 2-butene exbibit cis-trans isomerism but – –

2-yne does not? Cl Cl Cl
Sol. Alkynes are all linear molecules and hence there Due to the availability of vacant orbitals in chlorine,
is no chance of exhibiting geometrical isomerism. the negative charge is delocalised to a larger extent.
The same cannot take place in case of F as F does is present on more electronegative atoms, there-
not have vacant orbitals. So, p-chlorophenol, hav- fore, it is more stable in comparison to that ion
ing a weaker conjugate base, becomes a stronger which have negative charge on less electronegative
acid. atoms.
64. Unlike other aromatic amines, why is the following Thus, due to higher stability of benzoate ion, it is
amine strongly basic? able to provide more H+, so it is more acidic.
NO 2 → C6 H 5 O − + H +
C6 H 5 OH 
Less stable
NMe 2 → C6 H 5 COO − + H +
C6 H 5 COOH 
More Stable
So order of acidic strength C6 H 5COOH > C6 H 5OH
67. Identify the pairs of enantiomers and diastereomers

NO2 from the following compounds I, II and III.
Sol. Due to the presence of bulky –NO2 groups on CH3 CH3 CH3
its ortho positions, the –NMe2 group goes outside
the plane of resonance to avoid steric repulsion. The H OH HO H HO H
C – N bond rotates and hence the lone pair of N goes HO H HO H H OH
perpendicular to the plane of benzene ring. As a result
the resonance is stopped and hence the lone pair is CH3 CH3 CH3
readily available as a base. (I) (II) (III)
65. Explain the following observations.
−
Sol. (a) Enantiomers are those optically active
(i) CH3 – I OH
 → CH3OH + I– isomers which are mirror image to each other
− but not superimposable to each other. Diastereo-
(ii) CF3 – I OH
 → CF3H + IO– isomers are those optical isomer which are nei-
Sol. In the first case I is more electronegative than C ther mirror image nor super-imposable to each
and hence the positive charge is an the C atom. So other.
OH– attacks C and displaces I–.
In the second case due to the presence of three CH3 CH 3 CH3
F atoms, the electron deficiency of C increases. Hence H OH HO H HO H
it gives a positive charge on I. Hence OH– attacks
I and displaces CF3. HO H HO H H OH
CH 3 CH3 CH3
–
CF3 – I OH CF3– + IOH (I) (II) (III)
Hence I and III are enantiomers while I and II or II

and III are diastereomers to each other.
CF3H + IO–
68. CH 2 = CH – is more basic than HC ≡ C – . Why?
66. Although phenoxide ion has more number of Sol. CH 2 = CH – is more basic than HC ≡ C – because
resonating structures than benzoate ion, benzoic acid
electronegativity of C – of HC ≡ C – is higher in com-
is a stronger acid than phenol. Why? –
parison to such carbon of CH 2 = CH – . In H — C ≡ C,
Sol. In resonating structure of phenoxide, nega- –
tive charge is present on C-atom (which is less C-atom is sp-hybrid while in CH 2 = C H C-atom is
electronegativ(e) while in benzoate ion, nega-
sp 2 hybrid. so in C-atom of HC ≡ C – , s-orbital char-
tive charge is present on more electronegative –
atom. Hence in ionic structure, if negative charge acter (50%) is higher than that of CH 2 = C H (33.3%).
On the basis of attraction of electron in orbital s > p 70. Which of the following is more acidic and why?
> d > f, the electron attraction tendency of such C- NH3 NH3
–
atom of HC ≡ C – is higher than that of CH 2 = C H.
So rate of donation of pair of electron CH 2 = CH – is
higher than that of HC ≡ C – because basic strength is
directly proportional rate of donation of free pair of
electron. F
NH3
69. Match the Kavalues
Ka
Sol. is more acidic due to the –I effect of
(a) Benzoic acid 3.3 × 10–5
(b) O2 N COOH 6.3 × 10–5
F
(c) Cl COOH 30.6 × 10–
5
fluorine atom present.
(d) H3CO COOH 6.4 × 10–5 71. 7-bromo-1, 3, 5-cycloheptatriene exists as ionic
species in aqueous solution while 5-bromo-1, 3
(e) H3C COOH 4.2 × 10–
5
cyclopentadiene doesn’t ionize even in presence of
Ag+ (aq). Explain.
Sol. For matching their Ka values acidic strength ∝ K a . Sol. The C—Br bond in the case of 7-bromo-1,
Hence, 3, 5-cycloheptatriene is broken easily because the
Acid Ka
intermediate carbocation formed is very
(a) O2 N COOH 30.6 × 10–5
stable (aromatic as it contains) (4n +2) number of π
(b) Cl COOH 6.4 × 10–
5
e– i.e., follows Hückle rul(e) while it does not break
(c) easily in the case of 5-bromo-1, 3 cyclopenta diene
COOH 6.3 × 10–5
because carbocation formed here is highly unstable
(d) H3C COOH 4.2 × 10–
5
as it is anti aromatic i.e., does not follow

(e) H3CO COOH 3.3 × 10– 5
Huckel rule. (It contains 4π electrons)
2. Consider the following compounds:

STEP–I CHECK YOUR CONCEPT
NH2 NH2 NH2 NH2
1. Which among the following carbocations is most
stable:
⊕
(a) C (b) C6H5 — CH2
NO2 CN CH3
(1) (2) (3) (4)
Arrange these compounds in decreasing order of their
⊕
(c) C6H5 CH C6 C5 (d) H3C C CH3 basicity:
(a) 1 > 2 > 3 > 4 (b) 2 > 3 > 1 > 4
CH3 (c) 4 > 1 > 3 > 2 (d) 4 > 1 > 2 > 3.
3. Which one of the following compounds has maximum 9. What is the decreasing order of stability of the ions?
enol content in solution: + +
O H3C HC H3C HC
(a) H3C C CH2 COOC2 H5 CH3 O CH3

O (I) (II)
(b) H3C C CH2 CN +

H3C HC
O
CH3
(c) H3C C CH3 O (III)
(d) O
(a) I > II > III (b) II > III > I
4. Arrange given compounds in order of decreasing (c) III > I > II (d) II > I > III
acidity: 10. Most unstable carbanion among the following is
(1) CH3 — NO2
(2) NO2 — CH2 — NO2 (a) H5 C 6 CH 2
(3) CH3 — CH2 — NO2
(4) O2N CH NO2
(b) F3C CH2
NO2 H2 C
(a) 4 > 2 > 1 > 3 (b) 4 > 2 > 3 > 1 (c) CHO
(c) 3 > 1 > 2 > 4 (d) 3 > 1 > 4 > 2.
(d) C 6 H5
5. 2-Methylpenta -2, 3 diene is achiral because it has:
(a) a centre of symmetry 11. Fischer projection indicates
(b) a plane of symmetry (a) Horizontal substituents above the plane
(c) a C2 axis of symmetry (b) Vertical substituents above the plane
(d) both centre and a plane of symmetry. (c) Both horizontal and vertical substituents below
6. The following compound can exhibit the plane
H (d) Both horizontal and vertical substituents above
H3C
the plane
C C H
H 3C C 12. Which of the following structures are super impossible
H3C COOH
H Br
(a) geometrical isomerism Br Me H Me
(b) geometrical and optical isomerism Et OH
HO Et
(c) optical isomerism
(d) tautomerism. Me Me
7. The number of optically active isomers observed in 2, (1) (2)
3-dichlorobutane is: Br Me
(a) 0 (b) 2
Me H Br H
(c) 3 (d) 4
Et Me HO Et
8. Which of the following carbon free radical is the most
stable? OH Me
(a) Vinyl carbon free radical (3) (4)
(b) Benzyl carbon free radical
(c) Tertiary carbon free radical (a) 1 and 2 (b) 2 and 3
(d) Secondary carbon free radical. (c) 1 and 4 (d) 1 and 3
13. The racemisation of optically active compounds is 22. Dichloro ethylene shows.
driven by (a) Geometrical isomerism
(a) entropy (b) Position isomerism
(b) enthalpy (c) Both
(c) entropy and enthalpy (d) None
(d) element of symmetry 23. The compound having molecular formula C4H10O can
14. The number of isomers for the aromatic compounds show
having M. F. C7H8O is: (a) Metamerism
(b) Functional isomerism
(a) two (b) three
(c) Positional isomerism
(c) four (d) five
(d) All
15. The total number of isomeric optically active
24. A compound contains 2 dissimilar asymmetric carbon
monochloro isopentanes is:
atoms. The number of optical isomers is:
(a) two (b) three (a) 2 (b) 3
(c) four (d) one (c) 4 (d) 5
16. The spatial arrangement of atoms or groups in a 25. The greater the s-character in an orbital the _____ is
stereoisomers is called : its energy
(a) conformation (b) configuration (a) Greater (b) Lower
(c) inversion (d) none of these (c) Both (d) None
17. Which of the following species is most stable? 26. The type of isomerism observed in urea molecule is
⊕
(a) p – NO2C6H4–CH2 (a) Chain (b) Position
(c) Geometrical (d) Functional
⊕
(b) C6H5CH2 27. Number of possible isomers of glucose are
⊕ (a) 10 (b) 14
(c) p – Cl1 – C6H4 – CH2 (b) 16 (d) 20
28. Which of the following statement is correct?
(d) +&2±&+±&+. +
(a) Allyl carbonium ion (CH2=CH– C H 2 ) is more
18. Resonance structures of a molecule should have stable than propyl carbonium ion
(a) identical arrangement of atoms (b) Propyl carbonium ion is more stable than allyl
(b) nearly the same energy content carbonium ion
(c) the same number of paired electrons (c) Both are equally stable
(d) identical bonding (d) None
19. Nitrophenol, C6H4(OH) (NO2) can have: 29. In which of the following alcohols C – O bond breaks
(heterolytically) with greatest ease:
(a) No isomer ( only a single compound is possible)
(b) Two isomers (a) CH3CH2CH2OH
(c) Three isomers CH3
(d) Four isomers
(b) CH3 – CH – OH
20. Geometrical isomerism is possible in: CH3
(a) Butene-2 (b) Ethene (c) CH3 – C – OH
(c) Propane (d) Propene
CH3
21. Which of the following compounds will exhibit cis- CH3
trans isomerism?
(d) CH3 – C – CH2 – OH
(a) 2-butene (b) 2-butyne
(c) 2-butanol (d) Butanol CH3
30. Which of the following carbocation is least stable O

+
CH2 (c) C 6H 5 C C6H 5
+
(a) (b) CH = CH 2 O CH3
CH3 (d) C6H5 C C C6H5
+
(c) CH2 = CH − C H2 (d) CH3 – C+
CH3
H
36. Which of the following has the most acidic hydrogen?
31. A compound contains 2 dissimilar asymmetric carbon
atoms. The number of optical isomers is: (a) 3-hexanone (b) 2, 4-hexanedione
(c) 2, 5-hexanedione (d) 2, 3-hexanedione.
(a) 2 (b) 3
(c) 4 (d) 5. 37. Of the following order of reactivity of Cl with AgNO3,
which one is correct?
32. Which of the following compound is incapable of
exhibiting tautomerism (a) CH2 = CH –CH2Cl > CH3CH2CH2Cl > CH3CH =
CHCl
(a) O (b) O (b) CH2 = CH – CH2Cl > CH3CH2CH2Cl < CH3CH =
CHCl
O O (c) CH2 = CHCH2Cl < CH3CH2CH2Cl > CH3CH =
CHCl
(c) O O (d) CH CH OH (d) CH2 = CHCH2Cl < CH3CH2CH2Cl < CH3CH =
CHCl.
33. Which of the following carbocations is expected to be
most stable? 38. Among 1-pentene, cis-2-pentene and trans-2-pentene
CH3 the correct order of stability is
CH3
(a) 1-pentene > cis-2-pentene > trans-2-pentene
(b) 1-pentene > cis-2-pentene < trans-2-pentene
(a) (b)
(c) 1-pentene < cis-2-pentene > trans-2-pentene
(d) 1-pentene < cis-2-pentene < trans-2-pentene.
X H X H
CH3 CH3
STEP–II APPLY YOUR CONCEPT
(c) (d)
H H 1. In the following compounds,
X X OH OH OH OH
34. Which of the following species is/are aromatic
(a) (b) SbCl6 NO2

Ph CH3 NO2
(c) (d) (1) (2) (3) (4)
H
Arrange these compounds in decreasing order of their
Ph
acidity.
35. keto-enol isomerism is observed in (a) 3 > 4 > 1 > 2 (b) 1 > 4 > 3 > 2
O (c) 2 > 1 > 3 > 4 (d) 4 > 3 > 1 > 2.
(a) C6H5 C H 2. How many optically active stereoisomers are possible
for butane-2, 3-diol:
O
(a) 1 (b) 2
(b) C6H5 C CH3 (c) 3 (d) 4.
3. The optically active tartaric acid is named as D –(+) – 8 9 1

tartaric acid because it has a positive: 7 2
(a) optical rotation and is derived from D-glucose
(b) pH in organic solvent 6 3
(c) optical rotation and is derived from D – (+) – 5 10 4
glyceraldehydes (a) 1 and 4 (b) 1 and 2
(d) optical rotation only when substituted by deute- (c) 2 and 3 (d) 9 and 10.
rium.
11. Which is the strongest carboxylic acid among the
4. A solution of (+) -2-chloro-2-phenylethane in toluene following?
racemises slowly in the presence of small amount of
(a) Cl3CCO2H (b) Br3CCO2H
SbCl5 , due to the formation of:
(c) F3CCO2H (d) Cl2CH-CO2H
(a) carbanion (b) carbene
(c) free-radical (d) carbocation. 12. The compounds C2H5OC2H5 and CH3OCH2CH3 are
(a) enantiomers (b) geometrical isomers
5. Which of the following has the highest nucleophilicity:
(c) metamers (d) conformational isomers
(a) F– (b) OH –
(c) CH 3– (d) NH 2– . 13. Which of the following, compounds displays
geometrical isomerism?
6. Which of the following, has the most acidic hydrogen: (a) CH2=CHBr (b) CH2=CBr2
(a) 3-hexanone (b) 2, 4-hexanedione (c) ClCH=CHBr (d) Br2C=CCl2
(c) 2, 5-hexanedione (d) 2, 3-hexanedione.
14. Among the following the compounds having the most
+ acidic alpha - hydrogen is:
7. N H3 NH3
Z Y (a) CH3CHO (b) CH3COCH3
(c) CH3-C-CH2CHO (d) CH3-CO-CH2-CO2CH3
COOH ||
X O
Arrange in order of increasing acidic strength 15. The number of optically active isomers observed in
(a) X > Z > Y (b) Z < X > Y 2,3, - dichlorobutane is:
(c) X > Y > Z (d) Z > X > Y.
(a) 0 (b) 2
8. The correct order of basicities of the following (c) 3 (d) 4
compounds is:
NH 16. Allyl isocyanide has:
(a) 9 sigma bonds and 4 pi bonds
1 H3C C (b) 9 sigma bonds, 3 pi bonds and 2 non-bonding
NH2 electrons
(c) 8 sigma bonds and 5 pi bonds
2 CH3 — CH2 — NH2
(d) 8 sigma bonds, 3 pi bonds and 4 non-bonding
3 (CH3)2 NH
electrons
O
17. The percentage of `s’ character of the hybrid orbital
4 H3C C NH2 of carbon in ethane, ethene and ethyne respectively
are
(a) 2 > 1 > 3 > 4 (b) 1 > 3 > 2 > 4
(c) 3 > 1 > 2 > 4 (d) 1 > 2 > 3 > 4 (a) 25, 33, 50 (b) 20, 50, 33
(c) 25, 50, 75 (d) 33, 66, 99
9. The number of isomers for the compound with
molecular formula CBrClFI is: 18. Isomers which can be interconverted through rotation
around a single bond are
(a) 3 (b) 4
(c) 5 (d) 6. (a) conformers
(b) diastereoisomers
10. The most reactive positions for electrophilic substitu- (c) enantiomers
tion reaction of anthracene are (d) positional isomers
19. Keto - enol tautomerism is observed in CH3 CH3

(a) H5C6-CHO (b) H5C6-CO-CH3
(c) H5C6-CO-C6H5 (d) H5C6-CO-CH2-CO-CH3 (b)
20. The compound which has one isopropyl group is:
H3C CH3
(a) 2,2,3,3 -tetramethyl pentane
(b) 2,2 - dimethyl pentane CH3 CH3
(c) 2,2,3 - trimethyl pentane
(d) 2-methyl pentane (c)
STEP–III CHECK YOUR EXPERTISE CH3 CH3

Br Br
Confront the Conceptual Questions As the Present JEE
Pattern
(d)
replace Hawith D and
Hbwith H
C2H5 (X) Br Br Br Br
1. H Hb
a replace Hbwith D and 4. The maximum number of stereoisomers that could for
H Br Hawith H the compound below?
C2H5 (Y)
Cl Cl
Relation between (X) and (Y) is:
(a) enantiomers (b) diastereomers
(c) E and Z isomer (d) constitutional isomer
Cl Cl
2. Among the following, the Newmann projections of
meso-2, 3-butanediol are: (a) 6 (b) 10
Me Me (c) 8 (d) 16
H OH H OH 5. Determine the absolute configuration of the labelled
carbons (a and b)
P. Q.
a b
HO H H OH Cl
Cl
Me Me
Me Me
HO Me Me H (a) a = R; b = R (b) a = R; b = S
(c) a = S; b = R (d) a = S; b = S
R. S.
6. Which of the structure (a – d) will be produced if a
HO H H OH “ring flip” occurs in the following compounds in chair
H OH form?
(a) P, Q (b) P, R
(c) R, S (d) Q, S
3. Which of the following pairs of compounds is a pair o
enantiomers?
Br (a) (b)
Br
(a)
(c) (d)
Cl- Cl
7. Which of the salts have identical solubilities in CH3 CH3

methanol?
H Br Br H
C6H5 C6H5
(III) CH3 H H CH3
(I) H CH3 CH3 CO2–
Br Br
NH ⊕
3
H
Which of the following is correct for above struc-
NH3⊕ H tures?
I II III
(II) H C6H5 CH3 COO
–
(a) enantiomers diastereomers Enantiomers
(b) identical enantiomers Enantiomers
CH3 C6H5 (c) enantiomers diastereomers Identical
C6H5 C6H5 (d) enantiomers identical Identical
(III) NH3⊕ 10. Which of the following equilibria has the lowest
CH3 H CH3
DG?
H CO2– CH3
NH3⊕ C6H5 (a) H3C O O

O
O
(IV) C6H5 H CH3 H
CH3
–
CH3 COO
(b) H3C
(a) I and IV (b) I and III
(c) I and II (d) II and IV
CH3
8. The following compounds differ in respect of:
(c) H C O
OH OH 3 O
O O O
HO HO O
CH3
HO OH HO OH
OH OH (d) H C
3
O
(a) their chemical and physical properties O
(b) nothing
(c) the direction in which they rotate plane of polar 11. Among the following structures, select E isomers
ized light (arrows indicate the bonds to be considered)?
(d) their interactions with molecules. Br
CH3
F
Br H H F
(a) H3C
9. (I) CH2Br O
H3C CH3
H3C F
H CH3
H Br
Cl H CH2CH3 H Cl H
O Br
(b) H3C O
(II)
CH3 Cl H CH3 CH2CH3 Cl H O CH3
CH3 Cl 15. What are the correct designations for the structures
below?
Cl
H 3C
(c) CH3
H 3C
CO2H
CH3 (a) E, E (b) Z
(c) E, Z (d) No stereoisomers are
H3C CH3
possible
(d) D 16. Which one of the following isomeric structures has
CH3 the lowest energy?
H
(a) (b)
12. Which of the following molecules is/are chiral?
Br H Br H
(I) Cl (c) (d)
OH (e)
(II)
OH
OH 17. Among the following, the most stable isomer is:
OH
H COOH
(III) HO H OMe
(a) OCH3 (b)
COOH
HO
(a) I (b) II OMe
(c) III (d) I, II OMe OH
13. How many isomers are possible for the following
(c) OH (d)
molecule?
H 18. The most stable conformation of the following
CHCH = CHCOOH
H3C compound is:
Me
(a) 1 (b) 2
Me
(c) 3 (d) 4
14. What is the relationship between the molecules in the
following pairs?
CHO CH2OH t–Bu
H OH HO H
H OH H OH Me
(a) t–Bu Me
HO H HO H
H OH HO H
Me
CH2OH CHO
(Fischer projections) (b)
(a) enantiomers (b) diastereomers t–Bu Me
(c) identical (d) structural isomers
Me (a) A
has two centers, but B does not have any
because it has a symmetry plane
(b) A and B are enantiomers ^
(c) A and B are diastereomers
(c) t–Bu (d) A and B are not present in equal amounts
22. How many stereogenic centres does it contain?
Me
H O
Me OCH3
t–Bu
(d)
O
Me
H O
19. Which of the following molecules have non zero (a) 1 (b) 2
dipole moments? (c) 3 (d) 4
(I) Gauche conformation of 1, 2-dibromoethane 23. Which of the following statements best describes the
(II) Anti conformation of 1, 2-dibromoethane stereochemical relationships of compound, I, II and
(III) Trans-1, 4-dibromocyclohexane III shown below?
(IV) cis - 1, 4-dibromocyclohexane
COOH COOH COOH
(V) Tetrabromomethane
H H H H H H
(VI) dibromocyclohexane
H3C H H CH3 H CH3
(a) I and II (b) I and IV
(c) II and V (d) I, IV and VI H CH3 CH3 H H CH3
H H H H H H
20. Consider the following energy profiles where A reacts COOH
COOH COOH
with reagent R and gets converted to C, and B reacts
with the same reagent (R) under identical conditions (I) (II) (III)
and get converted to D. Compounds A and B are
(a) All compounds are chiral
enantiomers of each other. Which statement about
(b) None of the compounds is chiral
the transition states for these transformations must be
(c) I and II are meso compounds
true?
(d) I and II are diastereomers, and III is meso com
A+R pound
(e) I and II are chiral
B+R 24. The number of all the possible stereoisomers formed
by the given compound is:
C
(a) The two transition states are enantiomers

(b) The two transition states are diastereomers
(c) The two transition states are E/Z isomers
(d) The two transition states are constitutional
isomers (a) 2 (b) 3
(c) 32 (d) 64
21. An aqueous solution containing compounds A and
B shows optical activity. A and B are steroisomers. 25. A naturally occurring substance has the constituting
Which of the following possibilities cannot be shown below. How many isomers may have this
correct? constitution?
O
HO CH2Cl
(c) (d) all
HO CH = CHCH = CHCH2CH2CH3
O O
(a) 2 (b) 8
(c) 16 (d) 64 30. Total number of stereoisomers possible, for following
26. What, if anything, can be said about the magnitude compound is:
of the equilibrium constant K for the following
CH = CH – CH2CH3
equilibrium?
H H
CH = CH2
H CH(CH3)2 H 3C H
(a) 8 (b) 16
CH3 CH(CH3)2 (c) 32 (d) 64
31. Which of the following has unstable enol form?
(a) K=1
(b) K<1 O O O O
(c) K>1 (a) (b)
(d) No estimate of K can be made
27. The two compounds shown below are: O
O
H H O
O O (c) (d)
and
32. Which of following compound can show geometrical

H H isomerism?
Br Cl CH3
(a) diastereomers (b) enantiomers
(c) epimers (d) regiomers (a) C=C (b) C
28. The molecular formula of diphenylmethane l Cl CH3
F Et CH3
CH2 is C13H12; CH3
(c) C=C (d) C
CH3
How many structural isomers are possible when one Cl Et CH3
of the hydrogen is replaced by a chlorine atom?
(a) 6 (b) 4 33. (i) 1, 2-dichlorocyclopropane = w
(c) 8 (d) 7
(ii) 1, 3-dimethyl-cyclobutanes = x
29. In which of the following keto form is more (iii) 2-bromo-3-chlorobutane = y
dominating than enol form. (iv) 1, 3-dimethyI cyclohexane = z
O Calculate total number of stereoisomer of the above
compounds.
(a) (b) O O Sum of w + x + y + z =............
(a) 8 (b) 12
O (c) 14 (d) 10
Me 38. Which of the following is most stable conformer?

H C2H5 C2H5
Me
34. I. II. H Br H
H H CH 2 5
Me Me H (a) (b)
H H Br
H H Br
H CH3 Br
III. Me IV. H
C2H5 Br
Me Me Me H Br H C2H5
Mark out the correct order of stability (decreasing
(c) (d)
order) for the given molecules (I to IV):
(a) I > II > III > IV (b) I > II = III >IV H Br H C 2H 5
(c) IV > III > II = I (d) III > I = II > IV C2H5 Br
35. How many stereoisomers are possible for Gorlic acid:
39. Metamer of the compound P is
(C18H30O2)
O
CH = CH
CH(CH2)6CH = CH(CH2)4 COOH P= C O
CH2 – CH2
O
(a) 6 (b) 4
(c) 8 (d) 2 (a) O C
36. The major product (ester) of the following reaction is O
Me O Me
H2SO4 (b) O C
* *
C – C – OH + HO C
H Et O
D H
(c) O C
(a) A single stereoisomer (optically active)
(b) A mixture of diastereomers (both optically active)
(d) All of these
(c) A reacemic mixture (optically inactive)
(d) A mixture of four stereoisomers (two reacemic 40. How many products (structural isomers only) are
mixtures) formed by monochlorination of
37. Which of the following is most stable conformation CH3
Cl Cl
CH3 H Cl CH3
(a) (b)
CH3
H CH3 H CH3
CH
Cl H
H3C CH3
Cl Cl
Cl Cl
H (a) 13 (b) 12
(c) 15 (d) 14
(c) (d)
H CH3 41. Which of the following compounds after complete
H CH hydrogenation will form three monochloro structure
H CH3 3
CH3 isomeric products?
(a) 3 (b) 4
(a) (b) CH3 – CH – C – CH3 (c) 5 (d) 6
CH3 CH2 Br CH3 H CH3
46. are
and
H H Br H
(c) (d)
(a) Identical (b) Diasteromers
(c) Conformers (d) Homologs
42. Which of the following compounds will not exhibit 47. How many optically active products will be formed in
geometrical isomerism? the following reaction?
F
monochlorination
CH3 Cl
(a) (a) 3 (b) 4
H (c) 5 (d) 6
Br
I 48. How many spatial orientations are possible in the
following compound?
(b) CH = N – NH CH = CHCH3
l
Me Me
H H
(c) H H CHClCH3 Br
Me Me
(a) 3 (b) 4
⊕ (c) 5 (d) 6
(d) N ≡ N : Cl
49. The two structures I and II represent:
43. The geometrical isomerism is shown by CH3 CH3
CH2 CH2 H H H H
(a) (b)
H3C CH3 H3C H

H CH3
CHCl I II
(c) (d)
(a) Conformational isomers
CHCl (b) Stereoisomers
44. Geometrical isomerism is shown by (c) Constitutional isomers
(d) Identical
CHBr
(a) (b) 50. In the given four conformational isomers which of the
following has minimum torsional strain and minimum
vander waal strain.
CH3 CH3
CH – CH3 H
H CH3
(c) (d) a and b
CH3
H CH3
H CH
45. The total number of isomers for the compound with CH3 3 CH3
molecular formula C2BrClFI is: I II
CH3 CH3 54. The following two compounds are:

CH3 H CH3
H
H CH H CH3 , ,,
CH3 3
CH3 (a) Identical
III IV
(b) Conformational isomers
(a) I (b) II (c) Geometrical isomers
(c) III (d) IV (d) Structural isomers
51. Which of the following statements regarding the 55. Which of the following is optically inative?
projections shown below is true?
H
H3C Cl Cl
H + &+
(a) (b)
Cl CH3
H CH3 2
H Cl CH3
(a) (b) &+
(a) ‘a’ and ‘b’ both represent the same configuration &+ &+
(b) Both ‘a’ and ‘b’ are optically active
(c) (d)
(c) ‘b’ alone is optically active
(d) ‘a’ alone is optically active &+ &+
2+
52. Which of the following is an achiral molecule?
CH3 56. An organic hydrocarbon on oxidative ozonolysis
CH3 Br H produces oxalic acid and butanedioic acid. Its
H3C Cl structure is
(a) (b)
H Cl (a) (b)
H Cl
H CH3
&22+ (c) (b)
&+
+ 2+
+ 2+
(c) (d)
57. &±2 and
+& + + 2+
&+ &22+ 2
53. The correct stability order of following species is +±&±2 are

2
(a) Position isomers (b) Chain isomers
(c) Functional isomers (d) Metamers
[ \ 58. In which reaction a chiral reactant is giving a chiral
product.
& CH3
] Z C − C2H5
KMnO4/ OH−/
(a) x > y > w > z (b) y > x > w > z (a)
H
(c) x > w > z > y (d) z > x > y > w
HOC H CHO (i) O3

61. Which of the following statements is not correct?
(b) H
(ii) Zn/H2O (a) A compound whose molecule has D configuration
C=C H
Reductive ozonolysis will always be dextrorotatory
CH3 H CH3 (b) A compound whose molecule has D configuration
may be dextrorotatory or levorotatory
CH = CH2 (c) A compound whose molecule has R configuration
O3/Zn/H2O may be dexrotatory or levorotatory
(c) H CH2 − CH3
(d) A compound whose molecule has L configuration
CH2OH may be dextrorotatory or levorotatory
CH3 62. Identify the pair of enantiomers amongst the given
pairs:
H Cl
H2/Ni
COOH CH3
(d) C=O (a) D OH, HOOC OH
H Cl CH3 D
CH3 Ph CH3
59. Which of the following statements is true about the (b) HO CH3 HO Ph
follownig conformer (X)? H H
COOH
COOH OH
CH3 I
(X) (c) H OH3 HOOC CH3
I CH3 CH H
COOH
CH3 CH3
(a) ( X) is the most stable conformer of meso-2,3-
(d) H OH, HO Ph
Diiodo-2,3-dimethylbutanedioic acid
(b) The most stable conformation will be CH3 CH3
I
CH3 I 63. The stereochemical formula of deiastereomer ‘Y’ of
(Y) optically active compound ‘X’ is: X = 2,3-Dihydrox-
CH3 COOH butanedioic acid.
COOH 2+
(c) T
he dipole moment of (X) is not zero but that of + &22+
Y is zero. (a) +22& +
(d) None 2+
60. An unsaturated hydrocarbon on complete hydrogena- &22+

tion gives 1-isopropyl-3 methylcyclohexane, after + 2+
ozonoiysis it gives one mole of formaldehyde, one (b) +22& +
mole of acetone and one mole of 2,4-Dioxohexanedial. 2+
The possible structured of the hydrocarbon may be &22+
+2 +
(a) (b) (c) + 2+
&22+
2+
+ &22+
(c) (b) (d) +2 &22+
+
64. The correct stability order of following species is: (a) N(I) has more ‘s’ character in N-CH3 bonds
(b) N(II) has more ‘s’ character in N-H bonds
(c) N(I) has less ‘s’ character in N-CH3 bonds
(a) (b)
(d) None of these
[
\ 69. The acid strength order is:
(c) & (d) 2 2+ 2+
Z
]
(a) x > y > w > z (b) y > x > w > z 2 2+
(c) x > w > z > y (d) z > x > y > w , ,,
65. Which of the following does not represent the +2 2+ &+ &+
& &
resonating structure of
2 2
(a) (b) ,,, ,9
(a) I > IV > II > III (b) III > I > II > IV
(c) II > III > I > IV (d) I > III > II > IV
(c) (d)
70. Acid strength of the conjugate acids of the following
66. The most stable resonating structure of are:
xx
&+ 2
xx
&+ &+:
(i) N NH (ii) N NH

(a) +&í2í&+í&+
(iii) (iv)
(b) +&í2 &+í&+
N N

(c) +&í2 &+í&+ H
(a) I> II> III >IV (b) III> II> I> IV
(d) +&í2 &+í&+ (c) IV> III> II> I (d) None of these
67. In which of the following molecules all the effects O

namely inductive, mesomeric and hyperconjugation CH3 S
operate:? 71. If P ix mixed with NaOH solution.
H
(a) (b) &+ R
&O Q O
&+ Acid base reaction occurs and HO snatches H from
organic molecule. Which carbon will loses H easily?
(c) &2&+ (d) (a) P (b) Q
(c) R (d) S
&+
72.
(a) N(I) has more ‘s’ character in N-CH3 bonds
(b) N(II) has more ‘s’ character in N-H bonds OH
(c) N(I) has less ‘s’ character in N-CH3 bonds
(d) None of these COOH (x)
&+ + OH
+ & &+ + +
1 1
(z) HOOC
HO
68. Between DQG
, ,, COOH (y)
The correct acidic strength order of acidic hydrogen (a) I > II ; III > IV; V > VI ; VII < VIII
x,y and z is respectively. (b) I < II ; III > IV ; V < VI ; VII > VIII
(a) x > z > y (b) x > y > z (c) I > II ; 111 > IV; V> VI ; VII > VIII
(c) z > y > x (d) y > z > x (d) I < II ; III > IV ; V < VI ; VII < VIII
73. 76. For the reaction shown below, which of the following
H represents the number of transition states and interme-
diates that would be present in the reaction coordinate
(p) N NH (r) diagram?
OH
O N O
H4SO4
H Major product
∆
(q)
Number of Number of
The correct basicity order of atoms p, q and r is:
Transition States Intermediates
(a) p > q > r (b) r > p > q
(c) r > q > p (d) q > p > r (a) 3 2
(b) 4 3
74. (c) 5 4
O (d) 6 5
N N N
N
H H H 77. A. B. C.
I II III IV
The order of basicity is
(a) I > IV > II > III (b) I > II > IV > II Compare carbon-carbon bond rotation across A, B,
(c) III > II > IV > I (d) II > III > IV > I and C
(a) A > B > C (b) A > C > B
75. The correct order of acid and basic strength for the (c) B > A > C (d) B > C > A
following pair of compounds should be?
78. Which of the following statement is/are correct?
COOH COOH COOH 1. Cl – CH2 – CHO is more reactive than CH3CHO
CH3 due to –I effect of Cl
CHO CHO
I II III 2. is less reactive than for addition

COOH NH2 NH2 reaction
CH3 CH3 NO2 CH3
3. A
cetone will be less reactive than acetophenone
for addition reaction.
O
IV V VI
NH2 NH2 4. C6H4 − C – C6H5 will be more reactive than

CH3 O
C6H4 − C – CH3for addition reaction.

(a) 1, 2 and 3 are correct
VII VIII (b) Only 1 is correct
(c) 1, 2 and 4 are correct

(d) 1, 2, 3 and 4 are correct (a) (b)
79. Rank the following substances in order of decreasing Br
heat of combustion (maximum → minimum).
(c) (d)
CH3
CH3 Br
1. 2. Br
83. Most stable carbocation among the given example is:
CH3 CH3
⊕
CH3 (a) ⊕ (b)
3. 4.
⊕
(c) CH2 (d) CH3
⊕
CH3
–
(a) 1 > 2 > 4 > 5 (b) 3 > 4 > 2 > 1 +
SbF6
(c) 2 > 4 > 1 > 3 (d) 1 > 3 > 2 > 4 X
SbF5
84.
F F
F
80. F X
O2N
The stability of the product can be explained by
NO2
(a) F– is better leaving group than other group
I II III “X”
F F (b) This is an acid base reaction
H3C (c) Product stabilises by aromatisation
O O2N NO2 (d) Above reaction is not possible
IV V 85. Increasing order of acidic strength of the compounds:
Ease of nucleophilic substitution among these com-
pounds will be in the order. OH OH OH OH
(a) II > III > IV > V > I (b) I > II > III > IV > V NO2 CH3
(c) V > II > III > I > IV (d) IV > III > II > I > V
81. How many degrees of unsaturation are there in the
following compound? NO2 CH3
OH I II III IV
(a) II > I > IV > III (b) III < IV II > IV > III (d) III < IV < II < I
Me Me Me Me
OH
N N
(a) 6 (b) 7 Me Me
(c) 10 (d) 11
86. , ; Dipole moments
Br
alc. KOH Me Me
82. A, A is
NO2 NO2
Br (A) (B)
Br of above compound will be:
(a) (A) = 6.87D, (B) = 4.11D 91. Which of the following example has both the
(b) (A) = 4.11 D, (B) = 6.87 D resonating structure contributing equal to the
(c) (A) = 4.11D, (B) = 4.11D resonance hybrid
(d) (A) = 6.87D, (B) = 6.87D
⊕
(a) CH C CH CH CH3
87. Which of the following carbonyl compounds will 3
form carbanion most readily?

CH3
H 3C ⊕
O O CH3 C CH CH CH3
(a) (b) H3C
H 3C CH3 CH3
CH3
O ⊕
(b) CH3 C NH2 CH3 C NH2
(c) H3C O (d) H3C
CH3 O O
CH3
O O
88. Which of the following pairs of structures is not a pair (c) CH3 C CH3 C
of resonating structures? O O
⊕ ⊕
(a) H — C ≡≡ NH; H — C == NH (d) CH2 CH CH O
⊕
(b) CH3CH = CHCH3; CH3CH2CH = CH2 CH2 CH CH O
(c) CH — C CH — C — CH3;
3
92. The decreasing order of bond length of C = C bond in
O O the following compounds is:
CH3 — C — CH — C — CH3 H 3C
O O
⊕
(d) ; H 3C
I II III IV
⊕ (a) II > I > IV > III (b) III > I > II > IV
(c) IV > II > I > III (d) IV > I > II > III
89. Most stable carbocation among the following is:
(a) H3C — O (b) H C O 93. Which is the best leaving group in a nucleophilic
+
3 substitution reaction?
CH2 +
CH2 (a) SO3−
H 3C
+
(c) C NO2 (d) F3C – CH2+ SO3−
(b) F3C
H3C
(c) OH–
90. HNCO in isocyanic acid exist as following resonating (d) O
–
structures
O H—N—C O 94. Select the option that incorrectly defines the order of
H—N C
electron density in benzene ring.
H—N C—O OH CI NO2
The correct order of stability is
(a) I > III > II (b) I > II > III (a) > > >
(c) II > III > I (d) II > I > III
NH2 NO CN NO2 Br
O2N NO2
CI
(b) > > > (c) (d)
CN CH3 OH NO2
98. The product in the reaction
(c) > > > CH3 CH3
OH
NH2
(a) (b)
O OH OCH3
Br
(d) CH3 CH3
> > > Br
Br
(c) (d)
95. Which one is the least acidic among the following? OH
OH 99. Correct acidic strength order is:
O 2N NO2 O
(a) (b) H3C COOH
COOH
NO2 NO2 NO2
OH
NO2 (I) (II)
O O NO2
(c) H (d) H5C6
OH OH COOH COOH
NO2
96. Correct acidic strength order is
(III) (IV)
COOH COOH NO2
H3C CH3 NO2 NO2
(I) (II) (a) III > I > IV > II (b) I > III > II > IV
(c) II > III > I > IV (d) IV > III > II > I
NO2 NO2
100. W
hich of the following compounds have a dipole
COOH COOH moment?
(III) (IV)
(a) (b)
H3C CH3
NO2 SO3H
NO2
(a) IV > I < II < III (b) II < IV < III I > III O 2N
97. Which one of the following compound undergo 101. In which of the following first is more acidic than
nucleophilic substitution faster second?
OH OH
CH3
Br
Br (a)
(a) (b)
CH3
OH OH Hb
Ha
Me Me
104. CH3 will
(b)
⊕
Me Me
NO2 NO2
(a) Rearrangement to gain stabilization
OH OH (b) Eliminate Ha to gain stabilisation
(c) Both are correct
(c) (d) None of correct
OH 105. Which of the following has longest C – O bond:
CH3 O O
OH OH (a) (b)
(d) O
O
(c) (d)
OH NO2
⊕ CH2
CH
102. In the carbocation rearranges to
H2C 106. Among the following molecules, the correct order of
C - C bond length is
gain stability, it will rearrange to
(a) C2H6 > C6H6 > C2H2 > C2H4
CH3 ⊕
(b) C2H6 > C6H6 > C2H4 > C2H2 (C6H6 is benzene)
(a) H2C ⊕ (b)
(c) C2H4 > C2H6 > C2H2 > C6H6
⊕ (d) C2H6 > C2H4 > C2H2 > C6H6
⊕ CH2
(c) CH (d) H3C 107. CH2 = CH – CH = CH – CH = CH2 I
+ Θ
CH2 = CH – C H – CH = CH – C H2 II.
103. The correct order of acid strength in the following + Θ
CH 2 – CH = CH – CH = CH – C H III.
questions 2
OH Among these three canonical structures (through

OH OH
more are possibl(e) what would be their relative
Me Me Me
contribution in THE hybrid:
(c) I > III > II (d) III > I > II
NO2
108. For 1-methoxy-l, 3-butadiene, which of the following
I II III resonating structure is the least stable?
OH OH OH ⊕ ⊕
Me Me (a) H2C – CH = CH – O – CH3
⊕
(b) H2C – CH = CH – CH = O – CH3
Me Me Me Me ⊕
NO2 NO2 (a) H2C = CH – CH – CH – O – CH3
IV V VI +
(a) CH2 = CH – CH – CH – O – CH3
(a) III > IV > VI > V > II > I
(b) III > IV > VI > I > II 109. Among the following which statement is not correct:
(c) III > IV > V > VI > I > II (a) 4 nitrophenol is more acidic than 3, 5-dimeth-
(d) IV > III > VI > V > I > II yl–4–nitrophenol
114. Which is most stable?

(b) Among R2NH, and R – C ≡ N weakest
N
base is R — C ≡ N O O
(c) Bridge head carbocation is rarely formed
(d) p-fluorophenol is stronger acid than p-chlorophenol
(a)
110. For the following compounds, arrange the labelled O
proton in increasing order of their ease of deprotonation.
H2 OMe
MeO
OMe
O SO3H3 (b) MeO
H1
CH2
O
O O
(c) Ph – C – CH2 – CH2
(a) (2 < 3 < 1) (b) (1< 2 < 3)
(c) (3 < 2 < 1) (d) ( 1 < 3 < 2) (d) CH2 = CH
111. Arrange the following in increasing order of their rate NO2
of hydrolysis:
O O OH (lequiv.)
115. P.
Cl H 3C ∆
O O 1 NO2
Br
H5C2 H5C2
Where the major organic product (P) is:
O O NO2 NO2
O2N H 2N
O O (a) (b)
H5C2 H5C2 NO2 l
Br NO2
OH OH
(a) IV < I < III < II (b) IV < II < I < III
(c) III < IV < I < II (d) III < I < II < IV NO2 NO2
112. Compare the C — N bond-length in the following

species: (c) (d)
H2N l OH HO NO2
H2N H2N
Br Br
(i) (ii) (iii) 116. Which of the following is correct set of physical
properties of the geometrical isomers
O CH3
CH3 H Cl
(a) ii > i > iii (b) i > ii > iii
C C & C C
(c) iii > ii > i (d) i > iii > ii
H Cl H H
113. Arrange the following in their increasing order of
basicity: Dipole Boiling Melting Stability
moment point point
Ph – NHAC PhNH2 Ph2NH PhNHEt PhNEt2 (a) I > II I > II II > I I > II
(I) (ii) (iii) (iv) (V) (b) II > I II > I II > I II > I
(a) III II I >II I > II I > II
(c) I < III < II < IV < V (d) I < III < IV < II < V (d) II > I II > I I > II I > II
117. The most stable carbonian among the following is: 1+ 1+

CH2 CH2
(c) (d)
(a) (b) 1+ +1 1+
122. The correct basic strength order is:
1+ &+ 2
&+
CH2 CH2 & 1+
2
(c) (d) , ,,
2 2
& 1+ +1 &
OCH3 NO2
&+ &+
118. The correct stability order of following species is: ,,, ,9
I. II. (a) I > II > IV > III (b) IV > III > II > I
(c) III > II > IV > I (d) III > IV > II > I
III. C IV. 123. The correct order of acid and basic strength for the
following pair of compounds should be?
(a) I > II > IV > III (b) II > I > IV > III Acid strength:
(c) I > IV > III > II (d) III > I > II > IV &22+ &22+ &22+ &22+
119. For which of the following molecules m ≠ 0? &+ &+
Cl CN OH SH DQG DQG
I II III IV
I. II. III. IV.
Basic strength:
1+ 1+ 1+ 1+
Cl CN OH SH &+ &+
(a) only I (b) I and II DQG DQG
(c) only III (d) III and IV
120. Which of the following will give highest enol content? V VI VII VIII
2 2 (a) I > II; III > IV ; V < VI; VII < VIII
2 (b) I < II ; III > IV ; V < VI ; VII > VIII
(a) (b) (c) I > II; III > IV ; V > VI; VII > VIII
(d) K II; IU > IV ; V < VI; VII < VIII
2
124. Which of the following is the most basic?
2 2
+ + + +
1 1
(c) (d) &+ &+
+&
+&
2 2 (a) (b)
2
121. Which of the following is the least stable? 12 2&+
1+ 1+
+ + 1+
1+
1
(a) (b)
(c) (d)
1+ +& &+
+& &+ 2
12 +& &
125. The most acidic among the given compounds is 3. Chiral axis is present in
2+ 2+ a d
12
(a) (b)
(a) allene abC3 ed (b)
21 21 12
b e
2+ 2+
12 d
(c) (d) e d a
(c) a (d)
12 b
12 b e
12
4. The correct order(s) for the given pair of isomers is/are
CH3 CH CH3 H
MCQ WITH ONE OR MORE THAN 3
(a) C=C > C=C
ONE CORRECT ANSWERS
H H H CH3
1. Which of the following statements(s) is/are true about H H H COOH
the following compounds? (b) C=C > C=C
O HOOC COOH HOOC H
(Dipole moment)
O O H Cl Cl
I II III Cl
(c) C=C > C=C
(a) (I) and (III) are identical
Cl H H H
(b) (I) and (III) are geometrical diastereomers (Boling point)
(c) (I) and (II) are structural isomers. H3C H H3C COOH
(d) (II) and (III) are structural isomers. (d) C=C > C=C
2. Which of the following will show optical isomerism H COOH H H
as well as geometrical isomerism? (Water solubility)
CH3 5. Racemisation increases with:
(a) CH3
C (a) increases in stability of carbocation
H (b) increase in basicity of leaving group
(c) increases in solvent polarity
CH3 (d) increase in activation energy of rate determining
CH3
(b) step (rds)
C
CH3 CH3
CH3
CH3 CH3
(c) C 6. CH3
CH3
CH3 CH3
(I) (II)
CH3
CH3 Mark out correct statements regarding these
(d) C conformation:
H (a) conformation I and II both are equivalent in
CH3
stability
(b) conformation stability: II > I (a) I, II and III are functional isomers
(c) conformation II possesses pitzer strain (b) I and II re position isomers
(d) conformation I possesses trans-angular strain (c) III and IV are chain isomers
(d) III and IV are metamers
7. Consider following compounds:
OH 10. Which of the following statements is \are true about
OH the following compounds
CH – CH3
O
C2H5 O O
I II (I) (II) (III)
OCH3 CH2OCH3 (a) (I) and (III) are structural isomers
(b) (I) and (II) are geometrical diastereomers
(c) (II) and (III) are structural isomers
(d) (I) and (II) are identical
CH3
III IV 11. Which of the following is/are a meso compound.
CH2OH
Choose the correct statement(s) from the following:
(a) I, II and III are functional isomers (a) HO CH2OH
(b) I and II are position isomers
(c) III and IV are chain isomers OH
OH
(d) III and IV are metamers COOH
8. Which of the followning statements are not correct? H
(a) A meso compound has chiral centres but exhibit (b)
no optical activity NH2 COOH
(b) A racemic mixture is optically inactive because H NH2
of two equal and opposite rotation of same mol- Cl
ecules in mixture
(c) A meso compound has molecules which are su- (c) F Br
perimpossible on their mirror images even though Cl F
they contain chiral centres
Br
(d) A meso compound is optically inactive because the
rotation caused by any molecule is cancelled by COOH
and equal and opposite rotation caused by another
molecules that is the mirror image of the first H OH
(d) HO H
9. Consider following compounds
OH
OH CH – CH3 COOH
12. Which of the following pair represents the correct
relationship
C2H5 I II Relationship
I II NH2
OH Cl OH
OCH3 CH2OCH3 (a) Positional Isomers
NH2
Cl
CH3
III IV (b) Chain Isomer
Choose the correct statement(s)from the following
NH C3H7 H3C N C2H5 Which of the following statement(s) is/are correct?
(c) Functional Isomers (a) C

ation in the reactant side is approximately 1011
times less stable than that of product side
(d) CH3 – CH2 – CH2 – C – OCH3 (b) Cation in the reactant side is non-planar
(c) It is acid-base reaction
O (d) Reaction must be exothermic
CH3 – CH2 – C – OCH2 – CH3
Metamer Isomers 17. Among the given geminal diols, which is/are stable
O with respect to their corresponding carbonyls?
2+
13. Which of the following statements would be incorrect 2+
about this compound? (a) &&O (b) &) &)
NO2 2+
3 2+
2
1 5
2+ 2+
NO2 NO2 (c) (d)
Br 2+ 2+
(a) All three C – N bond are of same length 2
(b) C1 – N and C3 – N bonds are of same length but
18. Which of the following is highly polar aromatic
longer than C3 – N bond
species?
(c) C1 – N and C5 – N bonds are of same length but

longer than C3 – N bond
(d) C1 – N and C3 – N bonds are of different length but (a) (b)
both are longer than C5 – N bond
14. Which of the following contain same number of (c) 2 (d)
linearly arranged carbon atoms in their respective
molecules?
19. What are the stability orders of following reaction
(a) CH2 = CH – C = CH intermediates?
(b) HC ≡ C – C ≡ CH
(c) H2C = CH – CH = CH2 2+
(d) CH3 – C ≡ C – CH3
&
15. Consider the following compounds: (I) +&
&+
N N 2
H NH2 (II) +&
&+
(I) (II) (III)
&+
Which of the following statements are correct?
(a) I is more basic than II 2
(b) II is more basic than I and III &+

(c) III is more basic than II (III) + &

&+
(d) I is weakly acidic
+ &+
&+
(IV) + &

16. 3K&%)
±

±
%) 3K &+
(a) II > I > IV (b) I > III > II
+ + (c) I > IV > III (d) I > IV > II
20. Which of the following carboxylic acids could not be 1. Which of the compound is optically active?
resolved by reaction with an enantiomerically pure (a) P (b) R
chiral amine? (c) S (d) T
&2+
12 2. Which of the isomer is most stable?
(a) (a) R (b) S
21 (c) T (d) U
&2+ 3. Which of the isomer is least reactive toward E2
2 1 &2+ reaction (elimination bimolecula(r)?
(a) P (b) Q
(b)
+2& 12 (c) R s) U
12 +2& Passage-II

In many compounds there is a mixture of two or more struc-
(c)
turally distinct compounds that are in a rapid equilibrium
&2+ 21 are called tautomeres and the phenomenon as tautomerism.
A common form of tautomerism is that between a carbonyl
&2+ compound containing on a-hydrogen and its enol form
+ +
(d)
5 & & 5 5 & & 5
12 + 2 +
Generally keto form is more stable but compound in

which the enolic double bond is in conjugation with another
LINKED COMPREHENSION TYPE
double bond or in which enol is stabilised by internal hy-
drogen bonding, enol form predominates.
Passage-I
⊝
&O &O 4. R2 — C — C — R R2 — C = C — R
&O &O &O &O ||
O O⊝
(P) (Q) (I) (II)
&O &O &O &O Which structure (I or II) is more stable?
&O &O (a) I
(b) II
&O &O (c) Equal stability
&O &O &O (d) Do not compare because they are tautomer
&O
(R) (S) 5. In which of the following enol content is maximum?
(a) Ph2CHCHO
&O &O &O &O (b) NCCH2COOEt
&O &O (c) CH3COCH2COCH3
(d) PhCOCH3
&O &O
&O &O &O 2
&O
(T) (U)
&O 6. Compound can be identified by
&O &O &O
&O &O (a) NaHSO3 (b) Br2 water
Consider the given structures and answer A, B and C. (c) Fehling solution (d) FeCl3
Passage-III 8. Observe the following reaction:

Structural isomers have different covalent linkage of at- &+
oms. Stereoisomers are compounds that have same se- +22& &+
quence of covalent bonds but differ in the relative dispo- +
& 5¶5 5¶6

sitions of their atoms in space. Geometrical and optical 1+ 6HSDU
isomers are the two important types of configurational &O + DWLRQ
5¶ 3KHQ\OHWKVODPLQH 56 &KORURSURSDQRLFDFLG E\5HFU\
isomers.
The compound with double bonds or ring structure K\GURO\VLV VWDOOLVD
5¶ 5 5¶5
WLRQ
have restricted rotation, so exist in two geometrical forms.
K\GURO\VLV
The double bonds in larger rings (ring size 10 carbon or 5¶ 6 5¶6

larg(e) can also cause geometrical isomerism. The opti-
cal isomers rotate the plane of plane-polarised light. A Which statement is not correct about the above
sp3-hybridised carbon atom bearing four different types observation?
of substituents is called an asymmetric centre or chiral (a) The product mixture of step-1 is optically active
centre. A chiral object or molecule cannot be superim- (b) The products R’R and R’S have identical struc-
posed on its mirror image. Stereoisomers that are mirror tural formula.
images of each other are called enantiomers. The Stereo- (c) R’R is nonsuperimposable on R’S
isomers that are not mirror images of each other are called (d) R’R and R’S have same solubility in water
diastereomers. Diastereomers have different physical
properties. 9. Which statement is correct about the following pair of
A racemic mixture is optically inactive and contains compounds?
equal amounts of both the enantiomers. Resolution refers
to method of separating a racemic mixture into two pure
enantiomers. A meso compound is an optically inactive
stereoisomer, which is achiral due to the presence of an , ,,
internal plane of symmetry or centre of symmetry within
(a) Both give same product with Br2/CCl4 solution.
the molecule.
(b) I and II cannot be separated by fractional distilla
7. The pair showing identical species is tion
(c) I and II have different linkage of atoms.
(d) I and II after catalytic hydrogenation, followed
by photochemical bromination and then treatment
(a) + DQG + with alcoholic KOH followed by reaction with
&O &O HBr R2O2 give same major product.
0H %U 10. The number of chiral centres present in the following
+ 2+ + (W compounds is
(b) ' %U DQG ' 2+
&+2+
(W 0H
+ &22+ + 2
+ &22+ 2+ +
2+ +
(c) DQG 2+
2+ +22& 2+
+22& + + + +2
2+ 2' 6XFURVH
%U %U +2+& 2
DQG + 2+
(d) & &
&+ + +
+ &+ &+2+
&O &O 2+ +
(a) 7 (b) 8 14. The correct statement about ‘T’ is

(c) 9 (d) 10 (a) It has two stereoisomers
11. The following two compounds are: (b) It gives W an achiral product
(c) It has two asymmetric carbon atoms
(d) It has four stereoisomers and all are optically
active
, ,, PASSAGE-V
(a) Identical Compound X(C7H14O4) on ozonolysis gives (Y) and (Z),

(b) Conformational isomers (Z) is the aldhyde which gives only one oxime with NH2-
(c) Geometrical isomers OH. On treatment with I2\NaOH, (Y) gives yellow solid
(d) Structural isomers CHI3 alongwith compound given below.
Passage-IV &221D
Three optically active acyclic compounds P, Q and T +2 +

(molecular formula C5H9Br) give following reactions + 2+
+FDWDO\VW PROH
+ 2+
3 5 DFKLUDO &+%U
&+±2+
+FDWDO\VW PROH
4 6 FKLUDO &+%U
When (X) is treated with D2\Ni, it gives two optically active
2
:&+±&+2 compound (V) and (W).
7
8 &KULDO 15. compound (V) and (W) are
+FDWDO\VW PROH
(a) Enantiomers (b) Diastereomers
12. ‘P’ can be (c) Identical (d) Nuclear Isomers
(a) 2-Bromopent-l-ene 16. Compound (Y) can give _____ type of oximes on
(b) 3-Bromopent-l-ene treatment with NH2-OH
(c) 1-Bromopent-1-ene (a) 2 (b) 6
(d) 4-Bromopent-1-ene (c) 8 (d) 7
13. Which of the following is not Q?
17. Which of the following statement is true
&+%U
(a) ‘X’ gives positive test with 2,4-DNP and Br2 solu-
(a) + &+ tion
(b) Y gives positive with both 2,4-DNP and tollens
&+ &+ reagent
(c) Compound (V) give positive test with NaHCO3
&+ &+ 1+
(b) + %U (d) & is the isomeric amide of oxime of
&+ &+±&+ 2
&+ next higher homolog of Z.
(c) + PASSAVE VI
%U
The concept of resonance explains various properties of
&+±&+ &+ compounds. The molecules with conjugated system of p
&+&+ bonds, are stabilized by resonance and have low heat of hy-
drogenation. Hyperconjugative stabilization also decreases
(d) %U &+ &+ heat of hydrogenation. In aromatic rings a functional group
with a lone pair of electron exerts +m effect. Some func-
+ tional groups like –NO, –NC, –CH = CH2 can function
both as electron releasing (+m, +R) or electron withdraw- structures for the same molecule must have the same sigma
ing (–m, –R) groups. More extended conjugation provides framework (sigma bond form from the “head on’ overlap
more stabilization. of hybridized orbitals). furthermore, they must be correct
Lewis structures with the same number of electrons (and
18. The correct heat of hydrogenation order is consequent charge) as well as the same number of unpaired
(p) 1,3-Pentadiene electrons. Resonance structures with arbitrary separation of
(q) 1,3-Butadiene charge of charge are unimportant, as are those with fewer
(r) 2,3-Dimethyl-1,3-butadiene covalent bonds. these unimportant resonance structures
(s) Propadiene only contribute minimum (or not at all) to the overall. From
(a) p > q > r > s (b) s > q > p > r the above theory of resonance answer the followings.
(c) q > s > p > r (d) s > q > p > r
21. The correct resonation structure of 1, 3-butaliene is
±
19. The most stable carbocation is (a) &+ &+ &+ &+
(a) ±
(b) &+ &+ &+ &+

±
(b) (c) &+ &+ &+&+

(d) None of these
(c)
22. The correct stable resonating structure of benzene is
(d) ±
(a) (b)

20. The most stable resonating structure of following ±

compound is 2 1 1 2 ± ±
(c) (d) None of these

(a) 2±1 1 2 ±
23. Which resonating sturcture is not correct

(b) 2±1 1±2
(a) &+ &+±&+ &+±&+ &+

(c) 2±1 1 2 (b) 1+±&±1+ 1+±& 1+

(d) 2±1 1 2 1+ 1+
2 2
PASSAGE VII
(c) &+±&±1+ &+±& 1+
The key concepts of resonance are:
Resonance occurs because of the overlapping of
orbitals. Double bonds are made up of pi bonds, formed (d)
from the overlap of 2p orbitals. The electrons in these pi
orbitals will be spread over more than two atoms, and hence 1 1
are delocalized. Both paired and unshared electrons may be + +
delocalized, but all the electrons must be conjugated in a pi
system. If the orbitals do not overlap (such as in orthogonal
orbitals) the structures are not true resonance structures and ASSERTION AND REASON
do not mix. Molecules or species with resonance structures
are generally considered to be more stable than those Each of the following questions contain two statements:
without them. The delocalization of the electrons lower the Assertion (A) and Reason (R). Each question has four
orbital energies, imparting this stability. The resonance in choices:
benzene gives rise to the property of aromaticity. The gain
(a) A is true, R is true; R is the correct explanation of A.
in stability is called the resonance energy. All resonance
(b) A is true, R is true; R is NOT the correct explanation of A.
(c) A is true, R is false. &+±&+±&22+&+±&+±&+±&+

(d) A is false, R is true.
&O 2+
H[FHVV
Select the correct choice.
&+±&+±&22±&+±&+±&+
2+
&O
1. A: +& &+ &+ on catalytic deuteration &+±&+±&+±&+
2+
+ /HIWXQUHDFWHG
(Ni/D2 and D) gives racemic mixture.
R: Catalytic deuteration is syn-addition. Statement-2: The solution of reaction mixture at
time (t = 0), will be dexterorotatory because of
2. A: In n-butane the gauche conformation lies higher in (+)2-butanol
energy than the anti conformation. (a) Statement-1 is True, Statement-2 is True; State-
R: The gauche conformation has eclipsing interac- ment-2 is a correct explanation for Statement-1
tions. (b) Statement-1 is True, Statement-2 is True;
Statement-2 is NOT a correct explanation for
Statement-1.
3. A: is more stable than (c) Statement-1 is True, Statement-2 is False.
(d) State,emt-1 is False, Statement-2 is True.
O O O O
H 8. Statement-1: Ortho iodobenzoic acid is strongest
R: ‘ T’ has double bonds at anti position while (ii) has acid among all ortho halobenzoic acids.
double bonds on the same side, so has lot of elec Statement-2: Iodine exerts maximum ortho effect
tronic repulsion. (steric effect) so the acid weakening resonance effect
4. A: Restricted rotation about a bond is the necessary of aromatic ring is decreased
condition for geometrical isomerism. (a) Staternent-1 is True, Statement-2 is True; State-
ment-2 is a correct explanation for Statement-1.
R: Two different orientations are possible due to re (b) Statement-1 is True, Statement-2 is True; State-
stricted rotation about a bond if the end groups are ment-2 is NOT a correct explanation for State-
different. ment-1
5. A: Compounds having only one chiral centre can (c) Satement-1 is True, Statement-2 is False
have both enantiomer and diastereomer. (d) Statement-1 is False, Statement-2 is True
R: Diastereomer may or may not have chirality.
6. Statement-1: Restricted rotation about a bond is the MATRIX MATCH TYPE
necessary condition for geometrical isomerism.
Statement-2: Two different orientations are pos- 1. Match the Column (I) and (II)
sible due to restricted rotation about a bond if the end Column-I Column-II
groups are different. (Compounds) (isomers)
(a) Statement-1 is True, Statement-2 is True; State- A. CH3 – CH = CH – P. 2
ment-2 is a correct explanation for Statement-1 CH = N – OH
(b) Statement-1 is True, Staternent-2 is True; State-
ment-2 is NOT a correct explanation for State-
ment-1. B. Q. 4
(c) Staternent-1 is True, Statement-2 is False.
(d) Statement-1 is False, Statement -2 is True. C. C H3 – CH = CH – CH = R. 6
7. Statement-1: Aracemic mixture of 2-Chloropropanoic CH – CH = CH – CH3
acid is treated with excess of (+)-2-Butanol. The D. CH3 – CH = CH – CH = S. 8
reaction can be represented as follows: CH – CH = CH – Ph
2. Match the Column (I) and (II) Column-II (Nature)

Column-I Molecule P. cis-compound
H Q. trans-compound
CO2CH2CH2OH R. Optically active
S. Optically inactive
A.
CO2H 4. Match the Column I and II
H Column-I Molecule Column-II Property
H H H H
CO2CH2CH2O2C
A. C=C=C P. C
hiral centres contain-
B. ing compound
Br Br
CO2CH2CH2O2C
H H H CH3
CO2H B. Q. P
resence of
H
OH CH3 H stereocentre
C.
OH Cl
H
CO2H
C. Br F R. O
ptically active com-
CO2H H
pound
H
D. l
OH
CO2H CH3 H
HO
Column-II Nature D. C=N S. C
ompound containing
P. Chiral plane of symmetry
Et
Q. Achiral
R. Meso 5. Match the Column I and II
S. Compound containing even number of chiral
centers Column-I Column-II
Molecule Property
3. Match the Column I and II Cl
Column-I (Compound) H
CH3Br OH CH3
A. P. Meso compound
A. CH3 CH3
Cl
HO Br H
Br OH CH3
B. Q. Achiral
B. CH3 CH3
CH3HO Br H
Cl
Cl
Cl
C. H
Cl
Cl C. H R. Chiral
D.
Cl Cl
Cl H
H Me Me C COMe
C
D. Cl Cl S. C
ompound will show B.
geometrical isomerism
H H
H
6. Match the Column I and II C COMe
C. C
Column-I (Molecule)
CO2H H
C COMe
A. D. C
CO2H
Me
CH3 Column-II (Stereoisomers)
P. 2
Q. 0
R. 4
B. H S. 8
CH2Cl 8. Column-I
CH3 CO2H CO2H
OH H H OH
CH3 CH3 A.
Cl Br Cl OH HO Cl
C. X
CO2H CO2H
F H
Cl Br Br Cl
O
CH3 C Me B.
CH3 N
D. F
H
OH OH
C.
Column-II (Property)
P. Optically active
H
Q. Optically inactive CH3
F CH3 H
R. Degree of unsaturation is greater than 10 F
S. Reacts with NBS (N-bromo succinimide) D. C—C
7. Match the Column I and II H3C F H
F CH3
Column-I (Molecule) H
H
Me Me C COMe Column-II
C P. Meso compound
A. Q. Identical
R. Enantiomer
S. Diastereomers
9. Examine the following formulae and select those CHO CH3 CHO CHO
pairs that satisfy the following conditions: B. C=C
CH3 CHO CH C = C CH3
Column-I (Conditions) 3
A. Identical in all respects COOH OH H

H OH COOH
B. Conformational isomers
C.
C. Constitutional isomers COOH
H OH H OH
Column-II (Formulas) COOH
C2H5 Cl CH3
CH3 H 3C H H OH3 H Br
H
P. H D.
Q.
CH3 Br OH2I D CH2Cl
C2H5 H H D I
H CH3
Column-II
CH3 P. can be separated by fractional crystallisation
H3C H
H C2H5 Q. Can not be separated by fractional crystallisation
H R. Optically resolvable
R. H S.
CH3 H S. donot have identical boilling point
H3C H3C CH3 12. Match the items in Column I with Column II.
CH3 Column-I (Reaction)
H CH3 NH2
T.
HNO 2/Δ
(a)
H 3C H
CH3 CH 2 OH
10. Column I may match with more than one conditions (b) H+/Δ
of Column II.
Column-I (c) (CH 3 )2 − C = N − OH 
PCl5
→
A. Ph – CH = CH – Ph
B. (CH3)2C = CH – CH = Cl O O
CH3 (1) Mg/ether

(d)
C. CH2 = CH – CH = CH2 ( 2 ) H2 SO4
D. CHO CH – CH CHO Column-II (Features)
OH OH (i) Ring expansion
(ii) Ring contraction
Column-II
(iii) Carbocation
P. Ozonolysis followed by reaction with NH2 OH
(iv) Rearrangement
leads to more than one oxime product
Q. Can exhibit geometrical isomers 13. Match the items in Column I with Column II.
R. Compounds with this structure formula can be Column-I (Effects)
separated into different fractions upon fractional (a) CH2=CH-Cl
distillation CH3
S. Is capable of showing stereoisomerism
11. Column-I (b) (c)
D D
HO CH3 H3C OH
A.
D OH D OH
D D OH
CH3 CH3 HOOC OH
N x mole NH2
7. Br
CH3 CH
(d) 2
C
OHC H
Br
CH3
Column-II (Compound) value of X used for compilation of reaction will be:
(i) Resonance
8. Incorrect statement among these four:
(ii) Hyperconjugation
(i) I effect is permanent polarisation of sigma bond
(iii) Inductive effect
pair of electrons in the molecule.
(iv) Steric effect (ii) In resonation structures the hybridisation of at-
oms do not change.
SUBJECTIVE ANSWER TYPE (iii) In Hyperconjugative structures the hybridisation
of carbon atom change.
1. Total number of stereoisomes possible for molecule A (iv) Presence of methyl group on an anion always de-
will be stabilises the anion.
9. Maximum number of hyperconjugation forms of
H3C CH = CH structures:
CH = CH
10. In the following set of resonationg structures which

Cl2/hv Fractional sets have the second resonation structure more
2. A B
distillation
contributing than first:
Number of possible fractions of B are:
O O
3. The number of isomers for the compound with
molecular formula C2HDFCl is: I.
N N
4. Number of sp -sp sigma bonds in given compound A is:
2 2
⊕
OCH3 OCH3
II.
⊕
NH2 NH2
5. Write lowest molecular weight of saturated cyclic
hydrocarbon which has four substtituents. Molecular
⊕
weight = 98. O O
6. For the compound:
III.
OH
N N
Give the number 1 for presence of resonance only, O O O O
2 for presence of resonance and hyperconjugation
only, 3 for presence of resonance, hyperconjugation ⊕
and inductive effect and 4 for presence of resonance
IV.
hyperconjugation, inductive effect and electromaric ⊕
effect. Cl Cl
SOLUTIONS
CONCEPTUAL ASSIGNMENTS – STEP-I (4n + 2) π electrons. In the given case, (a), (b) and (c)
1. a 2. c 3. d 4. a 5. c qualify to be called as aromatic. \ (a), (b) and (c).
6. c 7. b 8. b 9. d 10. d 35. For a compound to exhibit keto-enol isomerism,
11. a 12. d 13. a 14. d 15. a presence of α-hydrogen is necessary. This is satisfied
16. b 17. d 18. a, b, c only by acetophenone. \ (b)
19. o-,m- and p-isomers, i.e., position isomers \ (c) H3C CH3
H H 36. (a)
20. C=C
O
CH3 CH3
H3C CH2 CH2
If either of the two doubly bonded carbon atoms has (b) C C CH3
same group or atoms attached on it, it will not show
geometrical isomerism.\ (a) O O
21. Due to the presence of asymmetric carbon atom. O
\ (b) H3C CH2 C
22. CH2 = CCl2 and CHCl = CHCl are position isomers; (c) C CH2 CH3
CHCl = CHCl also show geometrical isomerism.
\ (c) O
O
23. Alcohols show position isomerism; Ethers show
metamerism; Alcohol and ethers shows functional CH3
isomerism.\ (d) (c) H3C
24. a = 2n; where n is no. of dissimilar asymmetric
carbon atoms. \ (c) O
*
25. Bond energy order The most acidic hydrogen is the H attached to the C
sp–sp > sp2-sp2 > sp3-sp3 \ (a) in (b) as the negative charge on it after removal of
26. NH4CNO is functional isomer of urea. \(d) proton is extensively delocalized as compared to the
27. Glucose has four dissimilar asymmetric carbon atoms; all other due to the two carbonyl groups which are
a = 24. \ (c) adjacent to this carbon.\ (b)
28. Allyl carbonium undergoes resonance stabilization. 37. CH 2 = CHCH 2Cl is an allylic chloride that reacts
\(a) with AgNO3 in the cold to give a white precipitate of
29. Breaking of C – O bond results in formation of most AgCl.
stable tertiary carbocation. \ (c) CH3CH 2CH 2Cl gives a precipitate on warming.
30. Positive charge is on sp hybridized carbon.\ (b)
CH 3CH = CHCl is a vinylic chloride which is inert
31. a = 2n , where n is no. of dissimilar asymmetric even when heated. \ (a)
carbon atoms. \ (c) 38. In cis-isomers two alkyl groups on same side of
32. Benzoquinone cannot show tautomerism because the π plane create more steric hindrance, so trans-
isomers is more stable than cis. \ (d)
HO OH CONCEPTUAL ASSIGNMENTS-STEP-II
x y
1. d 2. b 3. c 4. d 5. c
compound can’t exist because carbon x and y will 6. b 7. a 8. b 9. d 10. d
get sp hybridized due to bond angle which should be 11. c 12. c 13. c 14. c 15. b
180°, which is not possible because the bond angle 16. b 17. a 18. a 19. b, d 20. d
between carbon x and y will be 120°. Hence the
ring will be highly strained. Hence it will not show SECTION-A
tautomerism. \ (c) Me Me
33. Here in the given problem, carbocation (b) is H H D
stabilized most, as the CH3 (e– releasing group) 1. (b) D (x) and (y) are
group is attached to the carbon bearing positive H Br H Br
charge. \ (b) Me Me
34. For a compound to be aromatic, there must be cyclic (x) (y)
delocalization with the closed loop formed must have diastereoisomer.
Me I → R – R – Configuration
Me II → S – S – Configuration
Me CH3
8. (c)
H OH
2. (b) H 60° 2+
OH H rotation 2 2 2+
H OH +2 +2
Me OH
Fischer New mann’s
of meso of meso +2 2+ 2+
+2
Me 2+
Me 2+
H Me H
Above 2-Compounds are mirror image of each other
60° 60° and are not super imposable so are enantiomers and
behave differently towards P.P.L.
H OH HO 9. (c)
H OH 10. (b)
OH Me
11. (c)
Me Br b
Me a Me Me
HO H
F a
Me D
b b Me
H O
OH Me a Me a
H
Me (E) b (E)

Anti
a = 1st priority; b = IInd priority
3. ( b) Compound give Atropi isomerism and is
optically active due to absence of plane and centre 12. ( d) Compound which do not have plane and centre
of symmetry of symmetry are optically active.
13. (d)
Me Me H H
C COOH
C=C
H3C
& H H
Me Total isomers = 22 = 22 = 4
Me
14. (c) In Fischer most oxidised end remains always on
are mirror image and are not super imposable on top so rotation of IInd str. by 180°. It is clear that I
each other so are enantiomers. and II are identical.
4. (b) When molecule is symmetrical and has even 15. (d) Given molecule doesn’t has C = C bond having
number of chiral centres then total number of different valencies and not has chiral centres so
isomers doesn’t show stereo isomerism.
= 2n–1 + 2n/2–1 16. (d)
O.A. meso 17. (a) ee isomer is most stable.
(O. A. = Optically active; a = axial; e = equotrial) 18. (c) 1, 3-trans cyclohexane has ae configuration 1,
5. (a) 4-cis cyclohexane has -ae configuration so str. of
6. (b) During flipping a ↔ e e ↔ a are inter convertal. molecule is
Me
flipping
H
t–Bu
7. ( a) Enantiomers have same solubility in optically
inactive solvents so (I) and (iv) have same solubility
because they are enantiomers Me
19. (d) Non-zero dipole has following molecules 26. (b)

Resultant
Br H
H Br
Br Br H i – Pr Me
H H
H H Me H H l – Pr
H 1, 3-repulsion (stable)
gauche 1, 3-repulsion
(less stable)
Dibromocyclohexane → stereo chemistry and
position are not mentioned so may be cis. equilibrium favours reactant so K < 1
20. (b) Enantiomers give different chemical product
27. (b) Given 2-Compound are mirror images of each
when they are reacted with optically active
other and are not super imposable on each other so
molecules and give different chemical product when
are enantiomers.
they are reacted with optically active molecules and
give diastero isomers so there T. S. of reaction also 28. (b) Isomers obtains are
have diastereo isomeric characters. Cl
21. (a) Compound ‘B’ may be meso but meso has plane
of symmetry with chiral centres. Ph – CH – Ph; Ph – CH2
22. (d)
Me Cl
N O Cl
* Ph – CH2 Ph – CH2
* OMe
* *
4 – chiral ‘C’ atoms Cl
O
O 29. (d)

23. (e) O OH
24. (b)
Me Me Me (1)
O OH
keto stable anti aromatic
unstable
Me Me Me
Centre of Symmetry
(2) O O O O–H
Only – 3 – Product possible.
25. (d)
Keto stable Bad steric clash
O [Non-planner]
HO CH2Cl
* *
HO * * CH = CH –CH = CH – C3H7
(3)
H
O O H
molecule (I) chiral centre = 4 (2) C = C along which O
it can shown G.I. = 2 keto violet Bredt’s
(more stable) rule
Total stereo isomers = 26 = 64
30. (a) 35. (b) The given compound

CH = CH C2H5
*
*
* (CH2)6 CH = CH (CH2)4 COOH
*
CH = CH2
total isomers =23 = 8 two stereocentres therefore it has four stereo isomers.
36. (a) Me O Me
31. (c) *
⊕
H
O OH C – C – OH + H – O – *C
–H2O
H D H Et
H
Stable H Anti aromatic Me O Me
unstable *
C–C–O – *C
32. (d)
H D H Et
Me Me
Since there is not carbocation formation at alkyl
C group in this reactions hence racemic mixture is not
Me Me formed.
37. (a) 38. (a) 39. (c) 40. (d)
can show G.I. Along the 5-membered ring.
33. (b) Cl
Cl Cl H H Cl H
Cl2
41. (c) (a) + H2 hυ
(i) Total = 3
H H Cl Cl H Cl (b) CH 3 + CH − C − CH 3
H2
| ||
Me H CH 3 CH 2
Cl2
(ii) Me CH3 + CH − C − CH hν
Me | |
H Me CH3 CH3 Cl
|
H H CH3 + CH − C− CH2Cl + CH3 − C − CH − CH3
| | | |
Total = 2 CH 3 CH 3 CH3 CH3
4 3 2 1 2 products
2
(iii) CH CH CH CH3 = 2 = Total = 4
3
* * (c) + H2
Cl Br Cl2
Me Me H hυ Cl+ +
Me H Me Cl
Cl
(iv) H H Me
H Me H
34. ( d) Axial substitutent experience 1, 3-diaxial (d) + H2

repulsive interaction (trans - annular strain) which
destabilize the molecule.
In structure III, both - Me substituents are present at Cl2
equatorial that’s no strain and most stable, Cl
hυ
In structure IV, both - Me substituents are present
at axial, that’s why highly energetic, least stable.
Structures I and II are equivalent, where one –Me 42. (d) 43. (d) 44. (d) 45. (d) 46. (b)
group at axial which destabilize. Hence, correct 47. (d) 48. (b) 49. (c) 50. (b) 51. (c)
order is: III > I ≈ II > IV 52. (a)
53. (c) X is a conjugated diene system. (d)

W is an isolated diene system CH3 CH3
Z is a cumulated diene system
Y is antiaromatic system H Cl H Cl
Hence stability order is X > W > Z > Y H2/Ni
C=O H OH– +
54. (c) I = Cis-Trans-Cis-Cis-Trans isomer of [10]
annulene H Cl
II = all-Cis isomer of [10] annulene H Cl
55. (b)
CH3
COOH CH3
COOH Plane of symmetry
O3 Achiral
56. (d) 2 + 2 (Achiral)
Oxidation
COOH COOH
CH3
57. (d) All isomeric esters are metamers.
CH3 H Cl
–
KMnO4/OH /∆ H
C C2H5 HO
58. (a) H H Cl
COOH
CH3
59. (b)
CHO CHO
H O O
(b) H O3/Zn 60. (a) + +
C=C H
H H
H
CH3 CH3 O
Chiral
CHO OHC
OHC
O
H CHO
61. (a) The configuration in a compound is independent
of its physical properties (optical activity)
CH3
Achiral
62. (b) 63. (b)
64. (c) X is a conjugated diene system.
CH = CH2 W is an isolated diene system
Z is a cumulated diene system
O3
(c) H Y is antiaromatic system
CH2 – CH3
Hence stability order is X > W > Z > Y
65. (b) There are unpaired electrons, others have no
CH2 – OH unpaired electrons.
Chiral
66. (b)
CHO O
67. (c) C CH3
H CH2 – CH3 + HCHO
CH3 + I
H.C.
CH2OH
has all effect inductive, mesomeric and
Chiral hyperconjugation.
O OH O O NH2 NH2
⊕ CH3
–2H
68. (a) Kb: > (due to ortho effect)
O OH O O 76. (b) 77. (c) 78. (b)

O O O O O O 1
79. (c) Heat of combution ∝ ∝
stability of molecule
no. 'c' atoms in molecule

O O O O O O
80. (c)
69. (d) H+X− N
81. (d) Degree of unsaturation = (C + 1) –  
70. (c) Stronger the base weaker is the acidic strength of  2
conjugate acid. 82. (d)
71. (a) Car anion at position V will be stabilized by both 83. (a) C⊕ stability ∝ + H on carbocation
oxygens. 84. (c) 85. (b) 86. (a)
Me Me
O H Me Me
72. (a) N
O N Me
C Me
O
OH Me Me
O
NO2 NO2
C
O less SIR so more more SIR less effective
H effective resonance resonance so has less Dipole
O
O 87. (c) 88. (b) 89. (a) 90. (a) 91. (c)
C OH 92. (b) 93. (b) 94. (d) 95. (b) 96. (d)
97. (d) 98. (c) 99. (b) 100. (a) 101. (a)
73. (b) 102. (c) 103. (b) 104. (a) 105. (b) 106. (b)
(–I) 107. (c) 108. (c) 109. (d) 110. (b) 111. (b)
112. (c) 113. (c)
74. (b) O
114. (a) Due to planarity of (a), the free radical is
N N stabilised but in (b) steric inhibition of resonance
N
N the free radical is less stable.
sp3 sp3 sp2
H H sp3 115. (b) 116. (c) 117. (d)
H (Resonance) 118. (c)
Order: I > II > IV > III I is a conjugated diene system, IV is an isolated
diene system
COOH COOH
CH3 III is a cumulated diene system, II is antiaromatic
system
75. (B) Ka: < (due to ortho effect)
Hence stability order is I > IV > III > II
119. (d) 120. (c) 121. (d) 122. (d)
COOH COOH
CH3 The basicity order will be inversely proportional to
resonance stability of lone pair.
Ka: > 123. (b) 124. (b)
125. (c) In 2, 4-Dinitrophenol both nitrosubstituents are
(due to +I effect of –CH3) involved in resonance stabilisation
NH2 NH2 SECTION-B
CH3
K b: < 1. (b, c, d),
I and II: Positional isomer; I and III: Geometrical

(due to +I effect of –CH3) isomer (cis and trans); II and III: Positional isomers
2. (c, d) 13. (abd) 14. (b, d) 15. (b, d)

CH3 CH3 16. (a, b, c, d) 17.(a, b, c, d) 18. (b, c)
CH3 CH3 19. (b, c, d) 20. (a, b, d)
C and C
CH3 H LINKED COMPREHENSION TYPE
CH3 CH3

1. (d) 2. (a) 3. (c)
3. (a, b, d)
Sol.
In allene, bi-phenyl, spirane, etc. the chiral axis is
present. Cl
4. (b, d) Cl Cl
5. (a, c) Increase in solvent polarity, increases toe (P) POS so molecule is
lifetime of carbocation and stability of carbocation optically inactive
facilitates longer attack from both face without Cl Cl
hindrance, hence racemisation more. Moreover
solvent polarity decreases the ion-pair interaction Cl
also.
6. (b, d) Cl
H Cl Cl
CH3
H (Q) Molecule has POS so
optically inactive
Cl Cl
Cl
H Cl
H CH3 Cl Cl

axial-axial (R) Molecule has POS and
trans-form COS so O.I
1,3-diaxial H - Me repulsive interaction Cl Cl
torsional strain Cl
trans-annular strain
(Type of torsional strain which is eclipsed strain Cl
arise due to 1, 3 or 1, 5 position) Cl Cl
CH3 (S) Molecule doesn’t has POS
CH3
and COS so optically active.
no 1, 2-eclipsed strain (pitzer strain) Cl Cl
no 1, 3-eclipsed strain (trans - annular strain) stable Cl
form
Cl
7. (a, d) For being functional isomers, functional group
should not match. Cl Cl
(Phenol and aliphatic alcohol are considered as
different functional groups) (T) Molecule has POS so O.I.
8. (c, d) A meso compound has minimum two chiral
centres and it has a plane of symmetry and it is Cl Cl
optically inactive. Cl
9. (a, d) For being functional isomers, functional group
should not match. 4. (b) 5. (c) 6. (d)
(Phenol and aliphatic alcohol are considered as CH3
different functional groups)
7. ( a) Both are identical species H3C – CH – Cl there is
10. (a, b, c)
asymmetric ‘C’ atom present.
11. (a, b, c, d)
B, C, D have pairs of compounds which have chiral
12. (b, c)
carbon and are non superimposible on each other.
8. ( d) R’R and R’S are diastereomers and have different CH3 O CH3 CH2
physical properties like water solubility, B.P., M.P, C C
etc. Mixture of diastereomers is optically active HO HO
hence product mixture in step 1 is optically active. H H
H OH + O = CH2 H OH
9. (d) (Z)
H OH H OH
H9C4 C 4H 9 H9C4 CH3 CH2 – OH CH2 – OH
C=C or C=C (Y) (X)
H3C CH3 H 3C C4H9
CH3 CH3
H2/Ni Br2/hv alc. KOH
DCH2 D D CH2D
CH3 CH3 HO H HO H D /Ni
H OH + H OH 2
*
H9C4 C C* C4H9 H OH H OH
CH2 – OH CH2 – OH
Br H HBr/R2O2
10. (c) Diastereomers

CH2OH
H * O 1
H 18. (b) Stability a
* OH H * heat of hydrogenation
* *
OH H HO
(p) H3C – HC = CH – HC = CH3
O
HOH2C O H.C. + Resonance
* ⊕
*
H OH H3C – HC – CH = HC – CH2
H * *
OH H CH2OH ⊕
(q) H C = CH – HC = CH H2C = CH = HC – C2
The star shown indicates chiral centre. 2 2
Resonance
11. (c) 12. (b) 13. (d) 14. (d) 15. (b)
16. (a) ⊕
(r) H2C = C – C = CH2 H2C – C = C – CH2
17. (d) (X) →
O3 /H 2 O
Y+Z CH3 CH3 CH3 CH3
Zn
Z is the smallest aldehyde e.g., CH2 = O which gives 6H – H.C. Resonance

only one oxime.
O O– (s) H2C = C = CH2 then the order of heat of
C hydrogenation is s > q > p > r
I2/OH HO H
+ CHI3 ⊕
Y H OH
H OH 19. (a)
⊕
⊕
CH2–OH ⊕
CH3 C O ⊕
⊕
HO H
so Y must be H OH ⊕
H OH
CH2 – OH Maximum charge separation stability increases
so X must be
20. (d) Maximum charge separation stability increases (c) Compound is trans and active.
⊕
(d) Compound is cis and inactive.
O N N=O O=N N=O 4. A. Q, R B. Q, S C. P, Q, R D. Q, S
(a) Compound doesn’t has chiral centre but has
⊕ stereocentre and is opticaesy active.
O=N N=O
(b) Compound has P. O. S and has C. O. S. and has
⊕ ⊕ 2- stereo centers.
O N N=O O=N N=O (c) Compound has chiral centre stereo centre and
⊕ optically active.
O=N N–O
(d) Molecule has POS and COS and is non-polar
Then and is (d) and O.I.
+ − − + 5. A. Q B. Q, S C. P, Q, S D. Q, S
21. (a) CH2 – CH – CH = CH2 (B) CH2 – CH – CH = CH2
(a) Molecule has P. O. S. so inactive.
− +
(d) CH2 – CH = CH – CH2 (D) None of these (b) Molecule has P. O. S. so inactive.
22. (b) (c) Molecule has P. O. S. so inactive doesn’t has
chiral centre so not meso and can show G. I.
23. (d)
(d) Compounds has P. O. S. and doesn’t has chiral
ASSERTION AND REASON centres but can show G. I.
1. ( d) Because of the presence of chiral carbon in 6. A. Q, R B. P, R, S C. Q, R, S D. P, S
alkene, both products obtained are not mirror 7. A. S B. R C. Q D. P
images. Therefore, diastereomers are obtained.
2. (a) 3. (a) 4. (a) 5. (d) 6. (a) H
Me Me C
7. (d) 8. (a) COMe
C
MATRIX MATCH TYPE
* *
1. A. Q B. P C. R D. S (a)
(a) Total No. of stereo isomers = 2n, When molecule
is unsymmetrical Total isomer = 2n, 23 = 8
(b) When molecule is symmetrical total no. of
stereoisomers H
Me Me C
(I) When n = even COMe
C
Total isomers = 2n–1 + 2n/2–1 (b)
(ii) When n = odd.
 n −1
 n −1
Total isomers =  2n −1 − 2 2  + 2 2 Optically active S. I. = 2n, 22 = 4 (S. I. = Stereoisomerism)
 
meso H
C COMe
2. A. P, S B. Q, R, S C. Q, R, S D. P, S C
Chiral molecules: Those molecules which do not (c)
have plane of symmetry, centre of symmetry are
optically active and are not super imposable on their n = 1; S. I. = 21 = 2
mirror images and are known as chiral molecules
vice versa are achiral.
Chiral Centre: Tetrahedrally bonded atom having H
C COMe
four different groups are known as chiralcentres. C
3. A. P, R B. Q, S C. Q, R D. P, S
(a) Compound is cis doesn’t have P.O.S. and C.O.S. (d) Me
so optically active. (P.O.S. = Plane of Symmetry)
n = 1; S. I. = 21 = 2
(b) Compound is trans and has C.O.S. so optically
inactive. (C.O.S. = Center of symmetry) 8. A. R B. Q C. Q D. P
COOH COOH
HO H H OH General Organic Chemistry 2.263
(a)
H Me
Cl OH HO Cl
F *
COOH COOH F
*
Me H
Both are mirror images of each other so are
enantiomers. Molecule has 2-chiral centres and C. O. S so it is
meso so both are identical.
e H b
b a Br Cl
F 9. (A) → R and T are anti structures (or) staggered
Cl Br a
(b) structure.
→ Q and S are same are gauche structures
F c
H (B) → P, Q and P, S are conformational isomer
(C) → P and R, P and T, Q and R, Q and T, R and S
Both are identical. isomers are constitutional.
10. (A - P, Q, R, S); (B - P, S); (C - P); (D - R, S)
OH HO
11. (A – Q, R); (B - P, S); (C - P, S); (D - P, S)
(c)
12. (a) (i), (iii) (b) (i), (iii)
(c) (i), (ii), (iii) (d) (i), (ii), (iii), (iv)
Mirror images but are super impossible so are
identical. 13. (a) (ii), (iii), (iv) (b) (i), (iii), (iv)
(c) (iv) (d) (iii), (iv)
H
Me SUBJECTIVE ANSWER TYPE
F
1. (8) 2. (8) 3. (6) 4. (4)
(d) 5. (98)
Me F or
H
Molecular weight = 98.
Molecule has centre of symmetry and 2-chiral centre
6. (3)
so meso compound.
7. (5)
value of X used for compilation of reaction will be:
8. (3)
9. (11)
10. (iv)
JUDGE YOURSELF AT AIEEE LEVEL
PREVIOUS YEARS’ AIEEE QUESTIONS (c) —CHO,—COOH,—SO3H,—CONH2

(d) —CONH2,—CHO, —SO3H,— COOH
1. The correct decreasing order of priority for the func- HO2C CO2H
tional groups of organic compounds in the IUPAC 2. The absolute configuration of
system of nomenclature is HO
HH OH
[2008]
[2008]
(a) — COOH,— SO3H,— CONH2, — CHO (a) S, S (b) R, R
(b) — SO3H, — COOH,—CONH2, — CHO (c) R, S (d) S, R
3. The IUPAC name of is (a) (CH3)2 CH < (CH3)3 C < (C6H5)2 CH < (C6H5)3 C
(b) (C6H5)3 C < (C6H5)2 CH < (CH3)3 C < (CH3)2 CH

(a) 1, l-diethyl-2, 2-dirnethylpentane (c) (C6H5)2 CH < (C6H5)3 C < (CH3)3 C < (CH3)2 CH
(b) 4, 4-dimethyl-5, 5-diethylpentane
(c) 5, 5-diethyl-4, 4-dimethylpentane (d) (CH3)2 CH < (CH3)3 C < (C6H5)3 C < (C6H5)2 CH
(d) 3-ethyl-4, 4-dimethylheptane
4. Which one of the following conformations of 9. Increasing order of stability among the three
cyclohexane is chiral? [2007] main conformations (ie, Eclipse, Anti, Gauche) of
2-fluoroethanol is [2006]
(a) Twist boat (b) Rigid
(c) Chair (d) Boat (a) Eclipse, Gauche, Anti
(b) Gauche, Eclipse, Anti
5. Which of the following molecules is expected to (c) Eclipse, Anti, Gauche
rotate the plane of polarised light [2007] (d) Anti, Gauche, Eclipse
CHO 10. The correct order of increasing acid strength of the
compounds is [2006]
(a) HO H (b)
(A) CH3CO2H (B) MeOCH2CO2H
SH Me
CH2OH
(C) CF3CO2H (D) CO2H
COOH
H 2N NH2 Me
(c) H H (d) H2N H (a) B < D < A < C (b) D < A < C < B
Ph Ph (c) D < A < B < C (d) A < D < C < B
H
11. The number and type of bonds between two carbon
6. Which of the following is the correct order of atoms in calcium carbide are [2005]
decreasing SN2 reactivity? [2007] (a) two sigma, two pi (b) two sigma, one pi
(a) RCH2X > R3CX > R2CHX (c) one sigma, two pi (d) one sigma, one pi
(b) RCH2X > R2CHX > R3CX
(c) R3C X > R2CHX > RCH2 X 12. Due to the presence of an unpaired electron, free
(d) R2CH X > R3C X > RCH2 X radicals are [2005]
(X = a halogen) (a) cations
(b) anions
7. The IUPAC name of the compound shown below is
(c) chemically inactive
[2006]
(d) chemically reactive
Cl 13. Tertiary alkyl halides are practically inert to
substitution by SN2 mechanism because of [2005]
(a) steric hindrance (b) inductive effect
(c) instability (d) insolubility
Br
14. Among the following acids which has the lowest pKa
(a) 2-bromo-6-chlorocyclohex-l-ene value? [2005]
(b) 6-bromo-2-chlorocyclohexene (a) CH3CH2COOH
(c) 3-bromo-l-chlorocydohexene (b) (CH3)2CH—COOH
(d) l-bromo-3-chlorocyclohexene (c) HCOOH
(d) CH3COOH
8. The increasing order of stability of the following free
radicals is 15. The decreasing order of nucleophilicity among the
[2006] nucleophiles [2005]
(a) CH3 C — O– (b) CH3O– (a) Heat of vaporisation

(b) Vapour pressure at the same temperature
O O (c) Boiling points
(d) Gaseous densities at the same temperature and
(c) CN– (d) H3C O
– pressure
S
22. Which of the following compounds is not chiral?
O [2004]
(a) (C), (B), (A), (D) (b) (B), (C), (A), (D) (a) 1-chloropentane
(b) 2-chloropentane
(c) (D), (C), (B), (A) (d) (A), (B), (C), (d)
(c) l-chloro-2-methyl’pentane
16. The reaction (d) 3-chloro-2-methyl pentane
O O 23. Amongst the following compounds, the optically active
alkane having lowest molecular mass is [2004]
R C X + Nu R C Nu + X
(a) CH3 — CH2 — CH2 — CH3
is fastest when X is [2005] CH3
(a) OCOR (b) OC2H5
(c) NH2 (d) Cl (b) CH3 — CH2 — CH — CH3
17. Which types of isomerism is shown by 2, H

3-dichlorobutane? [2005]
(c) CH3 — C
(a) Structural (b) Geometric
(c) Optical (d) Diastereo C2H5
18. The IUPAC name of the compound [2004] (d) CH3 — CH2 — C ≡≡ CH
is 24. Which of the following will have a meso-isomer also?

[2004]
HO (a) 2-chlorobutane
(a) 3, 3-dimethyl-l-hydroxy cyclohexane (b) 2,3-dichIorobutane
(b) 1, l-dimethyl-3-hydroxy cyclohexane (c) 2, 3-dichloropentane
(c) 3, 3-dimethyl-l-cyclohexanol (d) 2-hydroxypropanoic acid
(d) 1, l-dimethyl-3-cyclohexanol 25. The IUPAC name of CH3COCH(CH3)2 is [2003]
19. Which one of the following does not have sp2 (a) isopropylmethyl ketone
hybridised carbon? [2004] (b) 2-methyl-3-butanone
(c) 4-methylisopropyl ketone
(a) Acetone (b) Acetic acid (d) 3-methyl-2-butanone
(c) Acetonitrile (d) Acetamide
26. Among the following four structures I to IV:
20. Rate of the reaction
CH3 O CH3
O O
+ Z–
–
R C + Nu R C C2H5 CH C3H7 CH3 C CH C2H5
Z Nu (I) (II)
is fastest when Z is [2004] H CH3
(a) Cl (b) NH2
(c) OC2H5 (d) OCOCH3 H C⊕ C 2H 5 CH C2H5
21. For which of the following parameters the structural H

isomers C2H5OH and CH3OCH3 would be expected to
have the same values? (III) (IV)
(Assume ideal behaviour) [2004] It is true that [2003]
(a) all four are chiral compounds

(c) Cl + KOH
(b) only I and II are chiral compounds
(c) only III is a chiral compound.
(d) CH2CH2Cl + KOH
(d) only II and IV are chiral compounds
27. In the anion, HCOO– the two carbon-oxygen bonds 32. Following reaction
are found to be of equal length. What is the reason
(CH3)3CBr + H2O → (CH3)3COH+ HBr is an example
for it? [2003]
of [2002]
(a) Electronic orbits of carbon atom are hybridised (a) elimination reaction
(b) The C = O bond is weaker than the C—O bond (b) free radical substitution
(c) The anion, HCOO– has two resonating structures (c) nucleophilic substitution
(d) The anion is obtained by removal of a proton from (d) electrophilic substitution
the acid molecule
33. Following types of compounds (as I, II) [2002]
28. Which of the following compounds has incorrect
IUPAC nomenclature? (I) CH3CH CHCH3 (II) CH3 CH OH
O CH2CH3
(a) CH3CH2CH2COC2H5
(ethyl butanoate)
are studied in terms of isomerism in
(b) CH3CHCH2CHO (a) chain isomerism (b) position isomerism
(c) conformers (d) stereoisomerism
CH3
34. Racemic mixture is formed by mixing two [2002]
(3-methyl butanal)
O (a) isomeric compounds
(b) chiral compounds
(c) CH CH C CH CH (c) meso compounds
3 2 3
(d) enantiomers with chiral carbon
CH3
2-methyl-3-pentanone 35. Geometrical isomerism is not shown by [2002]
(d) CH3CHCHCH3 (a) 1, 1-dichloro-1-pentene
H3C OH (b) 1, 2-dichloro-1-pentene
2-methyl-3-butanol (c) 1, 3-dichloro-2-pentene
(d) 1, 4-dichloro-2-pentene
29. Underlined carbon is sp3 hybridised in
36. Arrange the carbanions,
(a) CH 3 CH = CH 2 (b) CH 3 CH 2 NH 2
(CH 3 )3 C, CCl3 , (CH 3 ) 2 CH, C6 H 5 CH 2 ,
(c) CH 3 CONH 2 (d) CH 3CH 2 CN
in order of their decreasing stability:
30. In the following benzyl/allyl system [2009]
(a) C6 H 5 CH 2 > CCl3 > (CH 3 )3 C > (CH 3 ) 2 CH
R — CH CH2 or R
(b) (CH 3 ) 2 CH > CCl3 > C6 H 5 CH 2 > (CH 3 )3 C
(R is alkyl group) (c) CCl3 > C6 H 5 CH 2 > (CH 3 ) 2 CH > (CH 3 )3 C
decreasing order of inductive effect is (d) (CH 3 )3 C > (CH 3 ) 2 CH > C6 H 5 CH 2 > CCl3
(a) (CH3)3C — > (CH3)2CH — > CH3CH2 –
(b) CH3CH2 — > (CH3)2CH —> (CH3)3C – 37. The alkene that exhibits geometrical isomerism is:
(c) (CH3)2CH — > CH3CH2 — > (CH3)3C –
(a) propene (b) 2-methyl propene
(d) (CH3)2C — > CH3CH2 — > (CH3)3CH –
(c) 2-butene (d) 2-methyl-2-butene
31. SN1 reaction is feasible in [2002] (2009)
(a) Cl + KOH
38. The number of stereosiomers possible for a compound
Cl of the molecular formula CH3 – CH = CH – CH(OH)
(b) + KOH – Me is:
(a) 3 (b) 2 (c) RCOO < NH 2 < HC ≡ C < R

(c) 4 (d) 6
[2009] (d) RCOO < HC ≡ C < NH 2 < R
39. The IUPAC name of neopentane is 41. Out of the following, the alkene that exhibits optical
(a) 2-methylbutane isomerism is
(b) 2, 2-dimethylpropane (a) 3–methyl–2–pentene
(c) 2-methylpropane (b) 4–methyl–1–pentene
(d) 2, 2-dimethylbutane (c) 3–methyl–1–pentene
[2009] (d) 2–methyl–2–pentene
[2010]
40. The correct order of increasing basicity of the given
conjugate bases (R = CH3) is [2010] 42. Identify the compound that exhibits tautomerism.
(a) Lactic acid (b) 2-Pentanone
(a) RCOO < HC = C < R < NH 2
(c) Phenol (d) 2-Butene
(b) R < HC ≡ C < RCOO < NH 2 [2011]
ANSWER KEYS
1. (a) 2. (b) 3. (d) 4. (c) 5. (a) 6. (b) 7. (c) 8. (a) 9. (c) 10. (c)
11. (c) 12. (d) 13. (a) 14. (c) 15. (b) 16. (d) 17. (c) 18. (c) 19. (c) 20. (a)
21. (d) 22. (a) 23. (c) 24. (b) 25. (d) 26. (b) 27. (c) 28. (d) 29. (b) 30. (a)
31. (a) 32. (c) 33. (d) 34. (d) 35. (a) 36. (c) 37. (c) 38. (c) 39. (b) 40. (d)
41. (c) 42. (b, c)
SOLUTIONS
1. The correct decreasing order of priority for the 5. The molecule, which is optically active, has chiral
functional groups of organic compounds in the IUPAC centre, is expected to rotate the plane of polarised
system is light.
— COOH > — SO3H > — COOK > COCl > CHO
— CONH2 > — CN > — CH = O
HO * H
2 2 COOH
2. HOOC COOH
3 3 H OHR CH2OH
H OH or
HO H R
HOR H1 One chiral centre ⇒ optically active
1 COOH
H2N NH2
6 2 H
H
3. 7 43 1 Ph Ph
5
Two chiral centres, but plane of symmetry within
molecule ⇒ optically inactive.
3-ethyl-4, 4 dimethylheptane
6. SN2 reactions are greatly controlled by steric factor.
4. R — CH2 — X, R2CH — X, R3C — X
1° 2° 3°
Chair form is unsymmetrical and has absence of any SN2 reactivity decreases as bulkyness of alkyl group
element of symmetry. increases.
Cl 12. Free radicals have unpaired electrons, so are neutral

1 and reactive.
6 2
7. CH3 + CH3 → CH3 — CH3
5
3 Br
4 13. In SN2 reaction, nucleophile and alkyl halide react in
Unsaturation (double bond) is given priority over one step.
halogen. So, the correct IUPAC name is 3-bromo-l- R R R
chlorocyclohexene. R Br + Nu
–
Nu C Br
C
8. Free radicals stability: R R
C6H5 C C6H5 > C6H5 CH
Thus, tertiary carbon is under steric hindrance, hence
C6H5 C6H5 reaction does not take place until (C—Br) bond
breaks.
highly stable by delocalisation R R
> CH3 C CH3 > H3C C H slow ⊕ –
R C Br R C + Br
CH3 CH3 R R
9-hyperconjugative
hydrogens and +I effect
which is an SN1 reaction.
9. HO – CH2 – CH2 – F
14. Out of the given acids, strongest is HCOOH.
+ + + (highest Ka value)
Since, pKa = – log Ka
Thus, lowest pKa is of HCOOH.
)į±
+
15. If acid is weak, its conjugate base (nucleophile) is
2²+į
strong and vice-versa.
Gauche conformation is comparatively more stable due O O
to hydrogen linkage in between F and H (at O-atom),
hence order is eclipse, and (staggered), gauche. (a) CH3 C O is a conjugate base of CH3COH (I)
–
O O (b) CH3O– is a conjugate base of CH3OH (II)

Me
(c) CN– is a conjugate base of HCN (III)
10. CH — C — OH < CH3 — C — O — H
(d) H3C SO3 is a conjugate base of
–
Me
O O SO3H (IV)
F H3C
< MeO — CH2 — C — OH < F C — C — OH
Thus, order of acidic nature is IV > I > III > II and
F nucleophilicity is B > C > A > D.
–I effect increases acidity
+ I effect decreases acidity. O O
– CF3 exerting more –I effect than MeO— 16. R – –
C X + Nu → R C Nu + X
– Me2CH— exerting more + I effect than — CH3
11. CaC2 (calcium carbid(e) is ionic. Best leaving group (poorest nucelophile) is ClQ, thus
fastest reaction is with Cl.
→ Ca 2 + + C 22 -
CaC 2 
* *
-
C ≡≡ C- 17. CH3 CH CH CH3
C 22− has one a and two p bonds. Cl Cl

There are two chiral C-atoms (*). (a) CH3CH2CH2CH2CH2Cl (no chiral carbon atom)
Thus, optical isomerism is possible. (b) CH3 CH CH2CH2CH3 (one chiral carbon atom)
5
6 4 Cl
18. *
1 3 (c) CH3 CH2 CH2 CHCH2Cl (one chiral carbon atom)
HO
2
CH3
Carbon with —OH group is given C1, thus it is 3,
* *
3-dimethyl-l-cydohexanol. (d) CH3 CH — CHCH2CH3 (two chirl carbon atoms)
O O CH3 Cl
19. (a) CH3 — C — CH3 (b) CH3 — C — OH
sp3 sp2 sp3 sp3 sp2 *
23. CH3 — CH —
O
CH2CH3
(c) CH3 — C N (d) CH3 — C NH2
sp contains asymmetric carbon atom, thus optically ac-
sp3 sp3 sp2
tive.
Acetonitrile does not contain sp2 hybridised carbon.
*
20. Cl– is the best leaving group being the weakest 24. (a) CH3 — CH — CH2CH3
nucleophile out of NH −2 , Cl–, O — C2H5 and
Cl
Note: if acid HX is weak, its conjugate base X– is
strong and vice-versa ne asymmetric carbon atom, forms d-and
O
l-optical isomers
NH3< C2H5OH < CH3COOH < HCl
Acidic strength increases CH3
–
NH2– > C2H5O > CH3COO > Cl
– –
plane of H —*C — Cl
(b) symmetry
Basic strength of conjugate base increases H —*C — Cl
21. In CH3CH2OH, there is intermolecular H-bonding CH3
while it is absent in isomeric ether CH3OCH3. meso due to
• Larger heat is required to vaporise CH3CH2OH as internal compensation
compared to CH3OCH3, thus (a) is incorrect. wo asymmetric carbon atoms. Forms d-, l- and
T
• CH3CH2OHis less volatile than CH3OCH3, thus meso forms.
vapour pressures are different, thus (b) is incor-
rect. (c) CH3 —*CH — *CH — CH2CH3
• bp of CH3CH2OH > CH,OCH3, thus (c) is incor-
Cl Cl
rect.
wo asymmetric carbon atoms but does not have
T
mass
Density = , due to ideal behaviour at a vol- symmetry. Hence, meso form is not formed.
volume
ume given temperature and pressure volume and (d) CH —*CH — COOH
3
molar mass are same. Hence, they have same vapour
density. OH
22. Chiral carbon has all the four different groups attached ne asymmetric carbon atom, meso form is not
O
to it. formed.
O (a)
25. CH3 — C — CH — CH3 (b) 1° carbocation

1 2 3 4 ⊕
CH3 (c) ⊕ arylic carbocation

3-methyl butan-2-one
or 3-methyl-2-butanone ⊕
(d) CH2 CH2
O
Unstable
keto (—C—) functional group is given priority. 1° carbocation
26. Chiral compounds are those which have one chiral 32. (CH3)3C –Br + H2O → (CH3)3C – OH + HBr
centre ie, all four atoms or groups attached to same
Br is substituted by –OH– (nucleophile)→ SN1 reac-
carbon are different.
tion (unimolecular substitution reaction)
–
O O H3C CH3 H3C H
27. H — C H—C 33. C C C C
– O and
O H H H CH3
O geometrical isomers
H—C (cis–trans)
O H H
Resonating (canonical)
structures of formate ion
CH3 C C CH3
incorrect
numbering
OH HO
CH2CH3 CH3CH2
4 3 2 1
28. CH3 — CH — CH — CH3
1 2 3 4
molecule is optically active
CH3 OH enantiomers
Correct numbering
Correct name3-methyl butan-2-ol functional group
or 3-methyl-2-butanol should be given Geometrical isomers and enantiomers both are stereo-
priority isomers.
H 34. Racemic mixture is an equimolar mixture of

enantiomers.
29. (a) CH3 — C CH2 (b) CH3 — C
– – — NH2 Cl CH2CH2CH3
H sp 2
H sp 3 35. C C
Cl H
O
At least two groups or atoms attached to doubly bond-
(c) CH3 — C
– NH2 (d) CH3 — CH
– 2 C
– N ed carbon atoms should be different.
sp2 sp 36. 2° carbanion is more stable than 3° and Cl is —I effect

group.
30. Both where R is attached to vinylic (≈ arylic) system H H H CH3
positive inductive effect occurs in the following 37. C C C C
order: CH3 CH3 H
H3C
—O– > —COO– > (CH3)3 C — > (CH3)2 CH — > cis Trans
CH3CH2 — > CH3 >
38. About the double bond, two geometrical isomers
31. SN1 (unimolecular nucleophilic substitution) reaction are possible and the compound is having one chiral
is favoured with stability of carbocation. carbon.
CH3 +
39. Neopentane is H C – C – CH 41. +& +& &+ RQO\±PHWK\O±±SHQWHQH
3 3
KDVDFKLUDOFDUERQ
CH3 &+
40. Correct order of increasing basic strength is 42. both 2-pentanone, phenol can exhibit tautomerism.
R–COO(–) < CH ≡ C(–) < NH2(–) < R(–)
CRACK THE IIT-JEE QUESTIONS

PREVIOUS YEARS’ IIT-JEE QUESTIONS
5. Which of the following molecules represents the

HYBRIDIZATION,
hybridisation sp2, sp2, sp sp from left to right atoms?
ISOMERISM AND NOMENCLATURE
[2003]
(a) H2C = CH — C ≡ CH
STRAIGHT CONCEPTUAL TYPE (b) HC ≡ C—C ≡ CH
(c) H3C—CH = CH—CH3
1. Which of the following compounds will exhibit (d) H2C = CH — CH = CH2
geometrical isomerism?
[2000] 6. An enantiomerically pure acid is treated with racemic
mixture of an alcohol having one chiral carbon. The
(a) 1-phenyl-2-butene
ester formed will be
(b) 3-phenyl-1-butene
(c) 2-phenyl-1-butene [2003]
(d) 1,1-diphenyl-1-propene (a) optically active mixture
(b) pure enantiomer
+ 0H (c) meso compound
0H
(d) racemic mixture
2.
+
0H 7. Monochlorination of 2-methylbutane produces
+ [2004]
Hydrogenation of the above compound in the presence (a) no optically active isomers
of poisoned palladium catalyst gives (b) two optically active isomers
[2001] (c) four optically active isomers
(a) an optically active compound (d) six optically active isomers
(b) an optically inactive compound
(c) a racemic mixture 8. The IUPAC name of C6H5COCl is
(d) a diastereomeric mixture [2006]
3. The number of isomers for the compound with (a) Benazal cholride (b) Benzyl chloride
molecular formula C2BrClFI is [2001] (c) Benzoyl chloride (d) Phenylchloro ketone
(a) 3 (b) 4 9. The number of stereoisomers obtained by bromination
(c) 5 (d) 6 of trans-2-butene is [2007]
4. Which of the following compounds exhibits (a) 1 (b) 2
stereoisomerism? (c) 3 (d) 4
[2001]
(a) 2-methylbutene-1 10. The number of structural isomers for C6H14 is
(b) 3-methylbutyne-l [2007]
(c) 3-methylbutanoic acid (a) 3 (b) 4
(d) 2-methylbutanoic acid (c) 5 (d) 6
2+ (d) I f the stereochemistry about the double bond in X is

cis, the number of enantiomers possible for X is 2
11. The IUPAC name of the compound is INTEGER ANSWER TYPE
&1 1. The total number of cyclic structure as well as

%U stereoisomers possible for a compound C5H10 is ____.
(a) 4-Bromo-3-cyanophenol [2009]
(b) 2-Bromo-5-hydroxybenzonitrile
2. The total number of cyclic isomers possible for a
(c) 2-cyano-4-hydroxybromobenzene
hydrocarbon with the molecular formula C4H6 is
(d) 6-Bromo-3-hydroxybenzonitrile
____. (2010)
MULTIPLE CORRECT CHOICE TYPE 3. The total number of contributing structure showing
hyperconjugation (involving C–H bonds) for the
1. The correct statement(s) concerning the structures E, following carbocation is [2011]
F and G is (are) [2008]
+& &+&+
2 2+ +& &+
+& +&
+& 2+
+& &+ + & &+
( ) *
(a) E, F and G are resonance structures REASONING TYPE

(b) E, F and E, G are tautomers
(c) F and G are geometrical isomers 1. STATEMENT-1: Molecules that are not
(d) F and G are diastereomers superimposable on their mirror images are chiral.
[2007]
2. The correct statement(s) about the compound given
below is (are) [2008] because
STATEMENT-2: All chiral molecules have chiral
&O + centres.
(a) Statement-1 is True, Statement-2 is True; State-
&+ ment-2 is correct explanation for Statement-1
+ & (b) Statement-1 is True, Statement-2 is True; State-
&O + ment-2 is NOT a correct explanation for State-
ment-1
(a) The compound is optically active (c) Statement-1 is True, Statement-2 is False
(b) The compound possesses centre of symmetry (d) Statement-1 is False, Statement-2 is True
(c) The compound possesses plane of symmetry
(d) The compound possesses axis of symmetry SHORT ANSWER TYPE
3. The correct statement(s) about the compound X,
H3C(H(O)HC—CH=CH—CH(O(H)CH3 is (are) 1. Identify the pairs of enantiomers and diastereomers
[2009] from the following compounds I, II and III.
(a) The total number of stereoisomers possible for X [2000]
is 6 &+ &+ &+
(b) The total number of diastereomers possible for X
+ 2+ +2 + +2 +
is 3 + +2 + + 2+
+2
(c) If the stereochemistry about the double bond in X
is trans, the number of enantiomers possible for X &+ &+ &+
is 4 , ,, ,,,
2. A recemic mixture of (±) 2-phenyl-propanoic acid (b) M andelic acid, C6H5CHOHCO2H, is readily raec-
on esterification with (+) 2-butanol gives two esters. mised by warming with aqueous sodium hydrox-
Mention the stereochemistry of the esters produced. ide. On the other hand, atrolactic acid, C6H5C(CH3)
[2003] (O(H)CO2H, is not racemised. Explain.
(c) The addition of hydrogen cyanide to carbonyl
3. (a) (–)-Lactic acid is racemised in aqueous sodium compounds is accelerated by bases and retarted
hydroxide. Explain. [2003] by acids Explain.
ANSWER KEYS
Straight Conceptual Type
1. (a) 2. (b) 3. (d) 4. (d) 5. (a) 6. (a) 7. (c) 8. (c) 9. (a) 10. (c)
11. (b)
Multiple Correct Choice Type

1. (b, c, d) 2. (a, d) 3. (a, d)
Integer Type
1. (7) 2. (5) 3. (6) 6 × H-atoms are there
Reasoning Type
1. (c)
Short Answer Type

1. Enantiomers—Isomers are mirror images of each other.
Diastereomers—Isomers are not mirror images of each other.
Hence,
Structures I and III are enantiomers
Structures I and II, and II and III are diastereomers.
2. Since during esterification no bond is broken, the resultant esters will be ++ and +– isomers.
3. (a) The racemisation occurs via the enol form as shown in the following.
2+ 2+ +
2
2 2
+2 2±
±+ ±+
+& & & +& & & +& & & & &
2 ±
2 ±
2 ±
+& 2±
+ ± 2+
(a) The methyl group in place of hydrogen atom in atrolactic acid prevents keto-enol tautomerism and hence racemisation.
(c) The addition of hydrogen cyanide proceeds as follows.
±
VORZ 2 +
2+
±
5& 2&1 5& 2 5&
IDVW
&1 &1
In bases, CN is formed from HCN while in acidic medium, the ionization of HCN to give CN– suppressed.
–
HINTS AND SOLUTIONS
STRAIGHT CONCEPTUAL TYPE +& + &+

&
1. Only 1-phenyl-2-butene will exhibit cis-trans
%U %U +
isomerism. %U +
&
2. –––––––––––––– + &+ &+
3. The six compounds will be PHVRGLEURPREXWDQH
Thus, only one stereoisomer is obtained.
%U ) %U ,
& & & & 10. The molecule C6H14 is an alkane. It can have the

&O , &O ) following carbon skeletons.
%U &O %U , &²&²&²&²&²&
& & & & &²&²&²&²&&²&²&²&²&
) , ) &O
& &
%U ) %U &O &
& & & &
, &O , ) &²&²&²&&²&²&²&
4. 2-Methyibutanoic acid has one asymmetric carbon & & &
atom.
Thus, the molecule C6H14 can have 5 structure isomers.
5. Choice a sp2, sp2, sp, sp Choice b sp, sp, sp, sp
Choice c sp3, sp2, sp2, sp3 Choice d sp2, sp2, sp2, sp2 MULTIPLE CORRECT CHOICE TYPE
6. ––––––––––––––– 1. E and F, and E and G involve the migration of a

proton from carbon atom to the adjacent atom. These
7. The possible products are
are keto-enol tautomers (choice b).
&O&+&+&+&+ &+&+ &+&+ F and G are cis- and trans- isomers and thus consti-
tute geometrical isomers (choice c).
&+ &O &+ F and G are diastereomers. These are optical isomers
that are not mirror images (choice d).
2SWLFDOO\LQDFWLYH 2SWLFDOO\DFWLYH
7ZRLVRPHUV 2. The given compound is
&O
+ +
&O + &O &O
&+&+&&+ &+&+&+&+&O
+& &+ Ł Ł
&+ &+
2SWLFDOO\LQDFWLYH 2SWLFDOO\DFWLYH &O + &+ &+
7ZRLVRPHUV
&+
8. The IUPAC r.ame of C6H5COCl is benzoyl chloride. &O +
9. The addition of Br2 across a double bond involves + &O
the formation of a bromonium ion intermediate &+
followed by the anti addition of Br–. For trans-2-
butene, the reaction proceeds so as to form meso-2, The compound is optically active and has diad axis
3-dibromobutane. of symmetry.
3. The configurations of the given compounds are as follows.
&+ &+
+2
2+
& &
+ + + +
& &
(QDQWLRPHUV
+ & & +
& + + &
+2 2+
&+ &+
&+ &+
+2
2+
& &
+ + + +
& &
3ODQHRIV\PPHWU\
+2 & & 2+ ,GHQWLFDO&RQILJXUDWLRQV
& + + &
+ +
&+ &+
&+ &+
+2
2+
& & (QDQWLRPHUV
+ + +
+ & &
& 2+ &
+2 +
+ & &
+
&+ +
&+
&+ &+
+2
2+
& &
+ + +
+ & &
&HQWUHRIV\PPHWU\
& + & ,GHQWLFDO&RQILJXUDWLRQV
+ +
+ & &
2+
&+ +2
&+
There are three isomers (R(R), (Ss) and (Rs) in each stereoisomers are possible. In these, (R(R) and (Ss)
of the two (cis and trans) configurations and hence six are enantiomers both in cis and irons configurations.
INTEGER TYPE 2. The possible isomers are

&+ &+ &+
1. The following are the isomers of C5H10

Hence, there are five isomers.
REASONING TYPE
The structure can exist as cis-trans isomers 1. Solution: Statement-1 is correct but statement-2 is not
and one optical isomer are possible. correct. For example 2,3-pentadiene has no chiral C’s,
Therefore, the total number of structures will be 7. yet it is a chiral molecule (it has two enantiomers).
INDUCTIVE AND RESONANCE EFFECTS

STRAIGHT CONCEPTUAL TYPE
2
(a)
1
1. Which of the following has the highest nucleophilicity?
2
[2000]
(a) F– (b) OH– 2
(b)
(c) CH 3− (d) NH2 1
2. An SN2 reaction at an asymmetric carbon of a 2

compound always gives [2001] 2

(a) an enantiomer of the substrate (c) 1
(b) a product with opposite optical rotation
(c) a mixture of diastereomers 2
(d) a single stereoisomer
2
3. For 1-methoxy-l, 3-butadiene, which of the following
(d) 1
resonating structures is the least stable? [2005]
2
(a) +& &+ &+ &+ 2 &+
6. Hyperconjugation involves overlap of the following
(b) +& &+ &+ &+ 2 &+ orbitals [2008]
(a) s-s (b) s-p
(c) +& &+ &+ &+ 2 &+
(c) p-p (d) p-p

(d) +& &+ &+ &+ 2 &+ 7. The correct stability order for the following species
is [2008]
4. The correct order of reactivity of the following types

of H atom towards radical substitution is [2005]
(a) allylic > vinylic > 1° H 2 2
(b) allylic > 1° H > vinylic , ,, ,,, ,9

(c) 1° H > allylic > vinylic
(a) (II) > (IV) > (I) > (III)
(d) vinylic > allylic > 1° H
(b) (I) > (II) > (III) > (IV)
5. Among the following, the least stable resonance (c) (II) > (I) > (IV) > (III)
structure is [2007] (d) (I) > (III) > (II) > (IV)
8. In the carbocation [2009]

REASONING TYPE
+ +
1. STATEMENT-1: Bromobenzene upon reaction

+ & & & & &+ with Br2/Fe gives 1, 4-dibromobenzene as the major
product
2+ + &+ and
STATEMENT-2: In bromobenzene, the inductive
the species H/CH3 that is most likely to migrate the
effect of the bromo group is more dominant than
positively charged carbon is
the mesomeric effect in direction of the incoming
(a) CH3 at C—4 (b) H at C — 4
electrophile.
(c) CH3 at C—2 (d) H at C—2
(a) STATEMENT-1 is True, STATEMENT-2 is True;
9. The correct stability order of the resonance structures STATEMENT-2 is a correct explanation for
[2009] STATEMENT-1
± ± ± (b) STATEMENT-1 is True, STATEMENT-2 is True;
+& 1 1 +& 1 1 +& 1 1 STATEMENT-2 is NOT a correct explanation for
±
+& 1 1 STATEMENT- 1
(c) STATEMENT-1 is True, STATEMENT-2 is
(a) (I) > (II) > (IV) > (III) False
(b) (I) > (III) > (II) > (IV) (d) STATEMENT- 1 is False, STATEMENT-2 is
(c) (II) > (I) > (III) > (IV) True
(d) (III) > (I) > (IV) > (II) (2008)
ANSWER KEYS
Straight Conceptual Type
1. (c) 2. (d) 3. (a) 4. (d) 5. (a) 6. (b) 7. (d) 8. (d) 9. (b)
Reasoning Type
1. (c)
HINTS AND SOLUTIONS
1. ––––––––––––––
+& &+±&+ &+±2±&+
2. ––––––––––––––
+&±&+ &+±&+ 2±&+ FKRLFHG
3. 1 methoxy-1, 3-butadiene is H2C = CH – CH = CH
2 – CH3 +& &+±&+ &+±2±&+
Its resonating structure may be visualized as follows
+&±&+±&+ &+±2±&+ FKRLFHF
+& &+±&+ &+±2±&+

+& &+±&+±&+±2±&+ FKRLFHD The structure +& &+±&+±&+±2±&+
+& &+±&+ &+±2±&+ (choice(a) is expected to be least stable as the move-

ment of electron is in the opposite direction to that of
+& &+±&+ &+±2±&+ FKRLFHE
electrons from oxygen of methoxy group
4. The correct order is allylic > 1° alkyl > vinylic Of the species (II) and (III), the species (III) will
The less positive DH for the dissociation of C—H be more stable due to the lone-pair of electrons on
bond, the more reactive is H atom. The order of DH’s oxygen atom. Hence, the order of stability is (I) > (III)
is allylic < 1° alkyl < vinylic. > (II) > (IV).
5. In the structure(a), the movement of Ti-electrons of 8. It is H at C—2 that migrates to give

–C = C– bond moves away from nitro group generating + +
positively charged C near to the neighbouring
positively charged N as shown in the following.
+& & & & &+
2
2

1 1 2+ + &+
2 2 The positive charge on C—2 is resonance stabilised
due to the neighbouring oxygen.
This leads to the least stability in the resonance struc-
ture. 9. The structure (I) will be the most stable as it maintains
conjugation.
6. Hyperconjugation occurs in a molecular of the type
The structure (IV) will be the least stable as it loses
conjugation and lesser electronegative carbon ac-
&+ where p orbitals of benzene quires negative charge
The structure (III) will be more stable than (II) as it
overlap with s orbitals of CH3 group. Hence, maintains a triple bond between two nitrogens. Hence,
hyperconjugation involves s - p orbitals overlap. the correct order of stability is (I) > (III) > (II) > (IV)
7. Electron-donating species stabilises carbocation. Reasoning Type

Hence, (I) is more stable than (III). 1. Bromobenzene is ortho- and para-director due to the fact
2° carbocation is more stable than 1° carbocation. that in the electrophilic substitution reaction, mesomeric
Hence, (II) is more stable than (IV). effect is more dominant than the inductive effect.
Hydrocarbon
3
Introduction
Compounds containing only two elements carbons and hydrogen are known as hydrocarbons. On the basis of structure and
properties, hydrocarbons are divided into two main classes viz aliphatic and aromatic. Aliphatic hydrocarbons are further
divided into different families namely alkanes, alkenes, alkynes and their cyclic analogs (cycloalkanes, cycloakenes and
cycloalkynes etc.)
Hydrocarbons
Aliphatic Aromatic
Saturated Unsaturated
Alkanes Alkenes Alkynes Arenes

Only CC σ bonds all CC σ and one CC σ and 2π 6C cyclic array
C sp3 hybridised π bonds C = C bonds C ≡ C all C sp2 hybridised
SATURATED HYDROCARBONS - ALKANES
Alkanes are open chain (acyclic) hydrocarbons comprising the homologous series with the general formula C n H 2n + 2
where ‛n’ is an integer. They have only single bonds and therefore are said to be saturated. Because of their low chemical
activity, alkanes are also known as Paraffins.
Cycloalkanes
They have one or more rings of carbon atoms. The simplest examples of this class consist of a single, unsubstituted carbon
ring. If a simple unbranched alkane is converted to a cycloalkane two hydrogen atoms, one from each end of the chain must
be lost. Hence, the general formula for a cycloalkane composed of n carbon in CnH2n.
3.2 Hydrocarbon
IUPAC NOMENCLATURE (see ‘Nomenclature’ for details)

The IUPAC system of alkane nomenclature is based on the simple fundamental principle of considering all compounds to
be derivatives of the longest single carbon chain present in the compound. The chain is then numbered from one end to
the other, the end chosen as number 1 is that which gives the smaller number at the first point of difference.
CH 3 CH 3
H3 C
H3 C CH 3 CH 3
2-methylpentane 3-methylhexane
When there are two or more identical appendages, the modifying prefixes di-, tri-, tetra-, penta-, hexa-, and so on are
used, but every appendage group still gets its own number.
CH 3 CH 3 CH 3
H3 C CH 3
CH 3 H3 C CH 3
H3 C CH 3
2,2-dimethylpentane 2,2,4,4-tetramethylpentane
When two or more appendage locants are employed, the longest chain is numbered from the end which produces the
lowest series of locants. When comparing one series of locants with another, that series is lower which contains the lower
number at the first point of difference.
CH 3 CH 3
H3 C H3 C CH 3
H3 C CH 3 CH 3
H3 C
CH 3 CH 3 CH 3 CH 3 CH 3
2,3-dimethylpentane 2,5,6-trimethyloctane 2,2,4-trimethylpentane
(not 3,4,7-trimethyloctane) (not 2,4,4-trimethjylpentane)
Several common groups have special names that must be memorized by the student.
A more complex appendage group is named as a derivative of the longest carbon chain in the group starting from the
carbon that is attached to the principal chain. The description of the appendage is distinguished from that of the principal
chain by enclosing it in parentheses.
Hydrocarbon 3.3
CH3
|
H–C–CH3
|
H–C–CH 3
| ≡
CH 3 CH 2 CH 2 CH 2 CHCH 2 CH 2 CH 2 CH 3
When two or more appendages of different nature are present, they are cited as prefixes in alphabetical order. Prefixes
specifying the number of identical appendages (di, tri, tetra and so on) and hyphenated prefixes (tert-or t, sec-) are ignored
in alphabetizing except when part of a complex substituent. The prefixes cyclo-, iso-, and neo- count as a part of the group
name for the purposes of alphabetizing.
When chains of equal length compete for selection as the main chain for purposes of numbering, that chain is selected
which has the greatest number of appendage attached to it.
CH 3
CH 3
CH 3
CH 3
H3 C
H3 C
When two or more appendages are in equivalent positions, the lower number is assigned to the one that is cited first in
the name (that is one that comes first in the alphabetic listing).
H3 C CH 3
H3 C CH 3 CH 3
CH 3
H3 C H3 C CH 3
3-ethyl-5-methylheptane 4-ethyl-5-isopropyloctane
CH 3 CH 3
H3 C
H3 C
CH 3
CH 3
CH 3
CH 3 H3 C
6-ethyl-3,3-dimethyloctane 6-ethyl-2-methyloctane
3,3,6 is lower than 3,6,6, at first point of difference 2,6 is lower than 3,7
3.4 Hydrocarbon
The complete IUPAC rules actually allow a choice regarding the order in which appendage groups may be cited. One
may cite the appendages alphabetically, as above, or in order of increasing complexity.
CH3
H3C CH3 H3C

H3C CH3
ethane CH3
CH3
propane
2,2-Dimethyl propane
CH3
CH3 H3C
H3C CH3
H3C CH3
H5 C2 CH3 C2 H5
2,2,4,4-tetramethylhexane 3-ethyl-2-methylpentane
CH3
H3C CH3
CH3 CH3
3,4,7-trimethylnonane
Table 3.1 The Unbranched Alkanes

Number of Name Formula Number of Name Formula
Carbon (n) (CnH2n+2) Carbon (n) (CnH2n+2)
1 Methane CH4 17 Heptadecane C17H36
2 Ethane C2H6 18 Octadecane C18H38
3 Propane C3H6 19 Nonadecane C19H40
4 Butane C4H10 20 Eicosane C20H42
5 Pentane C5H12 21 Henicosane C21H44
6 Hexane C6H14 22 Docosane C22H46
7 Heptane C7H16 23 Tricosane C23H48
8 Octane C8H18 30 Triacontane C30H62
9 Nonane C9H20 31 Hentriacontane C30H62
10 Decane C10H22 40 Tetracontane C40H82
11 Undecane C11H24 50 Pentacontane C50H102
12 Dodecane C12H26 60 Hexacontane C60H122
13 Tridecane C13H28 70 Heptacontane C70H142
14 Tetradecane C14H30 80 Octacontane C80H162
15 Pentadecane C15H32 90 Nnonacontane C90H162
16 Hexadecane C16H32 100 Hectane C100H202
Hydrocarbon 3.5
1. Write the UPAC name for the following
CH3
CH3
H3 C
i) H3 C CH3 ii) H3 C
H3 C
CH3 CH3 CH3
CH3 CH3
H3 C CH3
H3 C
iii) iv)
CH3 CH3
H3 C
CH3 CH3
SOLUTION
1. (i) 3,4,5-trimethyl heptane (ii) 2-ethyl-4-(1-methyl ethyl)octane
(iii) 3,4,5,6-tetramethyl octane (iv) 4,4-dipropyl heptane
Illustrations
1. Write condensed formulae for each of the following groups: (a) isobutyl (i-Bu), (b) 5-butyl (s-Bu), (c) t-bi (r-Bu),
(d) isopentyl (isoamyl), and (e) t-pentyl (t-amyl).
Ans. The prefix iso (or i-) may be used when there is a methyl group on the next-to-the-last C in the chi Prefixes sec- or
s- and ten- or t- indicate secondary and tertiary, respectively,
|
(a) (CH3)2CHCH2 — (b) CH3CH2CH(CH3),
(c) (CH3)3C —, (d) (CH3)2CHCH2CH2—, and
|
(e) CH3CH2C(CH3)2
2. Write the structural formulae for each of the following compounds: (a) 3-Chloro-2-methylhexane, (b) 2,3,4-tri-
methylpentane, (c) l,4-dibromo-2-methylbutane, (d) 2,2-dimethylpentane, and (e) 4-isopropylhep-tane.
Ans.
(a) CH3 — CH — CH — CH2CH2CH3
CH3 Cl
(b) CH3 — CH — CH — CH — CH3
CH3 CH3 CH3

3.6 Hydrocarbon
(c) BrCH2 — CH — CH2 — CH2Br
CH3
CH3
(d) CH3 — CH2 — CH2 — C — CH3
CH3
(e) CH3 — CH2 — CH2 — CH — CH — CH2 — CH2 — CH3
CH3CHCH3
3. For each of the following state why the given names are incorrect, and then give the correct IUPAC
(International Union of Pure and Applied Chemistry) names and write the corresponding condensed structural
formulae, (a) 2-Dimethylbutane, (b) 3-chloro-4-methylpentane, (c) 2-ethylhexane, (d) 3-isopropylpentane, and
(e) 1,1-dimethylbutane.
Ans. (a) Assuming that the "di" portion of the name is correct, each methyl group must have a numbered position
even if they are both on the same carbon: 2,2-dimethylbutane, (CH3)3CCH2CH3. (b) In the incorrect name the
chain of C’s is numbered from the end that gives higher rather than lower numbers: 3-chloro-2-methylpentane,
CH3CH(CH3)CHC1CH2CH3. (c) The ethyl group shoumd be part of the longest chain: 3-methylheptane,
CH3CH2CH(CH3)CH2CH2CH2CH3. (d) When there are two longest chains of the same lgngth, select the one with
the greater number of substituents: 3-ethyl-2-methylpentane, CH3CH(CH3)CH(C2H5)CH2CH3. (e) One of the
methyl groups on C1 is part of the longest chain: 2-methyl-pentane, CH3CH(CH3)CH2CH2CH3.
4. Provide the IUPAC names for each of the following: (a) (CH3)3CCH2C(CH3)3, (A) C(CH3)4, (c) CH3C(Cl)2CH
(CH3)2, and (d) (CH3CH2)2CHCH(CH3)CH2CH3.
Ans. (a) 2,2,4,4-Tetramethylpentane, (b) 2,2-dimethylpropane, (c) 2,2-dichloro-3-methylbutane, and
(d) 3-ethyl-4-methylhexane.
5. Write structural formulae for the five isomeric hexanes and name them by the IUPAC system.
Ans. Start with the longest chain, hexane, CH3CH2CH2CH2CH2CH3. Going to a five-carbon chain, a CH3 may be
placed either on C2 to produce 2-methylpentane, or on C3 to give 3-methylpentane. Starting with a four-carbon
chain, either a CH3CH2 or two CH3's must be added as side chains for a total of six C's. The CH3CH2 cannot
be placed anywhere on the chain because it would lengthen it. A CH3 would also extend the chain if it were
placed on either terminal C. Placing one CH3 on each of the central C's gives 2,3-dimethylbutane, and if both
are placed on the same central C, the isomer is 2,2-dimethylbutane. Note that each isomer has a distinctive
name. If two structural formulae have the same correct names, they are identical even if they are drawn
differently.
CH3
CH3CHCH2CH2CH3 CH3CH2CHCH2CH3 CH3 — CH — CH — CH3 CH3 — C — CH2CH3
CH3 CH3 CH3 CH3 CH3

2-Methylpentane 3-Methylpentane 2, 3-Dimethylbutane 2, 2-Dimethylbutane
6. Write the structures and identify all the 1°, 2°, 3°, and 4° C’s in (a) 2,2-dimethylpentane, and (b) 1-bromo-2,4-di-
methylpentane.
Hydrocarbon 3.7
Ans.
1° 1° 1°
CH3 CH3 CH3
1° 4° 2° 2° 1° 1° 1°
(a) CH3 — C — CH2CH2CH3 (b) CH2Br — CH — CH2 — CHCH3
3° 2° 3°
CH3
1°
7. Write all isomers for the simplest alkane having only one 4°, one 3°, and one 2°C.
Ans. The three kinds of carbons can be represented respectively as: & & and + & +. These units can be
jointed in three orders, (i) 4° - 2° - 3°, (ii) 4° - 3° - 2°, and (iii) 2° - 4° - 3°. (The reverse order gives the same
isomer.)
0H + 0H 0H 0H + + 0H 0H
(i) 0H & & & 0H (ii) 0H & & & 0H (iii) 0H & & & 0H
0H + + 0H + + + 0H +
Conformations
For Details, See Isomerism
Each carbon atom of alkanes is sp3 hybridized and all C—C and C—H bonds are strong sigma bonds. Since sigma bonded
carbon atoms can rotate about the C—C bonds, a chain of singly bonded carbon atoms can be arranged in any zigzag shape.
&
& & &
& &
& &
Such different arrangements of atoms that can be converted into one another by rotation about single bonds are called
conformations. Since conformations can not be isolated, they are not isomers. Conformations are of three types as:
Eclipsed (with highest energy, hence least stable)
Staggered (with lowest energy, hence most stable) and the intermediate conformations are called Skew conformation.
To represent such conformations we often use two kinds of three dimensional formulae: andiron or sawhorse formulae and
Newman projections. The energy required to rotate the ethane molecule about carbon-carbon bond is called torsional energy.
+ +
+
+ +
+ +
1HZPDQ
+
+ + +
+ + +
+ + + +
+ + 6DZKRUVH + +
+ 5HSUHVHQWDWLRQ +
(FOLSVHG, 6WDJJHUHG,, (FOLSVHG , 6WDJJHUHG ,,
3.8 Hydrocarbon
Illustrations
8. (a) How many conformations of ethane are possible? (b) Name and draw the conformation with the lowest and
the highest energies at room temperature. (c) What is the term used for low energy conformations? (d) How does
the distribution of conformations change with rising temperature?
Ans. (a) There are an infinite number of conformations of ethane. (b) The two extreme conformations in (b) have
the lowest and the highest energies at room temperature and are called staggered and eclipsed respectively.
They are shown in the figure below. For simplicity we are concerned with these two extreme conformations.
(c) Conformer. (d) The population of eclipsed-like conformations increases.
+
+ + ++
+ + +
+
+ RU ++ +
RU +
+ + +
+ + + + +
+ +
L 6WDJJHUHG ORZHVWHQHUJ\ LL (FOLSVHG KLJKHVWHQHUJ\
9. The energy barrier (DH) to rotation about the C — C bond in ethane is about 3 kcal/mol at room temperature.
(a) Draw a diagram showing the variation in energy with the rotation through 180° about the C—C bond of
ethane. (b) Assuming the contribution to AC of the entropy is negligible, calculate the distribution of staggered
and eclipsed conformations at 25 °C.
Ans. (a) See the following figure
(FOLSVHG (FOLSVHG
3RWHQWLDO(QHUJ\
NFDO
6WDJJHUHG 6WDJJHUHG

$QJOHRI5RWDWLRQ
(b) ∆G = ≅ ∆H, and so ∆G = – RT ln Kcp for the equilibrium: eclipsed ⇌ staggered.
[staggered] −300 cal/mol
K eq = and ln K eq = −DG/RT = = 5.059; K eq = 157
[eclipsed] (1.99 ca/mol ⋅ K) (298 K)
A Keq of 157 signifies that at 25°C over 99% (157/158) of the molecules are in a staggered conformation, even
though there is rapid rotation about the C—C bond.
10. (a) Draw sawhorse-wedge projection formulae for the two eclipsed conformations of butane. (b) Which
conformation has greater torsional strain? (c) What are the dihedral angles between adjacent Me’s?
Ans. (a) See figure below. (b) B has greater torsional strain because the two Me’s are exactly eclipsing each other. (c)
The dihedral angle is 0°. In A the Me's are farther apart and the dihedral angle is 120°.
0H
0H
0H
0H
$ %
Hydrocarbon 3.9
11. Draw the C1—C2 staggered and eclipsed conformations of propane.

Ans. See the following figure.
0H
+ + 0H
+
+
+ + + +
+
+
6WDJJHUHG (FOLSVHG
12. (a) Draw a graph relating potential energy to dihedral angle for propane and show the Newman projection for
each maximum and minimum in the graph.
3RWHQWLDO(QHUJ\

'LKHGUDO$QJOH
0H 0H 0H 0H
0H
0H 0H
13. Repeat problem in question 12 for butane, about C2—C3. Label and draw the structure at each maximum and
minimum.
3RWHQWLDO(QHUJ\

'LKHGUDO$QJOH
0H 0H 0H
0H 0H 0H 0H 0H 0H 0H
0H
0H
0H 0H
3.10 Hydrocarbon
14. Which has more torsional strain, butane or 2-methylbutane?

Ans. 2-Methylbutane. It has two staggered conformer's with two Me's adjacent to each other and one Me at a distance.
The third staggered conformer has all three Me's adjacent to each other, and has the highest energy. Butane has
only two Me groups to consider. There are two conformers with adjacent Me's, and one lowest energy conformer,
the anti form.
15. Draw the staggered conformations of 2,3-dimethylbutane in order of increasing energy.

0H 0H 0H
0H + 0H 0H + 0H
{
+ 0H + 0H + 0H
0H + 0H
16. Draw the eclipsed conformations of 2,3-dimethylbutane in order of increasing energy.

0H + +
+ + +
{ 0H
0H 0H
0H + 0H
+ 0H 0H 0H 0H 0H
Physical Properties
Physical Nature
State:
a)
(i) All are colourless and possess no characteristic odour.
(ii) Lower alkanes (C1 to C4) are gases, middle one (C5 to C17) are liquids and highers are solids.
(iii) The boiling point of alkanes increases with an increase in molecular weight due to increase in van der Waals
forces with increase in molecular weight, i.e.,
Boiling point: pentane < hexane < heptane
(iv) Also, the branching in alkanes gives a decrease in surface area (as the shape approaches to spherical), which
results in a decrease in van der Waals forces. The boiling point of isomeric alkanes shows the order: pentane
> isopentane > neopentane.
(v) The melting points of alkanes do not show a regular trend. Alkanes with even number of carbon atoms have
higher melting point than their adjacent alkanes to odd number of carbon atoms.
Melting order: propane < ethane < methane
( −172.0° C) ( −182.5° C)
( −187.7° C)
The abnormal trend in melting point is probably due to the fact that alkanes with odd carbon atoms have their
end carbon atom on the same side of the molecule and with even carbon atom alkane, the end carbon atom on
opposite side. Thus, alkanes with even carbon atoms are packed closely in crystal lattice to permit greater inter-
molecular attractions. Generally, however, branching that produces highly symmetrical structure results in
abnormally high melting points, e.g., 2,2,3,3-tetramethylbutane melts at 100.7°C, which is very high for such
a low molecular weight alkane. Cycloalkanes also have much higher melting points than their open chain
counterparts.
Hydrocarbon 3.11
Table 3.2 Melting Point and Boiling Point of Alkanes
Name Formula M.p., °C B.p., °C

Methane CH4 –183 –162
Ethane CH3CH3 –172 –88.5
Propane CH3CH2CH3 –187 –42
n-Butane CH3(CH2)2CH3 –138 0
n-Pentane CH3(CH2)3CH3 –130 36
n-Hexane CH3(CH2)4CH3 –95 69
n-Heptane CH3(CH2)5CH3 –90.5 98
n-Octane CH3(CH2)6CH3 –57 126
n-Nonane CH3(CH2)7CH3 –54 151
n-Decane CH3(CH2)8CH3 –30 174
n-Undecane CH3(CH2)9CH3 –26 196
n-Dodecane CH3(CH2)10CH3 –10 216
Isobutane (CH3)2CHCH3 –159 –12
Isopentane (CH3)2CHCH2CH3 –160 28
Neopentane (CH3)4C –17 9.5
Isohexane (CH3)2CH(CH2)2CH3 –154 60
3-Methylpentane CH3CH2CH(CH3) –118 63
2.2-Dimethylbutane CH2CH3 –98 50
2,3-Dimethylbutane (CH3)3CCH2CH3 –129 58
(CH3)2CHCH(CH3)2
b) Density: The density of alkanes increases with an increase in molecular weight and becomes constant at 0.76g/ml.
Thus, all alkanes are lighter than water.
c) Solubility:
(i) Alkanes being non polar are insoluble in water but soluble in non polar solvents, e.g., C6H6, CCl4, ether etc.
(ii) The solubility of alkanes decreases with increase in molecular weight.
(iii) Liquid alkanes are themselves good, non polar solvents.
Illustrations
17. Place each of the following alkanes in order of corresponding increasing boiling point (bp °C), and give your
reason for the order: pentane, hexane, and 2,3-dimethylbutane.
Ans. C5H12 with a lower molecular weight, has a lower bp than both C6H14 isomers. The branched 2,3-dimethylbutane
has a lower bp than the straight chain isomer because it is a more compact molecule with less surface area,
and thus has weaker intermolecular van der Waals attractive forces. The actual bp's are: pentane, 36 °C;
2,3-dimethylbutane, 58 °C; hexane, 69 °C.
18. (a) Predict which compound in each of the following pairs has the higher bp and give your reason: (i) pentane
and 1-chloropentane and (ii) 2-methylhexane and 2,2-dimethylpentane. (b) Both CF4 and hexane are nonpolar
and have approximately the same molecular weight, yet CF4 has a much lower bp (- 129 °C) than hexane (68 °C).
Explain.
3.12 Hydrocarbon
Ans. (a) (i) 1-Chloropentane. It is a more polar compound (the C — Cl bond has an appreciable dipole moment) and
has a higher molecular weight, (ii) 2-Methylhexane. It has a longer less-branched chain. Less-branching leads to
greater touchable surface area and, thus, greater van der Waals attractive forces. (b) CF4 is spherical and has less
approachable surface area for intermolecular attractive forces than the unbranched hexane. Think of two balls
that can touch only at a point and two strands of uncooked spaghetti in contact along their entire length.
19. Why does an oil forms slick on the surface of the ocean after a spill?
Ans. Alkanes, the chief constituents of petroleum, are insoluble and have a lower density than water.
20. Place the three isomeric pentanes in order of increasing stability at room temperature.
Ans. The stability of structural isomers generally increases with increased branching. Thus, pentane, CH3(CH2)3CH3 <
isopentane, (CH3)2CHCH2CH3, < neopentane, (CH3)4C.
Preparation
1. Reduction method
(a) Reduction of alkyl halides: (Substitution of halogen by H) Alkyl halide can be reduced into corresponding alkanes by
following reducing agents.
L /L$O+
5±; 5±+
LL 1D%+
LLL %X 6Q+
LY 3G±&+
Y 1D & + 2+
YL =Q ±&X íFRXSOH& + 2+
YLL =Q1D2+
YLLL =Q &+ &22+
L[ +J í 0J +2+
NOTE:
(i) LiAlH 4 with 3° R–X give elimination product as major product.
(ii) NaBH 4 reduces 3° and 2° R–X only.
LiAlH4 reduces primary and secondary alkyl halide to corresponding alkanes whereas tertiary alkyl halide is converted
into alkene due to strong base HQ. Secondary and tertiary alkyl halides can also be conveniently reduced to corresponding
alkane using NaBH4 but primary alkyl halides are passive with this reagent. If triphenyl tinhydride (Ph3SnH) is used as
reducing agent, all types of alkyl halides are reduced to corresponding alkanes. (It has no effect on joiner functional group
except NO2)
(b) Reduction with Zn/H+:
RX 
Zn
H+
→ R − H + ZnX
Here, the solvent used should be either a dilute solution of acid or any protic solvent, e.g., ethanol. Some reducing
agents are Zn + CH3COOH; Zn + HCl ; Zn + NaOH, Zn – Cu + NaOH; Al – Hg + EtOH; LAH + ether; ether; SBH –
ethanol.
Mechanism:
+c
=Q5±; >5=Q;@ 5+=Q;±
Hydrocarbon 3.13
(c) Reduction of Unsaturated Hydrocarbon:

The mechanism of Hydrogenation of alkenes and alkynes in presence of catalyst Ni, Pt, pd. here involves adsorption
of alkene or alkyne over the surface of metal containing absorbed hydrogen. Metal surface then transfer hydrogen to
alkene and alkyne forming alkane. When Ni is used, it is called Sabatier Sendren’s reaction. An alkene with bulky group
substituent suffers steric hindrance when it tends to adsorb on the metal surface. Therefore, more the substitution of bulky
group at double bond, more difficult will be its hydrogenation and less will be the heat of hydrogenation (hydrogenation is
exothermic; DH = –ve). Alkynes are more reactive than alkenes in hydrogenation reactions. Due to their linear arrangement,
they can easily be attacked by H2 absorbed on transition metal. These are syn-addition reactions.
1
Stability of alkene ∝
Heat of hydrogenation
5HDFWLRQ0HFKDQLVP
& & &±& &±&

+±+ + + + +
3( $ONHQH ¨+
70
$ONDQH
70 70 3URJUHVVRI5HDFWLRQ
When catalyst is Ni, the reaction is known Sabatier - Sanderen’s reaction
1. Rate of hydrogenation across double bond

+
5
&+ &+!5±&+ &+!5±& &±5!5±& &±5! & &+
5
+ + +
As the number of hyper conjugation in alkene increases, their rate of hydrogenation decreases.
(i) Adam’s Catalys (PtO-pt); Willkinson catalyst (Ph3P)3RhCI can reduce only double bond (not the functional group).
C H − CH = CH − COOH  willkinson
→ C6 H 5 − CH 2 − CH 2 COOH
6 5 catalyst
(ii) LAH can not reduce isolated double bond but if c = c is conjugated with benzene ring, carbonyl carbonyl group as well
as double bond both undergoes reduction.
C6 H 5 − CH = CH − CHO 
LAH
→ C6 H 5 − CH 2 CH 2 − CH 2 OH
(iii) Hydroboration Reduction:
%+
5±&+ &+ 5±&+±&+
&+&22+
' '
%' %'
5±&Ł&+ 5±& &+ 5±&Ł&+ 5±& &+
&+&22+ &+&22'
' +
(d) Reduction of alcohols: Alcohols can be reduced to corresponding alkane as
P / I2 / D
(a) R — OH  →R — H
(b) R — OH 
TsCl
→ R — O — Ts 
LiAlH 4
→R — H
3.14 Hydrocarbon
(e) Reduction of carbonyl compounds:

2
&OHPPHQVRQ5HGXFWLRQ
5±&±5 >=Q +J +&O@
5±&+±5
Mechanism:
+
5
+ H± +Պ
5& 2 5& 2+ IURP=Q
5&±2+ &±±2+
Պ Ւ 5 Պ
H± Ւ
5&++2 5&+ 5&+
Պ
Wolf-Kishner Reduction.
2
L 1+±1+
5±&±5 5&+±5
LL DOF.2+
Mechanism:
%DVH Ւ Ւ %±+
5& 2+ 11+ĺ5& 1±1+ 5±& 1±1+%DVH±+ĺ5&+1 5&+%DVH

2. (i) $ 1D
'(
,GHQWLI\$ (ii) How many hydrocarbon can be obtained by reacting the
+& %U
+&
DQG %U
+& +&

with Na in presence of D.E.
SOLUTION
;
2. (i) ; (ii) Three
2. From organo metallic compounds

Alkyl halides react with either Mg or Li in dry ether to give organometallics having a basic carbanionic site.
RX + 2Li 
dry ether
→ R − Li + + LiX then R − Li + + H 2 O 
→ RH + LiOH
;
RX + Mg 
dry ether
→ R − (Mg + X) then 50J;+ 2 5+0J
(Grignard Reagent )
2+
Hydrocarbon 3.15
The net effect is replacement of X by H.

R — Mg — X + H — OH 
→R—H
R — Li + H — OH 
→R—H
3. Wurtz Reaction
This involves coupling of two molecules of alkyl halide in presence of sodium metal leading to formation of an
alkane as:
5±±;1D;±±5 5±5
This method is suitable only for the preparation of symmetrical alkane, i.e., when only one type of alkyl halide is used.
If two different type of alkyl halides are used as R – X and R’ – X, besides the cross products R – R’, other products R – R
and R′ – R′ are also formed by self-coupling of two R – X or two R' –X .
Since alkanes have very close physical and chemical properties, they are difficult to separate. For the preparation of
unsymmetrical hydrocarbons, particularly alkyl hydrocarbon a modified procedure called Wurtz fittig reaction is employed.
&+
GU\
Wurtz fitting Reaction: &+%U1D%U±&+ HWKHU
NOTE:
This reaction takes place via formation of free radicals. Disproportionation takes place which leads to the formation of
alkene and alkane as by product.
CH 3 − CH 2 − Br + CH 3 − Br + Na
↓
CH 3 − CH 2 − CH 3 + CH 3 − CH 2 − CH 2 − CH 3 + CH 4 + CH 2 + CH 3 CH 3
This reaction is not shown by tertiary halide as they will prefer elimination to give alkene as a major product.
CH4 cannot be prepared by this method.
3° R—X do not give this reaction. Mechanisms have been proposed for this reaction.
Mechanism

R — X + Na → R + NaX
R + R 
→R—R
4. Corey-House synthesis
R — X + 2Li 
dry ether
→ R — Li + LiX
2R — Li + CuI 
→ R 2 CuLi + LiI
R 2 CuLi + R ′ — X 
→ R ′ — R + R — Cu + LiX
For good yields, R′X should be a primary halide; the alkyl group R in the organometallic may be primary for better yield.
For example,
&+
/L &X,
&+±%U &+±/L +& &X/L
0HWK\OEURPLGH 0HWK\OLWKLXP /LWKLXPGLPHWK\OFRSSHU
&+±&+ &+ &+
Q1RQDQH
&+ &+ &+,
Q2FW\OLRGLQH
3.16 Hydrocarbon
&+ %U
/L &X,
+& &+&+&+ &X/L

+& Q3HQW\OEURPLGH
&O &+
VHF%XW\OFKORULGH
&+
&+
&+ PHWK\ORFWDQH
5. Frankland’s reaction
R — X + R — X 
Zn / C2 H5 OH
D
→ R — R + ZnX 2
CH 3 — Br + CH 3 — Br 
→ CH 3 — CH 3 + ZnBr2
6. Kolbe Electrolysis
Mechanism
At Anode
2 2
±H±
5 & 2 $QRGH 2[LGDWLRQ
5 & 2 5&2
GLPHUL]H 5±5
5
±+ DONHQH
1
At Cathode : H+ + e– → H → H2
2
eg: Kolbe’s electrolysis of sodium propionate will give following products:
&+±&+±&+±&+
&+ &++
&+&+&22± &2&+±&+
&+&+&22&+&+
+
&+&+
H &+&+&22
±
2 2
&+±&+±&±2±2±&±&+±&+
$SHUR[LGH
CH4 can not be prepared.
Decarboxylation Reaction: A carboxylic acid on heating with soda lime (NaOH/CaO) loses CO2 forming alkane with one
carbon less than the parent acid as:
R – COOH + NaOH/CaO/D —→ R – H + CO2
Hydrocarbon 3.17
Mechanism
RCOOH + NaOH → RCOO– Na+ + H2O
2
5±&±2± &25±
Reactivity of acid towards decarboxylation depends on the stability of carbanion intermediate formed in the above
mechanism. Therefore an electron withdrawing group will favour decarboxylation. CaO absorbs CO2 and water facilitating
the formation of carbanion. Sodium formate, will give hydrogen gas.
HCOONa + H2O electrolys
 → H2 + CO2 + NaOH
D
RCOCH2COOH → RCOCH3 + Na2CO3
b-ketoacid decarboxylate even on heating without using soda lime.
Illustrations
21. Indicate the different ways that an alkyl halide can be converted to an alkane with the same skeleton.
Ans. Reduction using (a) Zn, H+, (b) LiAlH4, (c) Mg/anh. ether followed by H2O.
22. Give a method of preparation of propane from (a) an alkene and (b) an alkyl chloride.
Ans. (a) CH3CH=CH2 + H2 with a Pt, Pd, or Ni catalyst, (b) CH3CH2CH2Cl or (CH3)2CHCl with Zn and H+, or LiAlH4.
23. Write the structure of all the alkenes that can be hydrogenated to form 2-methylpentane.
Ans. The alkenes must have the same skeletal arrangement, (CH3)2CHCH2CH2CH3. There are four different positions
for the double bond; hence the four different alkenes are
&+ &+ &+ &+
&+&+&+&+ &+ &+&+&+ &+&+ &+& &+&+&+ +& &&+&+&+
24. Write the reaction of CH3CH2MgBr with methanol, CH3OH and identify the conjugate acid-base pair.
±
Ans. &+&+ ± 0J%U &+2+ &+&+ 0J%U &+2

EDVH DFLG DFLG EDVH
25. Prepare 2-deuteropropane from isopropyl bromide.

D2 O
(CH 3 ) 2 CHBr + Mg/ether → (CH 3 ) 2 CHMgBr  →(CH 3 ) 2 CHD
26. Prepare butane from chloroethane using the Wurtz synthesis.

2 CH 3 CH 2 C1 + 2 Na → CH 3 CH 2 CH 2 CH 3 + 2NaC1
27. Why is the Wurtz synthesis not a good method for preparing propane?
Ans. Two different alkyl halides must be used: ethyl and methyl chloride. When reacted in the presence of Na, three
reactions occur, giving a mixture of three products: methyl couples with methyl to give ethane; methyl with ethyl
to give propane; and ethyl with ethyl to give butane.
28. Discuss the limitations of the Wurtz reaction in terms of the structural requirements.
Ans. The alkane to be synthesized must have an even number og carbons and the left and right-handed parts must be
identical (symmetrical about a C—C bond). Only then can a single alkyl halkde be used to couple with itself.
3.18 Hydrocarbon
29. Which of the following alkanes cannot be synthesized by the Wurtz reaction in good yield? Explain.
(CH3)2CHCH2CH(CH3)2 (A), (CH3)2CHCH2CH2CH(CH3)2 (B),
CH3CH2C(CH3)2CH2CH3 (C), (CH3)3CCH2CH2CH3 (D)
Ans. Compounds A and C are symmetrical but they have an odd number of carbons and cannot be synthesized by
coupling one molecule with itself. Compound D is not symmetrical and has an odd number of carbons.
30. Prepare butane from chloroethane using the Corey-House synthesis.
Ans. CH 3 CH 2 C1 
1.Li
2.Cul
→ (CH 3 CH 2 ) 2 LiCu 
CH3 CH 2 C1
→ CH 3 CH 2 CH 2 CH 3
Chloroethane Lithium diethylcuprate
31. Starting with 1- and 2-bromopropane prepare 2-methylpentane.

Ans. (CH 3 ) 2 CHBr 
1. Li
2. Cul
→ [(CH 3 ) 2 CH]2 LiCu 
CH3 CH 2 CH 2 Br
→(CH 3 ) 2 CHCH 2 CH 2 CH 3
Lithium diisopropylcuprate
CHEMICAL PROPERTIES OF ALKANES

Alkanes are called paraffin’s (little affinity) due to low level of reactivity of alkane. Although alkanes are chemically unre-
active under ordinary conditions due to the presence of strong C – C bond and C – H bonds, they give following reactions,
(a) Oxidation (b) free radical substitution.
Oxidation
Although essentially inert in acid-base reactions, alkanes do participate in oxidation-reduction reactions but are less af-
fected by oxidising agents. Burning in air (combustion) is the best known and most important example. Combustion of
hydrocarbons is exothermic and gives carbon dioxide and water.
→ CO 2 + 2H 2 O
CH + 2O 2 
4
DH° = – 890 kJ (–212.8 kcal)
Methane Oxygen Carbon Water
dioxide
(CH 3 ) 2 CHCH 2 CH 3 + 8O 2 
→ 5CO 2 + 6H 2 O DH° = – 3529 kJ (–843.4 kcal)
2 − Methylbutane Oxygen Carbon Water
dioxide
Like alkanes, the low polarity of all the bonds in cycloalkanes means that the only intermolecular forces between
molecules of cycloalkanes are the very weak induced dipole - induced dipole forces, also known as van der Waals forces
which are easily overcome. As a result, compared to other functional groups, but like alkanes, cycloalkanes tend to have
low melting and boiling points.
Heat of Combustion of Cycloalkanes
3
(CH 2 ) n + nO 2 
→ n CO 2 + n H 2 O + heat
2
Table 3.3 Heat of Combustion of Cycloalkanes

Cycloalkane (CH2)n n Heat of Combustion (kJ mol–1)
Cyclopropane 3 2091
Cyclobutane 4 2744
Cyclopentane 5 3320
Cyclohexane 6 3952
Cycloheptane 7 4637
Cyclooctane 8 5310
Contd.
Hydrocarbon 3.19
Cycloalkane (CH2)n n Heat of Combustion (kJ mol–1)

Cyclononane 9 5981
Cyclodecane 10 6636
Cyclopentadecane 15 9885
Unbranched alkane
Ring strain: The instability of cycloalkanes due to their cyclic structures. The more ring strain a molecule possesses, the
more potential energy it has and the less stable it is. Ring strain is because of angle and torsional strain.
+ +
++
&
+
&
+
+ & & + +
+ +
+
1HZPDQQ¶VSURMHFWLRQRIF\FORSURSDQH
The Origin of Ring Strain in Cyclopropane and Cyclobutane: Angle Strain and torsional Strain
The carbon atoms of alkanes are sp3 hybridized and the bond angle is 109.5°. But the internal angle of cyclopropane is
60° and departs from the ideal value by a very large amount i.e., by 49.5°. The potential energy rise resulted from compres-
sion of the internal angle of a cycloalkane from normal sp3-hybridized carbon angle. The sp orbitals of the carbon atoms
cannot overlap as effectively as they do in alkane (where perfect Head-on overlap is possible). The hydrogen atoms of the
cyclopropane ring are all eclipsed and hence cyclopropane also has torsional strain.
Alkanes can undergo oxidation under special conditions to yield a variety of product, e.g.,
(i) 2CH 4 + O 2 573
 Cu
K /1100 atm
→ 2CH 3 OH
Methanol
(ii) CH 4 + O 2 MO
 2 O3
→ HCHO + H 2 O
Formaldehyde
(iii) 2R − CH 3 + 3O 2 Ag
 2O
→ 2RCOOH + 2H 2 O
Carboxylic acid
(iv) Alkanes having tertiary H can be oxidised to alcohols in presence of potassium permanganate.
(CH 3 )3 CH + O 
→ (CH 3 )3 C − OH
tert − butanol
Reaction with steam: Methane reacts with steam at 1273 K in presence of nickel catalyst forming carbon monoxide and
hydrogen. The method is used for industrial preparation of hydrogen.
CH 4 + H 2 O Ni
→ CO + 3H 2
Free Radical Substitution Reactions

Homolytic Bond Dissociation Energies and the Relative Stabilities of Radicals
Homolytic bond dissociation energies provide a convenient way to estimate the relative stabilities of radicals. The energy
required to break covalent bonds homolytically is called homolytic bond dissociation energy and abbreviated by the
symbol DHo. We find the following values of DHo for the primary and secondary C-H bonds of propane.
CH3CH2CH2-H (CH3)2CH-H
(DH = 98 k cal mol )
o -1
(DHo = 94.5 k cal mol-1)
3.20 Hydrocarbon
For the reaction in which the designated C-H bonds are broken homolytically, the values of DHo are those given below:

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DUDGLFDO

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These reactions differ in the amount of energy required and in the type of carbon radical being produced. More energy
must be supplied to produce a primary alkyl radical from propane than is required to produce a secondary carbon radical
from the same compound. This must mean than the primary radical has absorbed more energy and thus has greater poten-
tial energy. As the relative stability of a chemical species is inversely related to its potential energy, the secondary radical
must be more stable than the primary radical by 3.5 k cal . mol-1.
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The tertiary radical is more stable than the primary radical by 7 k cal mol-1. The kind of pattern that we find in these
examples is found with alkyl radicals generally; overall their relative stabilities are the following: Tertiary > Secondary
> Primary > Methyl
1. Halogenations: One of the important chemical reactions of alkanes is halogenation which is defined as the replace-
ment of hydrogen atom of the molecule by halogen atom. A mixture of alkanes and chlorine remains unaffected in the
dark but a vigorous reaction occurs when it is exposed to light or at a higher temperature.
hv or D
R — H + Cl2  → R — Cl + HCl
(i) This reaction is mainly given by those compounds which have at least one hydrogen present on sp3 hybrid carbon.
(ii) Reaction intermediate of the reaction is free radical which is always formed in propagation step I.The greater is the
stability of the resulting radical , the more is the reactivity.
(iii) Order of reactivity is F2 > Br2 > Cl2 > I2.
Fluorination is highly explosive and iodination is reversible due to formation of HI. This reaction can be made possible by
using oxidising agents like HgO, HIO3 etc.
Chlorinating agents: Chlorinating agents may be Cl2, SO2Cl2. Reagent initiator may be heat, light, TEL, Pb(OCOCH3)4/D
or peroxide. Presence of oxygen retard rate of reaction as O2 form a stable intermediate ROO• with R• radical.
Brominating agents: Brominating agents may be Br2 and NBS. Bromination with Br2 is carried out in the presence of UV
light whereas/bromination with NBS is carried out in the presence of CCl4 or CS2 and UV light.
Br2/hu gives bromination at benzyl, allylic and alkyl carbon whereas NBS gives bromination only at allylic and
benzylic carbons.
Hydrocarbon 3.21
Bromination is similar to chlorination, but not so vigorous. Iodination is reversible, but it may be carried out in the
presence of an oxidising agent such as HIO3, HNO3 etc., which destroys the hydrogen iodide as it is formed and so drives
the reaction to the right. For example,
&+ , &+ ,+,
+,+,2 , + 2
Iodides are more conveniently prepared by treating the chloro or bromo derivative with sodium iodide in methanol or
acetone solution. For example,
RCl + NaI 

acetone
→ RI + NaCl
This reaction is possible because sodium iodide is soluble in methanol or acetone, whereas sodium chloride and sodium
bromide are not. This reaction is known as Conant Finkelstein reaction.
As pointed above, the reactions takes place by free radical chain mechanism which proceeds in the following three
distinct steps.
(a) Chain initiations
hv or D
Cl — Cl → 2Cl [DH = +58 kcal/mole]
(b) Chain propagation
Cl + H — CH 3 
→ H — Cl + CH 3 [DH = –1 kcal/mole]
CH 3 + Cl — Cl 
→ CH 3 — Cl + Cl [DH = –23 kcal/mole]
(c) Chain termination
Cl — Cl  → Cl — Cl
CH 3 + Cl  → CH 3 — Cl
CH 3 + CH 3 → CH 3 — CH 3
The ease of substitution at various carbon atoms is of the order tertiary > secondary > primary, which is the same as
the stability of various alkyl radicals.
Bromination of alkanes has close similarities to chlorination except the rate of reaction is slow.
Fluorination of alkane is so violent that it results in the cleavage of C—C as well as C—H bonds.
∴ Reactivity of X 2 : F2 > Cl2 > Br2 > I 2 [I 2 does not react.]
The potential energy curve for the halogenation (chlorination) of alkane is shown as
3RWHQWLDOHQHUJ\
(DFW
5 &O

5±+&O

5±&O&O
3URJUHVVRIUHDFWLRQ
Reactivity-Selectivity Principle
1. Probability Factor: This factor is based on the number of each kind of H atom in the molecule. For example, in
CH3CH2CH2CH3 there are six equivalent 1o H’s and four equivalent 2o H’s. The ratio of abstracting a 1oH are thus 6 to 4,
or 3 to 2.
3.22 Hydrocarbon
2. Reactivity of H• : Since the rate determining step in halogenations is abstraction of hydrogen by a halogen atom be
the formation of alkyl radical, halogenation of alkanes follows order of stability of free radical is 3° > 2° > 1° > CH 3
The above order of stability of radicals is due to the ease of their formation from the corresponding alkane which in
turn is due to difference in the value of ∆H .
CH 3 — H 
→ CH 3 + H DH = 104 kcal

CH 3 — CH 2 — H 
→ CH 3 — CH 2 + H DH = 98 kcal

&+±&+±&+ &+± &+±&++ '+ NFDO
+
Reactivity of any H-atom µ number of H atoms of that kind × reactivity of that H
&+ &+

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+ '+ NFDO
+
Thus, the amount of energy required to form the various classes of radicals’ decreases in the order CH 3 > 1° > 2° > 3°,
i.e., it is easiest to form 3° radical and it is most difficult to form CH.3 . We can also interpret this in an alternative way
the case of abstraction of H atoms from hydrocarbon follows the sequence 3° > 2° > 1° CH 4 , which should also be
the case of formation of free radicals.
The above order of stability is in accordance with the stability of free radicals on the basis of delocalization of odd
electron. Order of stability of free radical is
Allyl > benzyl > 3° > 2° > 1° > methyl, vinyl.
3. Reactivity of X• : The more reactive Cl• is less selective and more influenced by the probability factor. The less
reactive Br• is more selective and less influenced by the probability factor, as summarized by the Reactivity-
Selectivity Principle. If the attacking species is more reactive, it will be less selective, and the yields will be closer to
those expected from the probability factor.
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Hydrocarbon 3.23
In the chlorination of isobutane abstraction of one of the nine primary hydrogens leads to the formation of isobutyl
chlorides, whereas abstraction of a single tertiary hydrogen leads to the formation of tert-butyl chloride. The probability
favour formation of isobutyl chloride by the ratio of 9:1. But the experimental results show the ratio roughly to be 2:1
or 9:4.5. Evidently, about 4.5 times as many collisions with the tertiary hydrogen are successful as collisions with the
primary hydrogens. The Eact is less for abstraction of a tertiary hydrogen than for abstraction of a primary hydrogen.
The rate of abstraction of hydrogen atoms is always found to follow the sequence 3o > 2o > 1o. At room tempera-
ture, for example, the relative rate per hydrogen atom are 5.0:3.8:1.0. Using these values we can predict quite well the
ratio of isomeric chlorination products from a given alkane. For example,
CH3CH2CH2CH3 
Cl2
→

CH3CH2CH2CH2Cl + CH3CH2CHClCH3
light, 25 C
n − butyl chloride no.of 1o H reactivity of 1o H

= ×
sec− butyl chloride no.of 2o H reactivity of 2o H
6 1.0 6 28%
= × = equivalent to
4 3.8 15.2 72%
Inspite of these differences in reactivity, chlorination rarely yields a great excess of any single isomer.
The same sequence of reactivity, 3o > 2o > 1o, is found in bromination, but with enormously larger reactivity ratios. At
127oC, for example, the relative rates per hydrogen atom are 1600:82:1. Here, differences in reactivity are so marked
as vastly to outweigh probability factors. Hence, bromination gives selective product.
In bromination of isobutane at 127oC,
Isobutyl bromide no.of 1o H reactivity of 1o H
= ×
tert − butyl bromide no.of 3o H reactivity of 3o H
9 1 9
= × =
1 1600 1600
Hence, tert-butyl bromide happens to be the exclusive product (over 99%).
Illustrations
32. Which of the following compounds yields only one product on monobromination?
(a) Neopentane (b) Toluene
(c) Phenol (d) Aniline
&+
Ans. &+ & &+ has twelve equivalent 1°H. Hence H forms only one product on monobromination.
&+
\ (A)
33. Write a balanced equation for the reaction of chlorine with an excess of methane.
Ans. CH 4 + C12 
hv
→ CH 3 C1 + HC1
34. What are all the possible organic products in the reaction of methane with chlorine?
Ans. The main product is CH3Cl, but further reaction occurs, leading to CH2Cl2, CHCl3> and CCl4.
3.24 Hydrocarbon
35. Experimentally, how can polychlorination of methane be minimized?

Ans. The proportion of different chloromethanes produced depends on the relative amounts of the reactants and the
reaction conditions. If a large excess of methane oves chlorine is used, the chance of chlorine reacting with
methane is greater than with any of the formed chloromethanes.
36. Why is monochlorination of ethane a more practical reaction than the monochlorination of propane?
Ans. Only one monochlorinated product is possible from ethane, while propane forms two isomeric propanes, 1- and
2-chloropropane.
37. Calculate the frequency of light required to break the Cl—Cl bond. The bond dissociation energy for chlorine
is 58 kcal/mol. Use the following conversion factor and constants in solving: 1 kcal = 4.18 X 103 J; Planck’s
constant h = 6.63 X 10~34 J • s/particle; speed of light (c) = 3.00 X 1010 cm/s.
Ans. First convert the bond energy to J/particle:
(58 kcal/mol) x (1 mol/6.02 X 1023 particles/mol) x (4.18 X 103 J/kcal) = 4.03 X 10-19 J/particle
Next, substitute this value into Planck’s equation: DE = h x v, where v is frequency:
v = (4.03 X 10-19 J/particle)/6.63 X 10-34 J • s/particle = 6.08 X 1014 s-1
For the wavelength (l): l =c/v = [(3.00x 10-8 m/s)/(6.08 X 1014 s-1)] x 109 nm/m = 493 nm. This wavelength is in
the blue part of the visible spectrum.
38. Calculate DH for the two propagation steps in the reaction of methane with chlorine. The bond energies for:
CH3—H, CH3 — Cl, H—Cl, and Cl —Cl are respectively 105, 85, 103, and 58 kcal/mol.
Ans. Step 1. (Breaking the CH3 —H bond) + (forming the H —Cl bond) = 105 + (- 103) = +2 kcal/mol
Step 2. (Breaking the Cl—Cl bond) + (forming the CH3—Cl bond) = 58 + (- 85) = - 27 kcal/mol
39. Using the bond energies given in Problem 4.74, explain why the following sequence of steps is
unlikely:
Step1. CH4 + Cl- → CH3C1 + H.; Step 2. H. + Cl2 → HCl + Cl-
Ans. DH for step 1 = 105 + (- 85) = +20 kcal/mol. This is a much higher value than the value of DH calculated in step
1 of Problem 4.74; therefore this reaction will not occur, regardless of the value of DH for step 2 (58 + (–103) =
-45 kcal/mol).
40. (a) Write the equations for the two propagation steps in the reaction of methane with bromine, (b) Calculate DH
for each step and the overall DH for the reaction. The bond energies for CH3—H, CH3—Br, H—Br, and Br — Br
are respectively 105, 71, 87.5, and 46 kcal/mol.
Ans. (a) Step 1. CH + Br• → HBr + .CH ;
4 3
Step 2. . CH + Br → CH Br + Br•
3 2 3
(b) 105 + (–87.5) = +17.5 kcal/mol 46+ (–71) = –25 kcal/mol

∆H for the reaction = step 1 + step 2 = + 17.5 – 25 = –7.5 kcal/mol.
41. The bond dissociation energies of the halogens F—F, Cl—Cl, Br—Br, and I — I are respectively 37, 58, 46, and
36 kcal/mol. Explain why we can eliminate the homolysis of the halogen molecule as the rate-determining step
in the halogenation of alkanes from these data.
Ans. If this step were rate-determining, the order of reactivity of alkanes should follow the order of homolysis of the
halogens, e.g., I2, F2 > Br2 > Cl2. This is not the observed order.
42. The reaction CH4 + Cl- → CH3 + HCl has an activation enthalpy (DH) of +4 kcal/mol and a DH° of + 2
kcal/mol. (a) Draw an energy profile diagram for the reaction, (b) What is the value of DH for the reverse
reaction?
Hydrocarbon 3.25
Ans. (a) See the following figure
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(b) DH for the reverse reaction equals DH minus DH for the forward reaction, or + 4-2= +2 kcal/mol.
43. (a) What is the activation energy for the reaction Cl. + Cl. → Cl2? (b) Draw an energy profile diagram for this
reaction.
Ans. (a) In this case, no bonds are broken, only bonds are formed. This reaction has zero activation energy. Chain
termination reactions, such as 2 . CH3 → CH3CH3, also have zero activation energies, (b) See the following figure.
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44. (a) What is the order of stability of alkyl radicals? (b) Place the following radicals in decreasing order of stability:
CH3CHCH(CH3)2, . CH2CH2CH(CH3)2, CH3CH2C(CH3)2.
Ans. (a) tertiary > secondary > primary > methyl.
(b) CH3CH2C(CH3)2 > CH3CHCH(CH3)2 > CH2CH2CH(CH3)2
45. How many monochlorinated products are obtained by the chlorination of isopentane and what is the percentage
of each assuming the reactivity ratio of 3°H : 2°H : 1°H = 5 : 3.8 : 1.
Solution: Isopentane on chlorination in presence of sun light gives five different monochlorinated products.
KY
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3.26 Hydrocarbon
Table 3.4
Product Reactivity Factor × Probability factor = Number of parts Percentage
(a) 1 × 6 = 6 20.6%
(b) 5 × 1 = 5 17.1%
(c) 3.8 × 2 = 7.6 26.0%
(d) 3.8 × 2 = 7.6 26.0%
(e) 1 × 3 = 3 10.3%
Total number of parts = 29.2
Selectivity of Bromine
Bromine is less reactive toward alkanes than chlorine hence bromine is more selective in the; site of attack when it does
react.
In bromination, the hydrogen atom abstraction step has very high energy of activation. Therefore a very small fraction
of all of collision between bromine atom and hydrocarbon molecules are energetically effective in bringing about bromina-
tion even at 300°C
&+ &+
e.g., %U
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Whereas chlorination give tertiary chloride (37%) and primary chloride (63%)
Illustrations
46. The relative reactivity of 1°: 2°: 3° hydrogens to chlorination is 1:3.8:5. (a) Calculate the relative amounts of
all the monochlorobutanes obtained from the reaction of butane with Cl2. (b) Calculate the percentages of the
different products
Ans. (a) There are six equivalent H atoms which lead to formation of 1-chlorobutane (A) and four equivalent H
atoms which lead to formation of 2-chlorobutane (B). The ratio of 1° to 2° H’s is 3 to 2. The relative amounts of
products are obtained from the product of the relative reactivity and the number of equivalent H’s.
A = 3 x 1 = 3 and B = 2 X 3.8 = 7.6, or 3 to 7.6.
(b) The percentages are obtained by dividing the relative amount of each product by the sum of the relative
amounts (3 + 7.6 = 10.6) and multiplying by 100.
Percentage of A = (3/10.6)100 = 28 and percentage of B - (7.6/10.6)100 = 72
47. Calculate the relative amounts of 1- and 2-bromopropane obtained from the bromination of propane. The relative
reactivity of 1°: 2°: 3° H’s to bromination is 1:82:1600.
Ans. The ratio of 1° to 2° H’s is 6:2, or 3:1. 1-bromopropane: 3 H’s x 1 = 3; 2-bromopropane: 1 H x 82 = 82. The
percentages are: 3/85 = 3.5% of 1-bromopropane and 82/85 = 96.5% of 2-bromopropane. Bromination gives
mostly 2-bromopropane.
48. Calculate the relative amounts of 1-bromo- and 2-bromo-2-methylpropane obtained from the bromination of
isobutane. Refer to problem 4.87 for the relative reactivities.
Ans. (CH 3 ) 2 CHCH3  → (CH 3 ) 2 CHCH 2 Br + (CH 3 ) 2 CBrCH 3
1−Bromo-2- 2 − Bromo − 2 −
methylpropane (E) methylpropane ( F )
For E: 9 H's × 1 = 9, and 9/1609 = 0.6%

For F: 1H × 1600 = 1600, and 9/1600/1609 = 99.4%
Bromination occurs almost exclusively at the 3° position.
Hydrocarbon 3.27
49. What is the reason for the higher selectivity in bromination compared to chlorination?
Ans. The Hammond postulate states that, for comparable reactions, the more endothermic (or less exothermic) reaction
has a transition state (TS) which more closely resembles the intermediate. The less endothermic (or more
exothermic) reaction has a TS which less closely resembles the intermediate and may more closely resemble the
ground state (reactants). Since attack by Br- on an alkane is more endothermic than attack by Cl-, its TS shows
more C—H bond breaking and more H—Br bond formation. Any stabilization in the intermediate radical also
occurs in the corresponding TS. Therefore, a TS leading to a 3° R- has a lower enthalpy than one leading to a 2°
R-, which in turn has a lower enthalpy than one leading to a 1° R-; the relative rates of H-abstraction by Br-are
3° > 2° > 1°. The TS for H-abstraction by Cl- has less C—H bond breaking and less H—Cl bond formation; the
nature of the incipient radical has less effect on the enthalpy of the TS and on the rate of its formation. Hence
there is less difference in the rate of formation of the three kinds of R×'s. Bromination is thus more selective than
chlorination.
50. Laboratory chlorination of alkanes is often done with sulfuryl chloride, SO2C12, instead of Cl2 because of its
convenience. What is the Lewis structure of SO2Cl2?

2
Ans. The structure is &O±6±&O
2

51. When sulfuryl chloride is used to chlorinate an alkane, an organic peroxide, ROOR is used as an initiator. SO2 is
also a product. Write a mechanism for the chlorination, including the role of the peroxide.
Ans. Step 1. ROOR → 2RO •
Step 2. RO • + R'H → ROH + •R'
Step 3. • R' + SO2Cl2 → R'Cl + • SO2Cl
Step 4. • SO2Cl → SO2 + Cl•
Step 5. Cl • + R'H → HCl + •R'
Steps 1 and 2 are initiation steps; steps 3, 4, and 5 are propagation steps.
52. (a) Write the propagation steps for the monofluorination of methane and calculate DH for each step.
(b) Would you expect fluorination of an alkane to show selectivity between the 1°, 2°, and 3° substitution? Bond
energies for HF, CH3— F, F2, and CH3— H are respectively 136, 108, 38, and 105 kcal/mol.
Ans. (a) Step 1. F• + CH4 → HF + •CH3 Step 2. •CH3 + F2 → CH3F + F•
+ 105 – 136 = –31 kcal/mol + 38 – 108 = –70 kcal/mol
(b) The extreme exothermicity of the hydrogen abstraction step 1 means that the transition state has very little
bond breaking, and thus there should be very little selectivity
Brain Teaser
53. An alkane, C6H14 gives two monochloroalkanes when chlorinated. What is the structure of the original alkane?
Ans. There are five isomeric hexanes. Only one, 2,3-dimethylbutane can give two different monochlorinated
compounds: 1-chloro-2,3-dimethylbutane, and 2-chloro-2,3-dimethylbutane.
When 2-methylbutane is chlorinated, the percentage of (CH 3 ) 2 – CH – CH 2 – CH 2 Cl is……….
Assuming reactivity ratio of 3°H : 2°H : 1°H for chlorination = 5 : 3. 8 : 1.
54. Explain why the free radical chlorination of methane occurs approximately twelve times faster than tetradeutero-
methane, CD4.
Ans. Although D and H are chemically identical, C—D bonds are slightly stronger than C—H bonds. Therefore
DH for abstraction of D is slightly greater than for H. Since abstraction is the slow step, removal of H will be
faster.
3.28 Hydrocarbon
55. List and compare the differences in the properties of the transition states during chlorination and bromination
that account for the different reactivities of 1°, 2°, and 3° H’s.
Ans. The differences may be summarized as follows:
Chlorination Bromination
1. Time of formation of transition state Earlier in reaction Later in reaction
δ" δ" δ" δ"
2. Amount of breaking of C—H bond* Less, H 3 C− −H − − − − Cl More, H 3 C− − − −H − − Br
3. Free-radical character (δ•) of carbon Less More
4. Transition state more closely resembles Reactants Products
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56. In the halogenation of alkanes other than methane there is another chain terminating reaction that can occur called
disproportionation. Write the mechanism for this reaction for -C2H5.
+ +

Ans. &+& +±&±&+ &+±&++& &+
+ +
Nitration
The displacement of an atom of hydrogen by a nitro group ( –NO 2 ) is called nitration. Alkanes can be nitrated with nitric
acid in the gas phase generally at 400–500°C.
400–500° C
R — H + HO — NO 2  → R — NO 2 + H 2 O
&+ ² &+ ² &+ ² 12 &+ ² &+ ² &+
+12 12
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Sulphonation
Sulphonation of a hydrogen atom of the alkane by sulphuric acid group (–SO3 H) is called sulphonation. The ease of sub-
stitution is tertiary ≥ secondary > primary.
Hydrocarbon 3.29
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Catalytic Cracking
When long chain alkanes are heated well above their boiling points (500 – 800°C) with or without a catalyst, they are broken
(or cracked) to yield smaller alkanes, alkenes and hydrogen. Such thermal decomposition with petroleum hydrocarbon is
often called cracking.
400 − 800° C
Long chain alkanes  → Smaller alkanes + alkanes + H2
Cracking
In the process of cracking, C – H bonds may rupture at various places. Thus, by breaking of single alkanes, the number
of product is quite large. For example,
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When the mixture of alkanes is heated at very high temperature in the presence of catalyst (alumina, silica and alu-
minium silicate, clay) and in the absence of air or oxygen, the process is known as catalytic cracking.
C8 H18 C2 H5
Alkane —→ Lower alkane + Alkane
NOTE:
Thermal decomposition of any organic compound is known as pyrolysis. When pyrolysis occurs in alkanes, it is called
cracking.
3.30 Hydrocarbon
Reforming
Reforming alters the molecular structures of the components of low-octane gasolines to form a higher octane fuel.
(a) Isomerisation: Straight chain alkanes are converted into their branched chain isomers when heated at 300°C in the
presence of anhydrous aluminium chloride.
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NOTE:
(a) For this reaction, alkane should have four or more than four carbons.
(b) B.pt. of product is always less than the B.pt. of reactant.
(c) Reactant and products are always chain isomers.
(b) Aromatisation: The conversion of aliphatic compound into aromatic compounds is known as aromatisation. Alkanes
having six or more carbon this reaction which takes place in the presence of catalyst (CrO3/Al2O3 or CrO3/Pt) at
600°C.
Hexane → Benzene ; Octane → Orthoxylene + ethylbenzene
Heptane → Toluene
NOTE:
(a) This reaction takes place by dehydrogenation, oxidation and cyclisation.
(b) Lower alkane (C ≤ 5) also undergoes dehydrogenation to give alkene.
Illustration
57. (a) Why are alkanes so inert? (b) Why do the C—C rather than the C—H bonds break when alkanes are pyrolyzed
(heated at high temperatures in the absence of O2)? (c) Although combustion of alkanes is a strongly exothermic
process, it does not occur at moderate temperatures. Explain.
Ans. (a) A reactive site in a molecule usually has one or more unshared pairs of electrons, a polar bond, an electron-
deficient atom or an atom with an expandable octet. Alkanes have none of these.
(b) The C — C bond has a lower bond energy (DH = +83 kcal/mol) than does the C—H bond (DH = + 99
kcal/mol).
(c) The reaction is very slow at room temperature because of a very high DH.
Insertion of Carbene
Insertion of carbene takes place between carbon and hydrogen.
H3C – CH2 – H + CH2N2 
hv
→ CH3 – CH2 – CH2 – H + N2
Insertion of carbene across unsymmetric alkanes takes place as follow:
&+±&+±&+±&+
&+1
&+±&+±&+ &+
&+±&+±&+
Hydrocarbon 3.31
LPG and CNG

The term LPG (liquefied petroleum gas) refers to mixtures of hydrocarbons containing three or four carbon atoms,
this includes propane (C3H8), propene (C3H6), n-butane(C4H10) , isobutene and various butenes with small amount of
ethane (C2H6). The major sources of LPG is natural gas. LPG is mainly used for manufacture of chemicals, as a fuel for
households and petrochemical industry. Small amount of ethyl mercaptans (foul smelling) are added in LPG to detect its
leakage.
CNG (Compressed Natural Gas) is highly compressed form of natural gas. Many vehicles are designed to operate on
CNG. Natural gas has octane rating of 130.
Illustration
58. (a) What is meant by ‘octane rating’? (b) Why does a high octane fuel have less tendency to knock in an automobile
engine?
Ans. (a) The term octane rating is based upon the performance of n-heptane, which is arbitrarily assigned an octane
value of 0, and isooctane (2,2,4-trimethylpentane), which is given a value of 100 when used as an automobile
fuel. A mixture of 85% isooctane and 15% heptane has an octane number of 85, as does any blend of gasoline
with the same combustion performance in the engine, (b) Branched chain hydrocarbons burn more smoothly
because, when they break down, they form more stable, less reactive 3° radicals. These radicals react more
slowly and smoothly with oxygen uhan the 1° or 2° radicals which form from the breakdown of a straight chain
hydrocarbon.
UNSATURATED HYDROCARBONS ALKENE
The general molecular formula for alkene is Cn H 2n .

Alkenes and cycloalkanes are isomeric compounds because both have the same general molecular formula.
Unsaturation Number
The empirical formula of an alkene, like that of an alkane, can be determined by combustion analysis. An alkene with one
double bond has two fewer hydrogens than the alkane with the same carbon skeleton. Likewise, a compound containing
a ring also has two fewer hydrogens in its molecular formula than the corresponding noncyclic compound. (Compare
cyclohexane, C6H12, with hexane, C6H14.) As this simple example shows, the molecular formula of an organic compound
contains information about the number of rings and double (or triple) bonds in the compound.
The presence of rings or double bonds within a molecule is indicated by a quantity called the unsaturation number,
or degree of unsaturation, U. The unsaturation number of a molecule is equal to the total number of its rings and
multiple bonds. The unsaturation number of a hydrocarbon is readily calculated from its molecular formula as follows. The
maximum number of hydrogens possible in a hydrocarbon with C carbon atoms is 2C + 2. Because every ring or double
bond reduces the number of hydrogens from this maximum by 2, the unsaturation number is equal to half the difference
between the maximum number of hydrogens and the actual number H:
2C + 2 − H
U= = number of rings + multiple bonds (3.1)
2
For example, cyclohexene, C6H10, has U = [2(6) + 2 – 10]/2 = 2. Cyclohexene has two degrees of unsaturation: one
ring and one double bond.
How does the presence of other elements affect the calculation of the unsaturation number? You can readily convince
yourself from common examples (for instance, ethanol C2H5OH) that Eq. 3.1 remains valid when oxygen is present
in an organic compound. What about halogens? Because a halogen is monovalent, each halogen atom in an organic
compound always reduces the maximum possible number of hydrogens by 1. Thus, if the number of carbons is C, the
3.32 Hydrocarbon
maximum number of halogens plus hydrogens is 2C + 2. If X equals the actual number of halogens present, the formula
for unsaturation number therefore becomes
2C + 2 − (X + H) 2C + 2 − X − H
U= = (3.2)
2 2
Another common element found in organic compounds is nitrogen. When nitrogen is present, the number of hydrogens
in a saturated compound increases by one for each nitrogen. For example, the saturated compound methylamine, H3C—
NH2, has 2C + 3 hydrogens. Therefore, if N is the number of nitrogens, the formula for unsaturation number becomes
2C + 2 + N − (X + H) 2C + 2 + N − X − H
U= = (3.3)
2 2
Illustrations
59. Find the degrees of unsaturation for (i) C6H14, (ii) C4H6, and (iii) C6H6.
Ans. (i) Zero. This molecular formula fits the alkane series, (ii) A molecule with four C’s needs 10 H’s to be an alkane.
The formula with six H’s lacks four H’s or two pairs of H’s and so it has 2° of unsaturation. (iii) A formula with
six C’s and only six H’s lacks eight H’s or four pairs of H’s; it has 4° of unsaturation.
60. What structural features induce degrees of unsaturation?
Ans. Rings and multiple bonds.
61. Draw structural formulae for all possible isomers of C4H6.
Ans. C4H6 has 2° of unsaturation as follows: two double bonds, H2C = CHCH=CH2 or H2C=C=CCH3; one triple bond:
HC ≡ CCH2CH3 or CH3C ≡ CCH3; two rings ; one ring and one double bond;
+& RU &+ RU &+ RU
62. Find the degrees of unsaturation for (a) C3H3Cl3, (b) C3H4O, and (c) C4H5N.
Ans. (a) Count halogens as if they were H’s; i.e., C3H6. The formula lacks two H’s and has 1° of unsaturation.
(b) Disregard O’s. C3H4 lacks four H’s and has 2° of unsaturation. (c) Disregard N but remove an H for each N.
C4H4 has 3° of unsaturation.
63. (a) A hydrocarbon (A) has 2° of unsaturation. Describe a quantitative chemical reaction that can be used to
determine whether A has two rings or one ring and one double bond or two double bonds or one triple bond.
(b) Would this test be applicable if A had a cyclopropane ring?
Ans. (a) Run a quantitative catalytic hydrogenation with one equivalent of A. If H2 does not add (react), A has two
rings. If one eq. of H2 reacts, A has both a ring and a C=C. If two eq. of H2 react, A has two double bonds or one
triple bond, (b) No. Cyclopropanes react with (add) H2.
NOMENCLATURE (See chapter ‘nomenclature’ for detail)

The IUPAC names of alkenes are given by replacing the –ane ending of the corresponding alkane with –ene. The two
simplest alkene are ethene and propene.
+ & &+ &+ ² &+ &+
,83$&(WKHQH ,83$& SURSHQH
&RPPHQ 1DPH HWK\OHQH &RPPHQ 1DPH 3U RS\OHQH

+ & & + ² & + ² & +
í
%XWHQH
QRW±EXWHQH
Hydrocarbon 3.33

& + ² & + ² & + ² & + & + ² & +
+H[HQH
QRW±KH[HQH

& + ² & + ² & + & + & + ² & + ² & + ² & + ² &+ ² &+ ² &+
&+ %U
&+

& +
PHWK\OEXWHQH %URPRSURS\OKH[HQH
Cycloalkenes and their derivatives are named by adapting cycloalkane terminology to the principles of alkene nomencla-
ture.
%U

&+ &O

&O
&\FORSHQWHQH 0HWK\OF\FORKH[HQH &KORURF\FORKHSWHQH %URPR&KORUR
QRWGKORUR F\FORKH[HQH
F\FORKHSWHQH
No locants are needed in the absence of substituents; it is understood that the double bond connects C – 1 and C – 2.
Substituted cycloalkenes are numbered beginning with the double bond, proceeding through it, and continuing in sequence
around the ring. The direction of numbering is chosen so as to give the; lower of two possible locants to the substituent.
Illustrations
64. (a) Write the structural formulae and give the common names for the alkenes (i) C2H4, (ii) C3H6, and (iii) C4H8
(three isomers). (b) Why do more structural isomers of alkenes exist than alkanes with the same number of C’s?
Ans. Replace the suffix -one from the alkane name by the suffix -ylene.
(a) (i) H2C = CH2, ethylene; (ii) CH3CH=CH2, propylene; (iii) H2C=CHCH2CH3, 1-butylene;
CH3CH=CHCH3, 2-butylene; H2C=C(CH3)2, isobutylene.
(b) Alkenes have more structural isomers mainly because of the several possibilities of positioning the double
bond in the carbon chain.
65. Supply IUPAC names for:
(a) CH3CH == CHCH2CH3, E &+&+&+ &+&+DQG F &+&+&+&+&+&+&+
&+ &+ &+
Ans. Select the longest carbon chain or ring containing the largest number of double bonds and change the suffix of
the parent alkane from -one to -ene. The alkenes use the same prefixes as the alkanes. The chain is numbered
from the end closer to the C=C, whose position is indicated by assigning the lower possible number to the first
doubly-bonded C. Substituents are designated as for alkanes. (a) 2-Pentene; (b) 4-methyl-2-pentene; (c) named
as a hexene, the longest chain with C=C, not as a heptane which is the longest C chain but does not include the
C = C; thus 3-n-propyl-1-hexene.
66. Give the common and systematic names for the double-bond containing groups:
(a) H2C=CH —, (b) H2C = CHCH2 —, (c) CH3CH=CH —, (d) H2C = C(CH3) —, and (e) H2C = .
Ans. When named systematically these are alkenyl groups, (a) Vinyl and ethenyl, (b) allyl and 2-propenyl, (c) propenyl
and 1-propenyl, (d) isopropenyl, and (e) methylene.
3.34 Hydrocarbon
67. Name the following as substituted derivatives of ethylene: (a) Cl2C = CHCl, (b) CH3CH = CHCH3, (c) (CH3)2C
= CH2, and (d) (CH2 = CH)2C = CH2.
Ans. (a) Trichloroethylene, (b) sym-dimethylethylene, (c) unsym-dimethylethylene, and (d) unsym-divinylethylene.
[Use sym (symmetrical) when each C of C=C has the same substituent and unsym (unsymmetrical) when both
substituents are on the same C.]
68. Supply IUPAC names for

(a) CH3CH == C(NO2)CH2CH3, (d) +& &+&+&+&O&+ &+&+0H
&+ 0H &+&+
&+
(b) Me2C == C(Me)CH(Me)2 (e)
&+
(c) 0H &+&+ &+&+&+ &+ (f) (H2C == CH)2CHCH2CH == CHCH3.
0H
Ans. (a) 3-Nitro-2-pentene; (b) 2,3,4-trimethyl-2-pentene; (c) 3,6-dimethyl-1,4-heptadiene (note the use of di to
indicate two C=C’s); (d) 4-chloro-3-(1-methylpropyl or ,s-butyl)-7-methyl-1,5-octadiene; (e) 1-methyl-5-ethyl-
1,3-cyclohexadiene; (f) the three C=C’s cannot be incorporated into a single chain; pick the longest chain with
two C=C’s; 3-ethenyl-1,5-heptadiene.
69. Supply the structural formulae for (a) 3-Methylenecyclopentene, (b) 4-allyl-3-propenyl-1,3-cyclohexadiene,
(c) bicyclo [2.2.1] 2,5-heptadiene, and (d) 2-ethenylbicyclo [4.4.0]-1,5,8-decatriene.
Ans. D E
&+ &+&+
&+
&+&+ &+
&+ &+
F G
70. (a) Write the structural formulae from the following incorrect IUPAC names: (i) 2-Methylcyclohexene,
(ii) 3-ethenyl-l-hexene, and (iii) 1,2,2-trichloro-4-pentene. (b) Give the correct names in (a) and describe the
given errors.
Ans. (a)
&+
(i) (ii) +& &+&+&+&+&+ (iii) ClCH2CCl2CH2CH == CH2
&+ &+
Hydrocarbon 3.35
(b) (i) 1-Methylcyclohexene. Number 1 is assigned to the C=C bond bonded to the Me; it can be omitted since it
is understood when no number is given, (ii) 3-Propyl-1,4-pentadiene because the chain must include both double
bonds, (iii) 4,4,5-Trichloro-1-pentene because C=C has priority and is assigned the smaller number even though
the substituents acquire higher numbers.
&+
3. write the name : (i) +&
&+
+&
+& &+
&+
(ii)
+& &+
(iii)
&+
SOLUTION
3. (i) 3,3-dimethyl-1-butene (ii) 3-(1,2-dimethyl propyl)-1,3-hexadiene
(iii) 4-cyclopentyl-2-butene
Structure and Bonding in Alkenes

SP
+ +

SP
+ +
Ethylene is planar, each carbon is sp2 hybridized and the double bond is considered to have a σ component and π
component. The σ component arises from overlap of sp 2 hybrid orbital along a line connecting the two carbon atoms, the
π component via a side-by-side overlap of two p orbital. Regions of high electron density attributed to π electrons, appear
above and below the plane of the molecule and are clearly evident in the electrostatic potential map.
Isomerism in Alkenes
Naming stereo isomeric alkenes by the E–Z: When the groups on either end of a double bond are the same and are structurally
similar to each other, it is simple matter to describe the configuration of double bond as ‘cis’ and ‘trans’.
3.36 Hydrocarbon
The terms ‘cis’ and ‘trans’ are ambiguous, however, when it is not obvious which substituents on the carbon is similar
to a reference substituents on the other. A completely unambiguous system for specifying double bond stereochemistry has
been developed based on an atomic number criterian for ranking substituents on the doubly bonded carbon. When atoms of
higher atomic number are on the same side of the double bond, then that double bond has Z configuration where Z stands
for Zusammen meaning together. When atoms of higher atomic weight are on opposite side of the double bond that double
bond is with E configuration. E stands for entegen means opposite.
+LJKHU &O %U +LJKHU &O ) /RZHU
/RZHU + ) /RZHU + %U +LJKHU

= (
Illustrations
71. Which alkenes do not have geometric isomers?

Ans. Alkenes with two identical groups on the same doubly-bonded C have no geometric isomers.
72. Determine which of the following alkenes have geometric isomers:
+& &+ + %U

(a) & & (b) & &

+& &O +
+
%U+& &+, +& &+ &+ &+
(c) & & (d) & &

,+& &+%U +& &+ &+
73. (a) Compare the relative stabilities of cis and trans isomers. (b) How are these determined by equilibration
experiments? (c) Explain the free energy difference, (d) What happens to the relative stabilities of trans and cis
diasteteomers as the size of the R’s increase?
Ans. (a) In general, trans isomers are more stable than cis. (b) A reaction is chosen that permits interconversion of
the geometric isomers (alkenes and cyclic compounds). When equilibrium is reached the mixture is analyzed.
The more abundant isomer is more stable. It is necessary to show that the same equilibrium mixture is attained
starting with either pure diastereomer. For example, when either cis- or trans-2-butene is placed in a strong acid
solution, each is converted to a mixture of 76% of the trans and 24% of the cis isomer. The ratio of isomers
showing the trans to be more stable than the cis by 0.66 kcal/mol. (c) The greater stability (lower free energy)
of the trans isomer is attributed to steric strain in the cis isomer due to the van der Waals repulsion forces of
large groups on the same side of the double bond, (d) The cis becomes increasingly less stable because of the
increasing repulsive force.
74. (a) Write the formula for the alkene hydrocarbon with the fewest number of C’s that exhibits geometric and
optical isomerism. (b) Provide the Fischer structural formulae and names for each stereoisomer.
Ans. (a) MeCH=CHC*HMeEt. (b) There are four stereoisomers as shown:
0H + + 0H + + + +
& & + 0H 0H + & & & & + 0H + & &
0H
+ + 0H 0H
& & & &
(W (W (W (W
( 6 ( 5 = 6 = 5
0HWK\OKH[HQH
Hydrocarbon 3.37
75. Give the structures and IUPAC names of the structural isomers and stereoisomers of pentene, C5H10.
Ans. Alkene isomers are deduced by writing the carbon skeletons and then introducing the double bond. The possible
skeletons are:
& &
&±±&±±&±±&±±& &±±&±±&±±& &±±&±±&
&
$ % &
From A we get:
+& &+&+ +& +&
+& &+&+&+&+ & & DQG & &
+ + + &+&+
3HQWHQH = 3HQWHQH ( 3HQWHQH
From B we get three structural isomers, none of which has geometric isomers.
H 2 C = C(CH 3 )CH 2 CH 3 (CH 3 ) 2 C = CHCH 3 (CH 3 ) 2 CHCH = CH 2
2 − Methyl −1− butene 2 − Methyl − 2 − butene 3− Methyl −1− butene
The central C atom of C is quaternary and cannot form a double bond to give an alkene.
76. Compare the net dipole moments of (a) 1,1-, and trans and cis-1,2-dichloroethene, and (b) (E)- and (Z)-2,3-
dichloro-2-butene.
Ans. (a) The two Cl’s of the trans isomer have equal and opposite bond moments leaving a net zero molecular dipole
moment. 1,1-Dichloroethene has a smaller angle of separation of the two Cl ‘s than has the cis isomer resulting
in a greater dipole moment.
&O + &O &O &O +
& & ! & & ! & &
&O + + + + &O
'LFKORURHWKHQH FLV'LFKORURHWKHQH WUDQV'LFKORURHWKHQH
&O &O &O 0H
(b) & & ! & &
0H 0H 0H &O
= (
In the (Z) isomer the strongly electronegative Cl’s on the same side of the p bond reinforce their electron-
withdrawal. Likewise, the electron-donating Me's have a reinforcing effect. Electron-donation and
electron-withdrawal on opposite sides of C = C enhance the dipole moment. The effects of Cl's and Me's on
opposite sides in structure (E) cancel each other resulting in a smaller dipole moment.
4. (i) Write down the possible number of geometrical isomer of 2,4-hexadiene
(ii) Arrange the following alkenes in there increasing order of stability.
&+ &+
(a) +& (b) +&
+ & &+ + +
(c) (d)
+ & &+ + +
3.38 Hydrocarbon
SOLUTION
+ + + +
+ & +
4. (i) &+ &+
+ + + & +
, ,,
+ & + + +
+ +
+ + &
+ &+ + &+
,,, ,9
(ii) Stability order
e<a<b<c<d
Physical Properties of Alkenes

(a) All are colouress and have no characteristic odour. Ethene has pleasant smell.
(b) Lower members (C2 to C4) are gases, middle one, (C5 to C17) are liquids, higher are solids.
(c) The boiling points, melting points, and specific gravities show a regular increase with increase in molecular weight,
however less volatile than corresponding alkanes.
(d) A cis isomer has high boiling and melting point than a trans because of more polar nature.
(e) Like alkanes, these too are soluble in non polar solvents.
(f) Alkenes are weak polar. The polaritiy of cis isomers are more than trans which are either non polar or less polar.
(e.g., trans butane-2- is non polar; trans pentene-2-is weakly polar).
Illustration
77. (a) Compare (i) the dipole moments, (ii) the boiling points, and (iii) the solubilities of alkenes and corresponding
alkanes. (b) Compare the dipole moments of H2C=CH2 and H2C=CHCH3.
Ans. (a) (i) Alkenes and alkanes are nonpolar although some alkenes have very small dipole moments [see fig. (b)
below], (ii) Since alkanes and the corresponding alkenes have approximately the same molecular weights and
polarity, their boiling points are almost identical, (iii) They are not soluble in polar solvents such as water but
are soluble in nonpolar solvents such as benzene and carbon tetrachloride, and weakly polar solvents such as
ether, (b) The electron-donating CH3, typical of R groups, induces a very small dipole moment making the C = C
slightly negative:
+ & +
(b) & &
+ +
Hydrocarbon 3.39
Stabilities of Alkenes
The stabilities of alkenes are governed by
(a) Degree of substitution: Double bonds can be classified as monosubstituted, disubstituted, trisubstituted and
tetrasubstituted. According to the number of carbon atoms directly attached to the C=C structural unit.
Alkenes with more highly substituted double bonds are more stable than isomers with less substituted double bond.
(b) Van der Waal’s strain: Alkenes are more stable when large substituents are trans to each other than when they are cis.
When two or more atoms are close enough in space that a repulsion occurs between them is one type of steric effect
and therefore trans isomers are more stable than cis isomer.
(c) Heat of hydrogenation: The additionof hydrogen is called hydrogenation. Hydrogenation reaction are exothermic
(negative DH0).
&+
&+
3W& &+ '+ ±NFDOPRO
&+ + +&
+ &
PHWK\OEXWHQH &+
&+
&+ '+ ±NFDOPRO
3W&
&+ + +&
+&
PHWK\OEXWHQH
&+
&+
3W& &+ '+ ±NFDOPRO
&+ + +&
+ &
PHWK\OEXWHQH
The preceding three catalytic hydrogenation reactions are from the same alkane. So the energy of the product is
the same for the each of three reactions. However, three reactants must have different energies. The reaction associated
with the least negative DH0 has the most stable reactant and the reaction with the most negative one has the least stable
reactant.
&+
&+
&+ &+
+& &+
3RWHQWLDO(QHUJ\
+& &+
+&
'+ ±NFDOPRO '+ ±NFDOPRO '+ ±NFDOPRO
The greater the number of alkyl groups attached to the doubly bonded carbon atoms, the more stable the alkene.
Relative stabilities of Alkenes

The greater is the number of attached alkyl groups (i.e., the more substituted the carbon atoms of the double bond), the
greater is the alkene’s stability. It is due to more hyperconjugation.
3.40 Hydrocarbon
5 5 5 5 5 + + 5 5 5
! ! ! ! !
5 5 5 + 5 + 5 + + +
7HWUDVXEVWLWXWHG 7ULVXEVWLWXWHG 'LVXEVWLWXHG
5 + + +
!
+ + + +
0RQRVXEVWLWXWHG 8QVXEVWLWXWHG
&+&+±&+ &+ &+±&+ &+ &+±& &±&+
+ +
+& +& +&
But in the following example, number of the hyperconjugation are same

+
&+±& &±&+ &+±& &±&+ &+±& &+
+ + + &+
FLV±±EXWHQH WUDQV±±EXWHQH ,VREXWHQH
Isobutene is more stable due to the more hyperconjugated structure

&+
& &+ &+±&+ &+ &+
+ &
+&+ Ւ
+ Ւ
&±&+ &+ &+±&+±&+

+ &
3ULFDUEDQLRQ 6HFFDUEDQLRQ
PRUHVWDEOH OHVVVWDEOH
Illustrations
78. Compare the stabilities of 1-pentene, cis- and trans-2-pentene, and 2-methyl-2-butene.
Ans. Since attached R’s increase stability, the least stable isomer is 1-pentene with one R, and the most stable isomer
is 2-methyl-2-butene with three R’s. Among the isomers with two R’s, trans-2-pentene is more stable than its cis
isomer.
79. (a) With the aid of an enthalpy diagram show how heats of combustion (DHc) can be used to compare stabilities
of geometric isomers of hydrocarbon alkenes. (b) Is the conversion of a cis to a trans-isomer exothermic or
endothermic? Why?
Ans. (a) As shown in the figure below, the enthalpies of the products of alkene combustion, CO2 and H2O, are always
less than those of the reactants, alkene and O2. 1-Butene and cis- and trans-2-butene are arbitrarily chosen. All
combustions are exothermic and have -DHc’s. Only isomeric hydrocarbons can be compared because only then
will the equivalent amounts of reactants and products be the same. The most stable isomer has the smallest
enthalpy, and the least negative DHc. We can safely use DHc instead of DGc because DSC is positive (eight moles
of products from seven moles of reactants) and constant for combustion of each isomer. (b) The isomerization is
exothermic because cis has a larger enthalpy than trans.
Hydrocarbon 3.41
%XWHQH
(QWKDOS\
FLV%XWHQH
WUDQV%XWHQH
&2+2
80. Are the following compounds isolable? Explain.
D + E + F G
+ +
Ans. (a) No. A trans-cyclohexene is too strained. The trans unit C — C=C—C cannot be bridged by the two remaining
C’s. (b) Yes. This trans unit can be bridged by six C’s. Eight-membered and larger rings can have a trans-
substituted C—C in the ring, (c) No. A molecule cannot have a C=C at a bridgehead C if each bridge has at least
one C and the bridges are not large. The C=C would require the bridgehead to flatten out—an impossibility. This
is known as Bredt’s rule, (d) Yes. Although there is a C=C at a bridgehead C, one of the bridges has no C and the
bridgehead C’s can flatten without ring strain.
81. Compare the C—H bond lengths and bond dissociation enthalpies of an alkyne, alkene, and alkane.
Ans. As a rule, ‘the more s character in the HO used by an atom, the closer are the bonding e-’s to the atom, and the
shorter and stronger is any of its s bonds." The decreasing order of C—H bond lengths is
− C −3 H > = C −2 H > ≡ C − H
sp sp sp
The decreasing order of bond enthalpies is

≡ C − H > = C −2 H > − C −3 H
sp sp sp
Preparation of Alkenes
1. Dehydration of Alcohols: In the dehydration of alcohol, the H and OH are lost from adjacent carbons; an acid catalyst
is necessary. The process may involve rearrangement of carbocation intermediate. The process is endothermic as a
bonds are broken π bonds are formed.
+ +
+ & & 2+ & & +2 '
$OFRKRO $ONHQH 2+ PDMRUSURGXFW

+62 +Պ
&+&+2+ +&&++2
&
(WK\ODOFRKRO (WK\OHQH
2+
+62
+2
&
Պ
2+
&+
+&
+62 + +
+& & &+ &++2
'
+&
2+
3.42 Hydrocarbon
H2SO4 and H3PO4 are the acids most frequently used in alcohol dehydration. KHSO4 is also often used. H3 PO4 is the
best acid for this purpose.
Regioselectivity of Alcohol Dehydration
2+ &+ +&
+62
+ & &+ +&
&
&+ &+ +& &+
0HWK\OEXWHQH 0HWK\OEXWHQH

Dehydration of this alcohol is selective in respect to its direction
&+ &+ &+
+32
'
2+

Regioselectivity of β elimination is governed by Zaitsev’s Rule.

Stereoselectivity in Alcohol Dehydration
In addition to being regioselective, alcohol dehydration are stereoselective. A stereoselective reaction is one which a single
starting material can yield two or more sterioisomeric products, but give one of them in greater amount than other.
+ & &+ +& &+ +& +

+62

'
2+ + + + &+
FLVSHQWHQH WUDQVSHQWHQH
5. Arrange the following in increasing order of dehydration.
2+ 2+ 2+
2+
, ,, ,,, ,9
SOLUTION
5. I < II < III < IV
2. Dehydrohalogenations of Alkyl Halide: Dehydrohalogenation is the loss of hydrogen and a halogen from an alkene.
+²&²&²; & & +;

Hydrocarbon 3.43
The reaction is carried out in the presence of a strong base such as sodium ethoxide (NaOC2H5) in ethyl alcohol as a
solvent.
+²&²&²;1D2&+ & & &+2+1D;
&O
+ +
1D2&+&+
+ +
+
Similarly, NaOCH 3 , KOC(CH 3 )3 are the preferred bases used in this process.
CH 3 – (CH 2 )15 – CH 2 – CH 2 – Cl →
KOC(CH3 )3
CH 3 – (CH 2 )15 – CH = CH 2
DMSO 25° C
The regeoselectivity of dehydrohalogenation of alkyl halide following Zaitesev rule of elimination predominates the
direction.
%U &+ +&
+& +&
&+ &+ +& &+
+&
PHWK\OEXWHQH PHWK\OEXWHQH

+ +
%U + +
.2&+ &+
&+±&+±2+
+

3. By Dehalogenation of vicinal Dihalides: A compound having two halogen atoms on adjacent carbon atoms is called
vicinal dihalide. Alkenes are formed when vic-dihalides are heated with zinc dust in ethyl alcohol.
General reaction:
%U
=Q
²&²&² & & =Q%U
&+&2+
%U
Specific examples:
&+&22+
&+±&+±&+=Q &+±&+ &+=Q%U
'
3URSHQH
%U %U
GLEURPRSURSDQH
%U
%U 1DO
DFHWRQH O%U±
Denomination by Zinc takes place on the surface of the metal and the mechanism is uncertain. With NaI, the reaction
takes place by E2 elimination. This reaction, however, is not of much practical utility because dihalides themselves are
prepared by the addition of halogen to an alkene.
3.44 Hydrocarbon
4. By controlled hydrogenation of Alkynes: Alkynes react with hydrogen in the presence of Lindlar’s catalyst to give
alkenes.
− CaCO3
CH 3 − C ≡ C − H + H 2 Pd

quinoline
→ H 3 C − CH = CH 2
Pr opene
( cis )
5. By Cracking of Alkanes: Alkanes when heated at 500 – 800°C in the absence of air decompose to yield lower
molecular weight alkenes, alkanes and hydrogen.
H3C – CH3 

600°
→ CH2 = CH2 + CH4 + H2
H3C – CH2 – CH3 

600°
→ CH3 – CH = CH2 + CH2 = CH2 + CH4 + H2
Illustrations
82. List the alkenes formed by the mainly industrial catalytic dehydrogenation (–H2) at 500 °C of CH3CH2CH2CH3.
Ans. In this b-elimination, the two H's can be removed from C1 and C2 or C2 and C3. The two geometric isomers of
2-butene are formed. In addition, loss of four H’s leads to a diene.
+& &+ +& +

+& &+&+&+ & & & & +& &+&+ &+
+ + + &+
%XWHQH FLV WUDQV%XWHQH %XWDGLHQH
83. (a) Give the structural formulae for the alkenes formed from the reaction of 2-bromobutane and ale. KOH.
(b) Select the major and minor products and rationalize your choice, (c) What is the order of preferential removal
of the type of H on dehydrohalogenation of alkyl halides? (d) In terms of R substitution, what general names are
associated with these products?
Ans. (a) H2C=CHCH2CH3 (A), cis-CH3CH = CHCH3 (B), and trans-CH3CH=CHCH3 (C). (b) Alkene stability increases
with increasing number of electron-releasing substituent R’s bonded to the sp2 C’s, and the relative yields depend
on their relative stabilities. A is the minor product because it has one R and is less stable than either 2-butene
diastereomer having two R’s. C is the major di-R alkene product because it is trans. (c) The order is 3° > 2° > T
(Saytzeff rule). If H’s represent wealth, we say ‘the poor get poorer’ because the H is best removed from the C
with the fewest number of H’s. A comes from removal of a 1° H from Cl and B and C come from removal of a
2° H from C3. (d) The more substituted alkene is the Saytzeff product, in this case B and C. The least substituted
is the Hofmann product, in this case A.
84. (a) What happens to the relative yields of Saytzeff and Hofmann product alkenes when Me3CO– replaces EtO– as
the base for dehydrohalogenation? (b) Account for the change in relative yields.
Ans. (a) The yield of 1-butene increases, (b) The bulkiness of (CH3)3CO– makes it more difficult for the more hindered
2° H to be abstracted, slowing the rate of formation of B and C, and favoring formation of A by removal of the
less hindered 1° H.
85. (a) Use transition state theory to account for the relative yields of cis and trans alkenes. (b) Would it matter if the
reaction showed kinetic or thermodynamic control? (c) How does replacing the Me’s of 2-bromobutane by f-Bu’s
affect the ratio of product diastereomers?
Ans. (a) In this one-step reaction the TS must begin to reflect the incipient alkene. Two TS’s are possible, a trans-
like and a trans like. The trans-like TS, being more stable, has the lower DH+ and its formation is the preferred
pathway, (b) No. The preferred product is both kinetically and thermodynamically controlled because the major
Hydrocarbon 3.45
stable product also has the lower enthalpy TS. (c) In 3-bromo-2,2,5,5-tetramethyIhexane, Me3CCH2CHBrCMe3,
the repulsion of the bulkier groups causes a substantial increase in the DH+ of the cis-like TS as compared to the
trans-like TS. Consequently, the trans diastereomer is practically the sole product.
86. List the possible products, in order of decreasing yield, from the reaction of 3-bromo-2,3-dimethylpentane with
ale. KOH.
(CH3)2C == C(CH3)CH2CH3 > CH3CH = C(CH3)CH(CH3)2
tetrasubstituted, R2C == CR2 trisubstituted, RHC == CR2
> H2C == C(CH2CH3)CH(CH3)2
disubstituted, H2C == CR2
87. Which isomers of C4H9Br yield only a single alkene on dehydrohalogenation? Give the structures of the alkenes.
Ans. The 1° halides: BrCH2CH2CH2CH3 → CH2=CHCH2CH3
BrCH2CH(CH3)2 →CH2 = C(CH3)2 The 3° halide (All vicinal H’s are equivalent):
(CH3)3CBr → CH2=C(CH3)2
88. Synthesize (a) cyclohexene from cyclohexane, and (b) propene from propane.
Ans. (a) Cyclohexane Cl2
hv
→ chlorocyclohexane alc
. KOH
→ cyclohexene
(b) CH 3 CH 2 CH Cl

hv
2
→ mixture of [CH 3 CH 2 CH 2 Cl + CH 3 CHClCH 3 ] alc
. KOH
 → propene
The mixture of chloropropanes need not be separated because they both give propene.
RU1DOLQDFHWRQH
89. (a) Complete the following general reaction: %U±&±&±%U=Q+2$F "
(b) Classify this general reaction for preparing alkenes.

Ans. (a) =C=C= + ZnBr2 (or 2NaBr + I2 if Nal is used), (b) Dehalogenation of vicinal dihalides, a b-elimination.
90. In terms of oxidation-reduction and using ethane derivatives, compare dehalogenation, dehydrogenation, and
dehydrohalogenation.
Ans. Each C bonded to Br in CH2BrCH2Br has an oxidation number (ON) of -1. Each doubly-bonded C in the alkene
has an ON of - 2. This decrease in ON indicates that the dihalide is reduced and debromination is a reduction.
(Zn is oxidized to Zn2+). During dehydrogenation of CH3CH3, the C’s that become doubly-bonded go from an
ON of - 3 to - 2. This increase in ON (it becomes less negative) signals an oxidation of the hydrocarbon. (The
H’s are reduced; they go from an ON of +1 when bonded to C, to 0 in H2.) In the alkyl halide, the C bonded
to Br has an ON of -1 and the a-C has an ON of - 3, for an average of - 2, the same as in the alkene. Hence,
dehydrohalogenation is not a redox reaction.
91. (a) Write a general equation for the reaction of an alcohol with concentrated acids such as H2SO4 or H3PO4 at
about 170 °C. (b) Classify this general reaction for preparing alkenes. (c) Why is alcohol dehydration a useful
reaction for alkene preparation?
+ 2+
+62
Ans. (a) &²& & & +2
(b) Dehydration
(c) Complex alcohols are readily synthesized.
92. (a) Complete the reactions of the following alcohols with H2SO4 at ~ 170 °C: (i) CH3CH2CH2OH,
(ii) CH3CHOHCH3, and (iii) (CH3)3COH. (b) Give the relative reaction rates of these alcohols.
Ans. (a) (i) CH3CH = CH2, (ii) CH3CH = CH2, and (iii) H2C = C(CH3)2. (b) Since the order of reactivity of ROH is 3°
> 2° > 1° > — CH3, (iii) > (ii) > (i).
3.46 Hydrocarbon
93. (a) Give the general and specific names for the intermediate formed in the slow step. (A) Explain why dehydration
proceeds in acid but not in base.
Ans. (a) The intermediate cation is called a carbocation (formerly called carbonium ion) and the name of the
corresponding parent alkyl group is used. Me2CH+ is the isopropyl cation, (b) Under basic conditions the very
poor leaving group OH– (a strong base) would have to be eliminated. The essential role of the acid is to convert
—OH to —OH2 so that the very good leaving group H2O (a very weak base) is eliminated instead.
94. In terms of TS theory, with the aid of an enthalpy diagram, account for the relationship of the relative reactivities
of RCH2OH, R2CHOH, and R3COH and the stabilities of the intermediate carbocations.
Ans. The order of reactivities is directly related to the order of stabilities of the incipient carbocations, 3° > 2° >
1° as shown in below fig. Note that this is the same order of stabilities of radicals The lowest DH+ is required
for the TS leading to the incipient carbocation of the 3° alcohol and the highest for the incipient C+ of the
1° alcohol.
G G G G G G
5&+±±±2+ 5&+±±±2+ 5&±±±2+
(QWKDOS\
'+Á 5&+ '+Á '+Á

6HFRQGDU\ 5&+

3ULPDU\ 7DUWLDU\ 5&

5&+2+ 5&+2+ 5&2+
3URJUHVVRI5HDFWLRQ
95. (a) Supply mechanisms for the following acid-catalyzed dehydrations: (i) HOCH2CH2CH2CH3 to mainly trans-
CH3CH = CHCH3 and (ii) CH3CH(OH)C(CH3)3 to mainly (CH3)2C = C(CH3)2. (b) Why are the 1° alcohols poor
starting materials for the synthesis of 1-alkenes?
Ans. (a) (i) The 1° RCH2 initially formed on the terminal C1 is less stable than the 2° R2CH+ produced by the hydride
shift of an H with its electron pair from C1 to C2. The hydride ion, H: – never forms. Instead it becomes attached
to the new C (rearrangement terminus) as it breaks free from its old C (rearrangement origin) as shown in the TS
for the hydride shift. (If a 1° RCH2+ is to be formed, it is likely the : H begins to rearrange before the carbocation
ever forms.) The reaction is completed when either the parent alcohol or the conjugate base of the acid removes
the very acidic H+ from C3 of the 2° R+ yielding 2-butene rather than the expected 1-butene.
+ + + +
+ KHDW

a+
&+&+&&2+ ±+2
&+&+&±&
+ + + +
%XWDQRO 5&+
+ +
a+
>&+&++&&+@Á &+&+&&+ WUDQV%XWHQH

+ +
5&+
The hydride shift is indicated by ~ : H over the reaction arrow.

(ii) Here a less stable 2° R2CH+ rearranges to a more stable 3° R3C+ by a methide OCH3 or :Me) shift whereby
Me with its bonding electron pair moves from C3 to C2. H3C= – is never set free but rather becomes partially
bonded to the rearrangement terminus while still partially bonded to the origin.
Hydrocarbon 3.47
+ 0H 0H
+KHDW a0H
&+&±&&+ ±+2
&+&+±&±&+
+2 0H 0H
'LPHWK\O± 5&+
EXWDQRO
0H 0H
±+
&+&+&&+ &+²& &²&+

0H 0H
±
5& 'LPHWK\O
EXWHQH
(b) The 1° RCH2+ would rearrange and a 2-alkene would result. Even if a 1-alkene were to form, it would tend to
rearrange in acid to a 2-alkene.
96. (a) Give structures for compounds that will form 2-pentene (disregard stereoisomerism) in best possible yields
when reacted with: (i) ale. KOH, (ii) Zn/HOAc, (iii) cone. H2SO4 + heat, (b) What is the best way to prepare only
(i) cis- and (ii) fran.s-2-pentene?
Ans. (a) (i) CH3CH2CHClCH2CH3. 2-Chloropentene would give some 1-pentene thereby reducing the yield,
(ii) CH3CHBrCHBrCH2CH3 (iii) CH3CH2CHOHCH2CH3 [See (i) for reasons why the 2-isomer should not be
used.] (b) Reduce CH3C=CCH2CH3 using (i) H2/Pd and (ii) Na/EtOH.
97. provide the structural formula and the name of the principal product from each of the following reactions:
(a) BrCH2CH2CH2CH2Br + alc. KOH (c) (CH3)3CBr + CH3COO–
%U
(c) (CH3)2CHCH(OH)CH3 + H2SO4 + heat (d) =Q LQDOFRKRO
+
+
%U
Ans. (a) H2C=CH— CH=CH2, 1,3-butadiene; (b) (CH3)2C= CHCH3, 2-methyl-2-butene; (c) H2C=C(CH3)2, isobutylene
(2-methylpropene); (d) cyclopentene.
Reactions of Alkenes
Chemical Properties of Alkenes

Alkenes are more reactive than alkanes. This is because
1. The p electrons of a double bond are located much farther from the carbon nuclei and are thus less firmly bound to
them.
2. The overlap of atomic orbitals in forming a p-bond is not as effective as that in s bonds. Thus a p-bond is weaker than
a s bond and more easily broken.
The important reactions of alkenes are addition reactions:

1. Electrophilic Addition Reaction
Addition reaction of alkene and alkynes takes place by attack of electrophile via formation of carbonium ion. If
electrophile is bulky, the intermediate will be a static cyclic transition state.
Some of the electrophilic addition reaction are regioselective. These reactions can be syn or anti type.
3.48 Hydrocarbon
2. Free radical addition reactions

If attacking reagent is free radical the intermediate will be alkyl free radical. Presence of peroxide favours homolytic fis-
sion and formation of free radicals.
O = O + R − H 
O2 /hv
→ R −O−O−H
alkyl hydroperoxide
+ & &+
+ 2±2±+
2 2KY
FXPHQHK\GURSHUR[LGH
3. Nucleophilic addition
If attacking reagent is a nucleophile, it is called nucleophilic addition reaction. Addition reaction of compounds having
multiple bond between two different atom are nucleophilic.
G ±G Ւ
&1² +
& 2+&1 &2 & 2+
&+ &1
&\DQRK\GULQ
Addition Reaction of Alkene and Alkyne are normally electrophilic and free/radical:
If strong electron withdrawing groups are directly attached to alkene, it will show nucleophilic addition.
1X
21 12 Ւ
2 1 12
& & 1X &±&
12 Ւ 12
21 2 1
4. Catalytic Hydrogenation
Alkenes reacts with hydrogen in the presence of platinum, palladium, rhodium or nickel catalyst to form the corresponding alkane.
R 2 C = CR 2 + H 2 → R 2 — CH — CH — R 2
Pt, Pd, Rh or Ni
+
3W
Illustration
98. (a) Give the products from catalytic hydrogenation of: (i) cis-2,3-dibromo-2-butene, (ii) trans-2,3-dibromo-2-
butene, and (iii) 1,2-dimethylcyclohexene. (b) Classify the mode of addition.
Ans. +
+ %U
WRSIDFH 0H
%U
%U 0H 0H
+DGGVIURP
& %U 0H
%U& ERWWRPIDFH %U +
0H
0H + VDPHPHVR
Hydrocarbon 3.49
+
%U
+
WRSIDFH 0H 0H
%U %U

+DGGVIURP
& 0H %U 0H
0H& ERWWRPIDFH 0H +
%U
%U +
HQDQWLRPHUV
WRSIDFH
+ +
+DGGVIURP
0H 0H
ERWWRPIDFH
0H 0H
0H 0H
+ +
VDPHPHVR
In (i) and (iii), the same meso product is formed whether H2 adds from the top or bottom face of the p bond. (b) Syn
5. Addition of Hydrogen Halide

A proton and a halogen add to double bond of an alkene to yield an alkyl halide. Addition proceeds in accordance with
Markovnikov’s rule, hydrogen adds to the carbon that has the greater number of hydrogens.
5 +; 5 &+
&+
;
&++&O &+
&O
In each of these, an unsymmetrically substituted alkene has given a single product rather than the mixture that
might have been expected. Thus, we can say that addition of H – X across alkenes are ‘regiospecific’ as only one of
the two possible directions of addition occurs.
&O
6ROH
SURGXFW +&±&±&+
+ & &+
& &++&O &KORUR0HWK\OSURSDQH
+ &
&+
0HWK\OSURSHQH 1RWIRUPHG
&+±&+±&+&O
&KORUR0HWK\OSURSDQH
3.50 Hydrocarbon
&+
&+&+
&+
+& &+

&
&+
&+
(QHUJ\
&+&+&O
&+
&+
& &++&O
&+
&+ &&O
5HDFWLRQFRRUGLQDWH
3RWHQWLDOHQHUJ\GLDJUDPIRUWKHDGGLWLRQRI+&OWRLVREXW\OHQH
6. Markovnikov’s Rule
The addition of H–X to an alkene is governed by this rule. It states that:
In addition of H–X to an alkene, the H gets attached to the carbon with fewer alky substituents and the X attaches to the
carbon with more alkyl substituents. [or hydrogen will add on that carbon which have more hydrogen, i.e., richer becomes
more richer]
+& &O
(WKHU
& &+ +&O +&±&±&+
+& &+
DON\OJURXSV 1RDON\OJURXSV &KORURPHWK\OSURSDQH
RQWKLVFDUERQ RQWKLVFDUERQ
PHWK\OSURSHQH
When both double-bond carbon atoms have same degree of substitution, a mixture of addition products results.
%U %U
(WKHU
+&+&±&+ &+±&++%U &+&+&+&+&+&+&+&+&+&+
%URPRSHQWDQH %URPRSHQWDQH
DON\OJURXS DON\OJURXS
RQWKLVFDUERQ RQWKLVFDUERQ
&+±&+±&+ &+±&+
+
&+±&+±&+±&+±&+ &+±&+±&+±&+±&+
Պ Պ
6HFRQGDU\FDUERQLXPLRQ 6HFRQGDU\FDUERQLXPLRQ
ZLWK+\SHUFRQMXJDWLRQ ZLWK+\SHUFRQMXJDWLRQ PRUHVWDEOH
Also, as these reaction proceed via. carbocation formation. So in the addition of HX to alkenes, the more highly sub-
stituted carbocation intermediate is formed lather than the less substituted one.
Hydrocarbon 3.51
+ &O
Պ &O±
&+±&±&+ +&±&±&+
+& &+ &+

& &++&O WHUW FDUERFDWLRQ VROHSURGXFW
+&
+ +
Պ &O±
+&±&±&+ &+±&±&+&O
&+ &+
3ULPDU\ FDUERFDWLRQ >1RWIRUPHG@
7. Addition of HBr
Addition of HCl and HI takes place according to Markovnikov’s rule, but the same is not followed in case of HBr.
Kharasch discovered that the addition of HBr to an alkene was affected the presence of peroxide such as benzoyl peroxide
or oxygen. Their presence causes the addition of HBr to proceed in an antimarkovnikov’s fashion. For example, when
propylene reacts with HBr in the presence of n-peroxide, the major product is n-propyl bromide, whereas in the absence
of peroxide, the major product is isopropyl bromide.
3HUR[LGH
&+&+&+%U
&+±&+ &++%U %U
1RSHUR[LGH
&+&+&+
Mechanism
The essence of the mechanism is that hydrogen and bromine add to the double bond homolytically rather than heterolyti-
cally; the intermediate is a free radical rather than a carbocation. Like halogenation of alkanes, this is a chain reaction, this
time involving addition rather than substitution.
SHUR[LGHV 5DG
&KDLQLQLWLDWLQJVWHSV
5DG+%U 5DG+%U
%U±& &± ±&±&±

%U
&KDLQSURSDJDWLQJVWHSV
±&±&±+%U ±&±&±%U
%U %U +
Decomposition of the peroxide (step 1) to yield free radicals is a well-known reaction. The free radical thus formed
abstracts hydrogen from hydrogen bromide (step 2) to form a bromine atom. In step (3) this bromine atom attaches itself
to one of the doubly bonded carbons; in doing this, it uses its odd electron and one of the p electrons. The other carbon is
left with an odd electron, and the alkene is thus converted into a free radical.
3.52 Hydrocarbon
This free radical, like the free radical initially generated from the peroxide, abstracts hydrogen from hydrogen bromide
(step 4). Addition is now complete, and a new bromine atom has been generated to continue the chain. As in halogenation
of alkanes, every so often a reactive particle combines with another one, or is captured by the wall of the reaction vessel,
and a chain is terminated.
%U±
&+±±&±±&+ &+±±&+±±&+
Պ
$FDWLRQ
+%U %U
&+±±&+ &+ ,VRSURS\OEURPLGH
3URS\OHQH $FWXDOSURGXFW
&+±±&+±±&+Պ
$FDWLRQ
)UHHUDGLFDODGGLWLRQ$QWL0DUNRYQLNRYRULHQWDWLRQ
+%U
&+±±&+±±&+

%U &+±±&+±±&+%U
$IUHHUDGLFDO QSURS\OEURPLGH
%U
&+±±&+ &+ $FWXDOSURGXFW
3URS\OHQH
&+±±&+±±&+
%U
$IUHHUDGLFDO
NOTE:
HCl and HI do not give anti-Marko/nikov-products in the presence of peroxides. This is because:
(a) The H–Cl bond (103 Kcal /mole) is stronger than H–Br bond (87 Kcal/mole). It is not broken by the alkoxy free radicals
obtained from peroxides.
(b) The H–I bond (71 Kcal/mole is/weaker than H–Br bond (87 Kcal/mole). It is broken by the alkoxy free radical
obtained from peroxides. But the iodine atom so formed readily combines with each other to yield iodine molecule
rather than attack the double bond in alkenes.
Illustrations
99. Compare the regioselectivity of the reactions of HBr with (a) CF3CH = CH2, (b) BrCH=CH2, and (c) CH3—O—
CH = CHCH3.
Ans. An electron-withdrawing group attached to the C that has fewer H’s would tend to destabilize a + on this C and
cause the addition to be anti-Markovnikov. Such is the case in (a), where the major product is CF3CH2CH2Br.
However, in (b) the electron-withdrawing inductive effect of Br is superseded by extended p delocalization of an

unshared electron pair from Br to C+, thereby stabilizing the R+, >%U²&+²&+ļ%U &+&+@. Thus,
the Markovnikov product, Br2CHCH3, is formed.
(c) Protonation of either C of the C == C gives a 2° R+. However, the O behaves like Br in delocalizing a pair of c
's to the adjacent C+, stabilizing the + charge, and H+ bonds almost exclusive to the carbon b to the O as follows:

>&+±2±&+±&+&+ļ&+±2 &+±&+&+@. The product is CH3 — O — CHBrCH2CH3. In general,
when the inductively electron-withdrawing group attached to the doubly-honded C has an unshared pair of e–'s.
Markovnikov addition is observed.
100. Predict the product of the reaction between Me2C=CH2 and ICl.
Ans. Cl is more electronegative than I making I the E+ that, according to the Markovnikov rule, adds to the C with the
greater number of H’s. The product is 2-chloro-1-iodo-2-methylpropane, Me2CClCH2I.
Hydrocarbon 3.53
## Practice Exercises
6. (i) Give the mechanism for the following conversion:
&+2+
&+
+&O
(ii) +& & &+ $LGHQWLI\$
&+ &+
7. Anti-Markovnikov addition of HBr is not observed is

(a) Propene (b) 1-Butene (c) But-2-ene (d) Pent-2-ene
8. Which of the following reactions will yield 2, 2-dibromopropane?
(a) HC ≡ CH + 2HBr → (b) CH3 – C ≡ CH + 2HBr →
(c) CH3 – CH = CH2 + HBr → (d) CH3 – CH = CH – Br + HBr →
9. Which one of the following compounds will give in the presence of peroxide a product different
from that obtained in the absence of peroxide?
(a) 1-butane (b) 1-butene, HBr (c) 2-butene, HCl (d) 2-butene, HBr
10. The principal organic compound formed in the reaction
CH2 = CH(CH2)COOH + HBr → Peroxide
…………. is
(a) &+±&+± (b) CH2 = CH(CH2)8COBr
%U
(c) &+±&+ &+ &22+ (d) &+ &+ &+ ±&+±&22+
%U %U
SOLUTIONS
6.

&+2+ &+2+
+
(i)
±+2

&+

±+ 5LQJ
([SDQVLRQ
3.54 Hydrocarbon
&+ &+
+
(ii) +& & &+ +& & &+±&+
&+ &+ &+

FDUERFDWLRQ
±0HWKH\O
VKLIW
&+
&+ &+
&O± & &+
+& & +& +& &+
&+
&O &+
7. Both carbons of double bond have equal number of hydrogens and thus it is symmetrical, alkane.
\ (C)
8.
%U %U
+%U +%U
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9. Peroixde effect is observed when unsymmetrical alkene is treated with HBr only (and not with HCl
and HI).
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10. Follows the peroxide effect

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8. Addition of sulphuric Acid

Alkene reacts with sulphuric acid to form alkyl hydrogen sulphates. A proton and a hydrogen sulphate ion adds to double
bond in accordance with Markovnikov’s rule. Alkene that yield tertiary carbocations on protonation tend to polymerise in
concentrated H 2SO 4 .
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Hydrocarbon 3.55
Illustration
98. Isobutylene gas dissolves in 63% H2SO4 to yield a deliquescent white solid, A. When heated in water, the solid
changes to a liquid, B, bp 83 °C. Give the structures of A and B.
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9. Addition of Halogens
The addition of halogens to alkenes, like the addition of protic acids, is believed to be electrophilic addition, and to involve
two steps. Again, the first step involves the formation of a cation. But this cation, in most cases, is not a carbocation, but
something new to us: a halonium ion. Let us see what a halonium ion is, and what evidence there is for its formation.
Let us use addition of bromine as our example. In step (1), bromine is transferred from a bromine molecule to the
alkene: not to just one of the doubly bonded carbons, but to both, forming a cyclic bromonium ion.

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Step (1) does indeed represent electrophilic addition. Bromine is transferred as positive bromine: that is, without a pair of
electrons, which are left behind on the newly formed bromide ion. In step (2), this bromide ion, or more probably another
just like it, reacts with the bromonium ion to yield the product, the dibromide.
What is being proposed here is not a p-complex, in which the (acidic) bromine molecule is held by the (basic) p cloud
of the alkene. Bromine is bonded by two p bonds—one to each carbon—to form a ring. A p-complex of molecular Br2 and
alkene may, however, be a reversibly formed precursor of the bromonium ion.
The transfer of a proton from a strong acid to an alkene, while new to us, does fit into a familiar framework of acid-
base reactions. But how are we to understand the transfer of positive bromine from a bromine molecule? To begin with,
it is an acid-base reaction—although not in the Lowry-Bronsted sense. Just as alkenes are bases, so halogens are acids, of
the Lewis type.
We can understand this reaction better if we change our viewpoint. From the standpoint of a halogen molecule, the
reaction with an alkene is nucleophilic substitution. Acting as a nucleophile, the alkene attaches itself to one of the bromines
and pushes the other bromine out as bromide ion. Bromide ion is the leaving group; and, as we have seen, bromide ion is
a very good leaving group.
This mechanism is based on the following facts:
(a) the effect of the structure of the alkene on reactivity;
(b) the effect of added nucleophiles on the products obtained;
(c) the fact that halogens add with complete stereoselectivity and in the anti sense;
(d) the direct observation of halonium ions under superacid conditions; and
(e) the role played by halonium ions in neighboring group effects.
3.56 Hydrocarbon
We shall examine each of these pieces of evidence: (a) and (b) now, and (c) and (d) in later chapters.
First, there is (a) the effect of the structure of the alkene on reactivity. Alkenes show the same order of reactivity toward
halogens as toward the acids already studied: electron-releasing substituents activate an alkene, and electron-withdrawing
sub-stituents deactivate. This fact supports the idea that addition is indeed electrophilic— that the alkene is acting as an
electron source, and that halogen acts as an acid.
Next, there is (b) the effect of added nucleophiles on the products obtained. If a halonium ion is the intermediate, and
capable of reacting with halide ion, then we might expect it to react with almost any negative ion or basic molecule we care
to provide. The bromonium ion formed in the reaction between ethylene and bromine, for example, should be able to react
not only with bromide ion but also—if these are present—with fluoride ion, iodide ion, nitrate ion, or water.
The facts are in complete agreement with this expectation. When ethylene is bubbled into an aqueous solution of
bromine and sodium chloride, there is formed not only the dibromo compound but also the bromochloro compound and
the bromoalcohol. Aqueous sodium chloride alone is completely inert toward ethylene; chloride ion or water can react only
after the halonium ion has been formed by the action of bromine. In a similar way, bromine and aqueous sodium iodide or
sodium nitrate convert ethylene into the bromoiodo compound or the bromonitrate, as well as the dibromo compound and
the bromoalcohol. Bromine in water with no added ion yields the dibromo compound and the bromoalcohol.
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Now, this elegant work certainly shows that ethylene reacts with bromine to form something that can react with these
other nucleophiles—but it need not be a bromonium ion. On this evidence alone, the intermediate cation could be the
simple open carbocation BrCH2CH2+. As we shall see, it was the stereochemistry of the reaction that led to the concept of
an intermediate bromonium ion, a concept that has since been supported by actual observation of such ions.
When cis-2-butene adds bromine, the product is a racemic form of 2-3-dibromobutane. When trans-2-butene adds
bromine the product is the meso compound. Thus, we find that a particular stereoisomeric form of the starting material
react in such a way that it gives a specific stereoisomeric form of the product. Thus, the reaction is stereospecific.
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Hydrocarbon 3.57
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9. Halohydrin formation
As we have seen, addition of chlorine or bromine in the presence of water can yield compounds containing halogen and
hydroxyl on adjacent carbon atoms. These compounds are thus chloroalcohols or bromoalcohols. They are commonly referred
to as halohydrins: chlorohydrins or bromohydrins. Under proper conditions, they can be made the major products. For example,
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There is evidence, of a kind we are not prepared to go into here, that these compounds are not formed by addition of
preformed hypohalous acid, HOX, but by reaction of the alkene with, successively, halogen and water.
Mechanism
→ HO − X + + HX
H 2 O + X 2 
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3.58 Hydrocarbon
Halogen adds (step 1) to form the halonium ion; this then reacts, in part, not with bromide ion, but with water (step 2
and 3 ) to yield the protonated alcohol. Whatever the mechanism, the result is addition of the elements of hypohalous acid
(HO— and —X), and the reaction is often referred to in that way.
Propylene, we see above, gives the chlorohydrin in which chlorine is attached to the terminal carbon. This is typical
behavior for an unsymmetrical alkene; orientation follows Markovnikov’s rule, with positive halogen going to the same
carbon that the hydrogen of a protic reagent would.
Now, this orientation would be perfectly understandable if the intermediate were an open carbocation: the initial
addition of halogen yields the more stable carbocation—secondary, in the case of propylene. But the stereochemistry
indicates that the intermediate is not an open carbocation, but a cyclic halonium ion.
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Illustrations
102. (a) Give the product(s) with the correct stereochemistry for the reaction of cyclohexene with (i) Br2, (ii) Br2 in
the presence of NaCl, and (iii) Br2 in CH3OH. (b) Is Br2 addition stereoselective and if so what course does it
take?
Ans. (a) (i) trans-1,2-Dibromocyclohexane (A), (ii) A + trans-1-bromo-2-chlorocyclohexane (no dichlorocyclohexane),
and (iii) A + mw.s-1-bromo-2-methoxycyclohexane. (b) Yes, trans or anti. The addition is also said to be
antarafacial, that is, groups of the addend bond from opposite faces of the double bond.
103. (a) Give the stereochemical structure of the reaction product of Br2 with (i) cis-2-butene and (ii) trans-2-bu’ene.
(b) In terms of its stereochemistry, characterize this type of reaction.
Ans. (a) (i) rac-2,3-Dibromobutane and (ii) meso-2,3-dibromobutane. (b) Diastereospecific.
104. (a) What mechanistic facts and interpretations emerge from the product formations in Problems 102 and 103?
(b) Give a mechanism for the Br2 addition. Illustrate with cis- and trans-2-butene.
Ans. (a) (i) The addition is electrophilic, inferred from the absence of any 1,2-dichlorocyclohexane (which would
require a source of Cl+).
(ii) It is not a one-step reaction, inferred from the intrusion of the nucleophiles Cl– and MeOH in formation
of byproducts.
(iii) Addition is anti (trans); one Br adds to the face above the p bond, the second Br adds to the face below.
Anti addition also precludes a one-step mechanism which would require the two Br's to approach from
the same side of the p bond to give cis-1,2-dibromocyclohexane. Such an addition is called cis, syn, or
suprafacial.
(iv) The diastereospecificity of the 2-butene reactions indicates the absence of an open carbocation interme-
diate whose p AO could be attacked from both the top and bottom giving a mixture of diastereomers.
Furthermore, the same carbocation would form from both cis- and trans-2-butene and should then give
the same product distribution. The intermediate must preserve the stereochemistry of the starting materi-
als and is a bridged cation.
(b) The first step is the formation of a bridged cation, called a bromonium ion. In the second step, the nucleophile
(mainly Br– but also nucleophilic solvents or added anions) adds to the face away from the bridging group to
yield the anti addition product.
Hydrocarbon 3.59
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Formation of the bromochloro and bromomethoxy compounds (see Problem 102) requires attack on the bro-
monium ion by Cl– and MeOH respectively. Br2 does not ionize into Br+ and Br–. More likely, the p e– ‘s attack
one of the Br’s displacing the other as Br–, initially giving a p complex that moves on to a three-membered ring
bromonium ion (Fig. 7-6).
– C +
– C + + Br Br Bromonium ion + Br–
105. (a) Give the product of the reaction of (CH3)2C=CH2 with Br2 in H2O and account for its orientation in terms of
the bromonium ion. (b) What intermediate ion is formed in the reaction of alkenes with Cl2 and H2O?
Ans. (a) With this unsymmetrical alkene the X+ adds to the terminal C with more H’s to give the bromohydrin
(CH3)2C(OH)CH2Br, l-bromo-2-methyl-2-propanol. The bromonium ion of this alkene has Br attached to two
different C’s and the product formation is a question of which C is the more active site toward bonding with
the nucleophilic H2O. When the nucleophile is poor (H2O) and the solvent has a high polarity (H2O), the C that
can best be an incipient R+ is the more reactive site. In this bromonium ion it is the 3° C to which the O of H2O
forms the bond, eventually giving the product, (b) Cl+ replaces Br+ to give a chloronium ion, another example of
a halonium ion.
106. Give the product, indicating the stereochemistry when pertinent, for each of the following reactions: (a) cyclohexene
+ KI/H3PO4, (b) cyclopentene + Br2 in H2O, (c) cis- or trans-2-pentene + HBr, and (d) 1-methylcyclohexene + Cl2
in H2O.
Ans. (a) Iodocyclohexane. This reagent is cheaper than using HI. (b) Anti addition yields rac-trans-2-bromocyclopentanol.
Br Br
H H
+
H H
OH HO
rac-trans-2-Bromocyclopentanol
(c) 3-Bromopentane and rac-2-bromopentane.
(d) OH H + H HO through intermediate chloronium ion
Me Cl Cl Me
racemate
3.60 Hydrocarbon
Selective radical bromination: allylic substitution of H by Br

Because radical brominations are so selective, they can be used successfully in the lab to make alkyl bromides. There
are relatively few ways of functionalizing an unfunctionalized centre, but radical allylic bromination is one of these. Just
as tertiary radicals are more stable than primary ones, so allylic radicals are even more stable than teriary ones. In the
presence of a suitable initiator, bromine will therefore selectively abstract an allylic hydrogent atom to give an allylic
radical that can then be trapped by a molccule of bromine to regenerate a bromine radical (chain propagation) and produce
the allylic bromide.
initiation Br2 → 2 × Br•
NOTE:
Bond energy for tertiary C–HL 364 kJ mol–1.
Bond energy for allylic C–H: 397 kJ mol–1.
Remember though that these figures were determined in the gas phase, and here our reactions are in solution. Nonetheless,
because salvation effects are more or less the same for all radicals, we expect the order of the bond strengths to remain the
same in both phases.
propagation H Br
Br
HBr Br Br
Br
However, there is a problem with this reaction if bromine itself is used, because an alternative radical addition reaction
can compete with radical abstraction.
Br Br
competing Br
addition Br Br
Br
reaction
NOTE:
This competing reaction is a radical addition across a double bond. You have also met an analogous polar addition across
an alkene that reaction is suppressed here by using a nonpolar solvent, usually CCl4.
The first step of this competing addition reaction is, in fact, reversible; the reaction is driven forward by the partici-
pation for a second molecule of bromine that traps the product alkyl radical. This side-reaction can be prevented if the
concentration of Br2 in the reaction is kept very low. One possibility is to add Br2 very slowly to the reaction mixture,
but it is better not to use bromine itself, but a compound that releases molecular bromine slowly during the reaction. That
compound is N-bromosuccinimide, or NBS.
NBS, CCl4 hv Br
85% yield
NOTE:
NBS (N-Bromo Succinimide) is known to be a source of bromine because the rations of products obtained from its
reactions are identical with those obtained from reactions using small amounts of bromine.
O
N Br
O
N-bromosuccinimido
(NBS)
Hydrocarbon 3.61
The reaction occurs through a bromonium ion and is stereospecifically anti on each isomer of the alkene.
O
OH
⊕
Br Br
Br N
H2O
OMe O OMe OMe
NOTE:
NBS is a radical generator in nonpolar solvents but in polar solvents, especially water, it supplies electrophilic bromine.
Illustrations
107. Compare the reactions of H2C = CHCH3 with Cl2 or Br2 (X2) at (a) room temperature, (b) high temperature, or
with uv radiation, or low concentrations of X2.
Ans. (a) H2CXCHXCH3 by normal addition, (b) H2C = CHCH2X by substitution at the allylic C.
108. Give the products of the reactions of cyclohexene in CCl4 with (a) sulfuryl chloride, Cl2SO2, (b) t-butyl
hypochlorite, Me3COCl, and (c) N-bromosuccinimide (NBS).
O
O
CH2 C
NBr or NBr
CH2 C
O O
N-Bromosuccinimide
Ans. All three reactions are allylic substitutions.
109. (a) Show how NBS, written in abbreviated form as N – Br, produces small concentrations of Br2, the actual
allylic bromination reagent, (b) Account for the fact that small concentrations of Br2 are conducive to allylic
substitution while high concentrations give addition.
Ans. (a) In order for NBS to react, a small amount of H2O must be present to generate (by hydrolysis) trace amounts
of HBr. HBr reacts with NBS to give trace amounts of Br2 rather than adding to C=C.
N – Br + HBr N – H + Br2
(b) When Br2 acts as an electrophile to give the bromonium ion, Br- is produced. In nonpolar solvents, such as
CCl4, such an ion needs to be stabilized, a feat accomplished by another molecule of Br2, giving the more stable
Br3–. The rate expression for addition is second order in Br2: rate = k[alkene][Br2]2. With very low concentrations
of Br2 the [Br2]2 term becomes negligible and the rate of addition becomes extremely small; substitution
predominates.
110. (a) Give all possible products from the reaction of NBS with 4-methyl-2-pentene. (Disregard geometric
isomerism.) (b) Predict the relative yields with an explanation.
Ans. (a) Ha and Hb in Ha3CCH = CHCHb Me2 are allylic.
BrCH2CH=CHCHMe2 (A)
NBS
1. Removal of H → [H2CCH = CHCHMe2
a H2C = CHCHCHMe2]
H2C=CHCHBrCHMe2 (B)
3.62 Hydrocarbon
H3CCH=CHCBrMe2 (C)
NBS
2. Removal of Hb → [H3CCH = CHCMe2 H3C = CCHCH=CMe2]
H3CCHBrCH=CMe2 (D)
(b) Since Hb is 3° allylic, it is more reactive than the 1° allylic Ha and consequently path 2 and its ensuing prod-
ucts dominate over path 1 and its products. The decreasing order of yields is D (path 2, more substituted) > C
(path 2, less substitute) > A (path 1, more substituted) > B (path 1, less substituted).
111. Give all the products of the reaction of 3-methylmethylenecyclohexane with NBS.
Ans. There are six products, including two pairs of cis-trans diastereomers that arise from allylic rearrangement and
two products that do not.
Me Me Br Br
CH2Br + CH2 + Me CH2
Me –H
a
1-Bromomethyl-3-methyl- cis- and trans-2-Bromo-3-methyl-
a
cyclohexene methylenecyclohexane
CH2
b Me Me Me
b
–H CH2Br + Br CH2 + CH2
1-Bromomethyl-5-methyl-
cyclohexene Br
cis- and trans-2-Bromo-5-methyl-
methylenecyclohexane
1eq . Br2
11. (i) A
hν
NBS LiAlH4
(ii) B C
Identify A, B and C
SOLUTION
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Hydrocarbon 3.63
11. Epoxidation
Peroxy acids transfer oxygen to the double bond of alkenes to yield epoxides the reaction is a sterospecific syn addition.
O
R2 C = CR 2 + R — C — OOH R 2 C — CR2 + R — COH

O
O
CH3 CH3
+ CH 3 — COOOH O + CH3 COOH
Mechanism
H3C
H3C CH3 H3C O R
O R C C
C
+ O O +
C O
C
H O H3C H
H3C CH3
H3C
Alkene Peroxy acid Epoxide Carboxylic Acid
The peroxy acid transfers an oxygen atom to the alkene in a cyclic single step mechanism. The result is the syn addition of
the oxygen to the alkene, with formation of an epoxide and a carboxylic acid.
12. Acid-Catalyzed Hydration
Addition of water to the double bond of an alkene takes place in aquous acid. Addition occurs according to Markovnikov’s
rule. A carbocation is an intermediate and is captured by a molecule of water acting as a nucleophile.
H+
RCH = CR 2 + H 2O R — CH 2 — CR 2
OH
H+
H 2 C = C(CH 3 ) 2 + H 2O (CH 3 )3 COH
H+
H 2 C = C(CH 3 ) 2 + H 2 O H 3C — C(CH 3 ) 2
OH
Mechanism
CH2 H
H H
+ slow H C C + O H
Step 1: H3C CH3 + H O H 3
CH3
The alkene accepts a proton to form more stable 3° carbocation.
CH3
H CH3 H
C fast +
Step 2: H C CH + O H H3C C O H
3 3
CH3
The carbocation reacts with a molecule of water to form a protonated alcohol.
3.64 Hydrocarbon
CH3 H H CH3 H
+ fast +
Step 3: H C C O H + O H H3C C O H + H O H
3
CH3 CH3
A transfer of proton to a molecule of water leads to a product.
Illustrations
112. (a) What principle relates the mechanisms of dehydration of alcohols and hydration of alkenes? (b) What
experimental conditions favor dehydration rather than hydration?
Ans. (a) The principle of microscopic reversibility states that every reaction is reversible, even if only to a
microscopically small extent. Furthermore, the reverse process proceeds through the same intermediates and
transition states, but in the opposite direction.
H+ + RCH2CH2OH ⇌ RCH = CH2 + H2O
(b) Low H2O concentration and high temperature favor dehydration because the volatile alkene can be removed
from the reaction mixture by distillation, thereby shifting the equilibrium to the right. Alkenes are hydrated
at lower temperatures with dilute acid which provides a high concentration of the reactant H2O to shift the
equilibrium to the left.
113. (a) Write the major product from the reaction of an unsymmetrical alkene, such as isobutylene, with the following
unsymmetrical addenda: (i) HBr, (ii) H2O(H+), and (iii) ClOH. (b) State the rule for getting the correct answers
to part (a), (c) Give the general name for the reactions that give mainly one of several possible products.
Ans. (a) (i) (CH3)3CBr, (ii) (CH3)3COH, and (iii) (CH3)2COHCH2Cl. (b) The Markovnikov rule states that E+ adds to
the double-bonded C that has more H’s, followed by addition of :Nu– to the C with less H’s. If E+ is a proton,
‘the rich get richer’, (c) Regioselectiue.
12. Which of the following alkene on acid catalysed hydration form 2-methyl propan-2-ol.
(a) (CH3)2CH = CH2 (b) CH3 – CH = CH2
(c) CH3 – CH = CH – CH3 (d) CH3 – CH2 – CH = CH2
SOLUTION
12. Addition of H2O occurs according to Markownikoff’s rule.
CH3 CH3
+
H
CH3 – C = CH 2 + H2O CH3 – C + CH3
CH3
\ (A)
Hydrocarbon 3.65
12. Hydroboration-Oxidation
With the reagent diborane, (BH3)2, alkenes undergo hydroboration to yield alkylboranes, R3B, which on oxidation give
alcohols. For example,
H2C = CH2 H2C = CH2
(BH3)2 CH3CH2BH2
Diborane H2C = CH2
(CH3CH2)2BH (CH3CH2)3B
OH –
Triethylboron
(CH3CH2)3B + 3H2O2 3CH3CH2OH + B(OH)3
Triethylboron Hydrogen Ethyl alcohol Boric acid
peroxide
The reaction procedure is simple and convenient, the yields are exceedingly high, and, as we shall see, the products are
ones difficult to obtain from alkenes in any other way.
Diborane is the dimer of the hypothetical BH3 (borane) and, in the reactions that concern us, acts much as though it
were BH3. Indeed, in tetrahydrofuran, one of the solvents used for hydroboration, the reagent exists as the monomer, in the
form of an acid-base complex with the solvent.
H H H H H
H B B B H BO
H H H H H
Borane Diborane Borane-tetrahydrofuran
complex
Hydroboration involves addition of BH3 (or, in following stages, BH2R and BHR2) to the double bond, with hydrogen
becoming attached to one doubly bonded car: bon, and boron to the other. The alkylborane can then undergo oxidation, in
which the boron is replaced by—OH.
Hydroboration Oxidation
H2O2, OH–
C=C +H–B C–C C–C
Alkene H B H OH
Alcohol
H–B = H – BH2, H – BHR, H – BR2
Thus, the two-stage reaction process of hydroboration-oxidation permits, in effect, the addition to the carbon-carbon
double bond of the elements of H—OH.
Reaction is carried out in an ether, commonly tetrahydrofuran or ‘diglyme’ (diethylene glycol methyl ether,
CH3OCH2CH2OCH2CH2OCH3). Diborane is commercially available in tetrahydrofuran solution. The alkylboranes are not
isolated, but are simply treated in situ with alkaline hydrogen peroxide.
Mechanism of hydroboration (regio- and stereoselectivity of the reaction)

Much of the usefulness of hydroboration-oxidation lies in the ‘unusual’ orientation of the hydration. The —OH takes
the position occupied by boron in the intermediate alkylborane, and hence the final product reflects the orientation of the
hydroboration step. But is this orientation really ‘unusual’?
The orientation appears to be unusual because hydrogen adds to the opposite end of the double bond from where it adds
in ordinary electrophilic addition. But the fundamental idea in electrophilic addition is that the electrophilic part of the
reagent—the acidic part—becomes attached, using the p electrons, in such a way that the carbon being deprived of the p
electrons is the one best able to stand the deprivation. In the addition of HZ to propylene, for example, the proton attaches
itself to C-1; in that way the positive charge develops on C-2, where it can be dispersed by the methyl group. A secondary
carbocation is formed instead of a primary.
δ+
HZ
CH3 – CH = CH2 CH3 – CH = CH2 CH3 – CH – CH3 + : Z
⊕
Z
3.66 Hydrocarbon
Now, what is the center of acidity in BH3? Clearly, boron, with only six electrons. It is not at all surprising that boron
should seek out the p electrons of the double bond and begin to attach itself to carbon. In doing this, it attaches itself in
such a way that the positive charge can develop on the carbon best able to accommodate it. Thus:
δ+
CH3 – CH = CH2
δ
H – B –− H
H
Unlike ordinary electrophilic addition, however, the reaction does not proceed to give a carbocation. As the transi-
tion state is approached, the carbon that is losing the p electrons becomes itself increasingly acidic: electron-deficient
boron is acidic but so, too, is electron-deficient carbon. Not too far away is a hydrogen atom held to boron by a pair of
electrons. Carbon begins to take that hydrogen, with its electron pair; boron, as it gains the p electrons, is increasingly
willing to release that hydrogen. Boron and hydrogen both add to the doubly bonded carbons in the same transition
state:
δ+
CH3 – CH CH2 Transition state for
δ− hydroboration
H B
In view of the basic nature of alkenes and the acidic nature of BH3, the principal driving force of the reaction is almost
certainly attachment of boron to carbon. In the transition state attachment of boron to C-l has proceeded to a greater extent
than attachment of hydrogen to C-2. Thus, loss of (p) electrons by C-2 to the C(1)—B bond exceeds its gain of electrons
from hydrogen, and so C-2, the carbon that can best accommodate the charge, has become positive.
On theoretical grounds it has been postulated that the step we have described must follow a preliminary step in which
boron attaches itself to both carbon atoms, or perhaps to the p electrons.
Thus, orientation of addition in hydroboration is controlled in fundamentally the same way as in two-step elec-
trophilic addition. Hydrogen becomes attached to opposite ends of the double bond in the two reactions because
it adds without electrons in one case (as a proton, an acid), and with electrons in the other case (as a hydride ion, a
base).
Because of the Lowry-Brfnsted treatment of acids and bases, we tend to think of hydrogen chiefly in its proton
character. Actually, its hydride character has considerably more reality. Solid lithium hydride, for example, has an ionic
crystalline lattice made up of Li+ and H–; by contrast, a naked unsolvated proton is not encountered by the organic
chemist.
We are already familiar with the facile transfer of hydride from carbon to carbon: within a single molecule (hydride
shift in rearrangements), and between molecules. Later on, we shall encounter a set of remarkably versatile reducing
agents (hydrides like lithium aluminum hydride, LiAlH4, and sodium borohydride, NaBH4) that function by transfer of
hydride ion to organic molecules.
This is a syn addition, i.e., hydrogen and boron add from the same side of double bond. The trialkyl borane formed can
be used for various synthetic reactions described below.
There is an easier way out to arrive at the product of hydroboration oxidation process. The overall process is the
addition of H2O. In this process –OH group adds to less sterically hindered carbon of the double bond and ‘H’ adds
to the other carbon of the double bond. The ‘H’ comes from BH3 whereas –OH group comes from oxidizing
agents OH⊝/ H2O2.
1 BD3/T.H.F
2 OH /H2O2 OH
D
Hydrocarbon 3.67
Mechanism for oxidation

O OH O
H H H + H2O
O O
R
R
R B
O R B O
R H H
O R O
R O R
B O R B O R
R O R
hydrolysis of trialkony borome
3R – OH + H3BO3
The orientation of hydroboration is affected, not just by the polar factor we have just described, but also by a steric factor:
attachment of the boron moiety of the reagent (not just —BH2, remember, but the larger —BHR and —BR2) takes place
more readily to the less crowded carbon of the double bond. Since this in general would lead to the same orientation as
would the polar factor alone, it is not easy to tell which factor is in control. We can, however, expect this much: the bulkier
the substituents on the alkene, the more important the steric factor; the more strongly electron-releasing or electron-
withdrawing the substituents, the more important the polar factor.
(BH3)2 H2O2, OH CH3 H

syn-Addition
H3C H OH
methylcyclopentane trans-2-Methyl-1-cyclopentanol
RX
RNH2 ROH
RNHR′ X2 RH
NH2Y base H2O2
R′N3 OH–
R′CO2H
RSR′ isomerization
(R′S)2
heat
AgNO3 heat with alkene

R–R R3B R–H
OH–
CH2 = CHCOZ (i) CO

(ii) OH–, H2O2
RCH2CH2COZ BrCH2COZ
(i) CO, (i) CO, H2O R3COH
or
LiAlH4 (ii) H2O2,
N2CHCOZ
(ii) H2O2, NaOCOCH3
X = Br, l phosphate
RCH2COZ buffer RCOR
Y = Cl, OSO3H
Z = H, R′, OR′ RCHO
3.68 Hydrocarbon
Illustrations
114. (a) Supply the condensed formulae and names for the products from the reaction of three moles of propene and
only one mole of BH3 in tetrahydrofuran (THF), a cyclic ether. (b) Give the formulae of the intermediate products
formed in this stepwise reaction. (c) Name this addition reaction. (d) Identify the electrophile and regiospecificity.
(e) Why must BH3 be used in an ether solution and how is it made?
Ans. (a) Pr3B,tripropylborane, an organoborane. (b) PrBH2, propylborane, and Pr2BH, dipropylborane.
(c) Hydroboration. (d) BH3 is the electrophile and, since it adds to the C with the greater number of H’s, it is a
Markovnikov-type addition. (e) BH3 by itself does not exist. Its dimer B2H6 is known, but it is air and moisture
sensitive. When B2H6 is dissolved in THF, it breaks down to BH3, which is stabilized by forming a coordinate
covalent bond with the O of the ether, R2O:BH3.
115. (a) Give the monoalkylborane formed from Me3CCH=CH2(E) and B2H6/THF. (b) What mechanistic information
about hydroboration is afforded by the isolation of the product in (a)? (c) Provide a mechanism for the reaction.
(d) Can the trialkylborane of E be formed? Explain.
Ans. (a) Me3CCH2CH2BH2. (b) It cannot be a typical two-step reaction whose first step generates a 2° R+,
(a) Me3CCH2CH2BH2, that would undoubtedly rearrange to the more stable 3° R+, Me2CCHMeCH2BH2.
(c) The addition is believed to occur in two steps. Step 1 is the formation of the p complex A between boron and
the p bond. In step 2, A goes through a four-centered TS, B, to the product.
H t BH2 H
H
H H H
B H B H H C C
H H R
C C H H H
A C C C
H H B product, R = CMe3
R R
(d) The dialkylborane (Me3CCH2CH2)2BH is too sterically hindered to add to the hindered alkene.
116. (a) Give the products from the reactions of tripropylborane, formed from propene and BH3, with (i) H2O2 + OH–
and (ii) Br2. (b) What is the net regiospecificity of the addition to propene? (c) Name each type of reaction.
Ans. (a) (i) CH3CH2CH2OH and (ii) CH3CH2CH2Br. (b) Anti-Markovnikov. (c) (i) Hydroboration-oxidation and
(ii) hydroboration-halogenation (specifically, bromination).
117. (a) Give the product from the hydroboration-oxidation of 1-methylcyclopentene. (b) Classify the mode of
addition.
H H H2O2/OH– H
Ans. BH3/THF
Me Me
Me BH2 OH
1-Methylcyclopentene H H
trans-2-Methylcyclopentanol
118. Deduce the structures of the products from hydroboration-bromination of: (a) (Z)- and (E)-2,3-dideutero-
2-butene and (b) 1,2-dideuterocyclohexene.
Ans. (a) Syn-addition gives a racemic mixture of the diastereomer A from the (Z)-alkene and B from the (E)-alkene.
D
1. BH3/THF Br Br
C Me H D + D H
D C 2. Br2
Me Me D
D
Me Me Me
(Z)-2,3-Dideutero-2-butene rac, erythro-2-Bromo-2,3-dideuterobutane, A
D
1. BH3/THF Br Br
Me C Me 2. Br2 H D D H
C Me Me
Me + Me
D D D
(E)-2,3-Dideutero-2-butene rac, threo-2-Bromo-2,3-dideuterobutane, B
Hydrocarbon 3.69
1. BH3/THF
D D + D D
2. Br2
D D
H Br Br H
rac, cis-1, 2-Dideuterobromocyclohexane
119. From 1-pentene (A) prepare (a) CH3CH2CH2CHDCH3 (B), (b) CH3(CH2)3CH2D (C), (c) CH3CH2CH2CHDCH2D
(D) (use 3 methods).
Ans. (a) A BD
3 / THF
→(CH 3 CH 2 CH 2 CHDCH 2 )3 B HOAc
 → B.
(b) A BH
3 / THF
→(CH 3 CH 2 CH 2 CH 2 CH 2 )3 B DOAc
 → C.
(c) React A with (1) D25/Pd, (2) D2NND2 + H2O2, (3) BD3/THF, then DOAc → D.
14. Oxymercuration-demercuration
Alkenes react with mercuric acetate in the presence of water to give hydroxy-mercurial compounds which on reduction
yield alcohols.
Oxymercuration Demercuration
NaBH3
C = C + H2O + Hg(OAc)2 —C — C— —C — C—
Alkene Water Mercuric OH HgOAc OH H
acetate
—OAc = CH3COO—
The first stage, oxymercuration, involves addition to the carbon-carbon double bond of —OH and —HgOAc. Then, in
demercuration, the —HgOAc is replaced by —H. The reaction sequence amounts to hydration of the alkene, but is much
more widely applicable than direct hydration.
There is easier way to get the product of oxymercuration and demercuration. The overall process is the addition of H2O
molecule. First, we add H⊕ to the C=C to form the more stable carbocation, but we do not rearrange the carbocation even
when rearrangement is possible. Thereafter we add OH⊝ to the carbocation. Remember ‘OH’ group comes from H2O and
‘H’ comes from NaBH4.
The method described above does not correspond to the actual mechanism but it is very effective when you want to get
the product of any mercuration–demercuration.
+J'2
1D%+
+
2'
2'

GRQRWJRIRUUHDUUDQJHPHQW
RIWKLVFDUERFDWLRQ
3.70 Hydrocarbon
The two-stage process of oxymercuration-demercuration is fast and convenient, takes place under mild conditions, and
gives excellent yields—often over 90 per cent. The alkene is added at room temperature to an aqueous solution of mercu-
ric acetate diluted with the solvent tetrahydrofuran. Reaction is generally complete within minutes. The organomercurial
compound is not isolated but is simply reduced in situ by sodium borohydride, NaBH4. (The mercury is recovered as a ball
of elemental mercury.)
Oxymercuration-demercuration is highly regioselective, and gives alcohols corresponding to Markovnikov addition of
water to the carbon-carbon double bond. For example,
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&+ &+
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&+
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Oxymercuration involves electrophilic addition to the carbon-carbon double bond, with the mercuric ion acting as
electrophile. The absence of rearrangement argues against an open carbocation as intermediate. Instead, it has been
proposed, there is formed a cyclic mercurinium ion, analogous to the bromonium and chloronium ions involved in
the addition of halogens. In 1971, Olah reported spectroscopic evidence for the preparation of stable solutions of such
mercurinium ions, and they have since been observed in the gas phase.

²&²&²
+J
The mercurinium ion is attacked by the nucleophilic solvent—water, in the present case—to yield the addition product.
As hi halohydrin formation, the Markovnikov orientation is just what we would expect if the intermediate were an open
carbocation, with the mercuric ion adding in such a way as to form the more stable cation.
Rearrangements can occur, but are not common. The reaction of 3,3,-dimethyl-1-butene shown above illustrates the
absence of the rearrangements that are typical of intermediate carbocations.
Mercuration can be carried out in different solvents to yield products other than alcohols. This use of solvomercuration
as a general synthetic tool is due largely to H. C Brown.
Hg(OAC)2, H2O NaBH4
Norbornene
OH
exo-Norborneol
Hydrocarbon 3.71
Illustrations
120. (a) Supply the structures for A and B in the following two-step reaction:
Hg(OAC)2 NaBH4 /NaOH
C3H7CH = CH2 A B
THF/H2O
(b) What is the net regiospecificity of this hydration? (c) Name (i) the first step and (ii) the second step. (d) Why
is this hydration procedure superior to acid-catalyzed hydration of most alkenes? (e) What is the final state of Hg?
Ans. (a) A is C3H7CH(OH)CH2— HgOAc, an organomercurial alcohol; B is C3H7CH(OH)CH3. (b) Markovnikov
addition, (c) (i) Oxymercuration (a type of solvomercuration) and (ii) demercuration. (d) It precludes
rearrangement, (e) Reduction to Hg°.
121. (a) Give the stereoisomer formed when cyclohexene is oxymercurated. (b) Suggest a mechanism for the
oxymercuration step.
Ans. (a) Trans. (b) The electrophile of Hg(OAc)2 is AcOHg+ that adds to C=C to form a mercurinium ion similar to a
bromonium ion. The mercurinium ion then reacts with H2O (not OAc–) at the more substituted C for the same
reason and in the same way as does the bromonium ion.
+
HgOAC HgOAc
–
OAc
H2O [RCH – CH2] RCH – CH2 + HOAc
mercurinium ion
OH
122. Give, in tabular form, the major alcohol formed by (a) oxymercuration-demercuration, (b) H+-catalyzed hydration,
and (c) hydroboration-oxidation of: (i) 1-heptene, (ii) 1-methylcyclohexene, (iii) methylenecyclobutane, and
(iv) bicyclo[2.2.1] heptene (norbornylene).
Ans. See Table 3.5.
In compound (iv), AcOHg+ attacks from exo side, H2O from the endo side (trans) to give the endo alcohol, while
BH3 approaches from the exo side to give the exo alcohol (syn addition). The intermediate R+ from the H3O+
attack reacts to give the more stable product, which is the exo alcohol.
Table 3.5
(a) (b) (c)

(i) C5H11CHOHCH3 C5H11CHOHCH3 C6H13CH2OH
Me Me
(ii) H Me
OH OH
HO H
Me H CH2OH
(iii)
H
OH OH
H H OH
(iv)
OH OH H
3.72 Hydrocarbon
123. Contrast (a) H+-catalyzed hydration. (b) hydroboration-oxidation, and (c) oxymercuration-demercuration in
terms of (i) regiospecificity, (ii) mode of addition, and (iii) susceptibility to rearrangement.
Ans.
(a) (b) (c)
(i) Markovnikov Anti-Markovnikov Markovnikov
(ii) No clear stereospecificity Syn No clear stereospecificity
(iii) Yes No No
Remember, acid catalyzed hydration of alkene produces alcohol with the rearrangement of carbocation, (whenever
possible) but hydroboration, oxidation oxymercuration-demercuration are the processes to get alcohol without
rearrangement. The following reactions explain this point.
2+
+ 2
2+
%+7+)
±
2+ +2
2+
+J 2$F +2
1D%+
Hope that you can find the mechanism of these reactions to get those product.
15. Dimerization
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+& +& +&
&+ &+
+& +&
&+ &+
WULPHWK\OSHQWHQHWULPHWK\OSHQWHQH
Illustration
124. The reaction of Me2C=CH2 with H2SO4 or HF gives two isomers, C8H16. (a) Give their structural formulae and
designate the major isomer. (b) What is the general name for this reaction? (c) Account for the unexpected
product ratio. (d) Provide a mechanism. (e) Why cannot HCl, HBr, or HI be used as acid catalysts?
Ans. (a) Me3C — CH=CMe2 (minor) (A); Me3C —CH2C(Me)=CH2 (major) (B)
(b) The reaction is called dimerization.
(c) The expected Saytzeff product A is sterically hindered because the bulky t-butyl group is cis to a Me.
Hydrocarbon 3.73
(d) Step 1. Me2C = CH2 + H+ → Me3C+

Step 2. 0H&+& &0H 0H&±&+±&±&+
³WDLO´ ³KHDG´ + 0H +c
HOHFWURSKLOH QXFOHRSKLOH GLPHULF5
+ +
Step 3. R + −
H
→ A and R + −H
→B
Step 2 is a Markovnikov addition of an electrophile. Attack at the ‘tail’ gives the 3° R+; attack at the ‘head’ would
give the much less stable 1° carbocation Me3C—CMe2CH2.
(e) The acid catalyst must have a weakly nucleophilic conjugate base to avoid addition of HX to C=C. Cl–, Br–,
and I–, the conjugate bases of HCl, HBr, and HI respectively, are good nucleophiles that bind to R+.
Addition Dimerization and Polymerization

16. Alkylation of Alkene
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17. Polymerisation
When large number of smaller molecules combines at high temperature and high pressure in the presence of a catalyst to
form large molecules is called polymerisation. The simple compounds from which the polymers are obtained are called
monomers. For example
KLJKWHPSSUHVVXUH
Q &+ &+ &+±&+
&DWDO\VW Q
3RO\WKHQH
KLJKWHPSSUHVVXUH
Q &+±&+ &+ &+±&+
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&+
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&+ &+ &+±&+
Q
KLJKWHPSSUHVVXUH
Q
&DWDO\VW
3RO\VW\UHQH
3.74 Hydrocarbon
These reactions are normally promoted by free radical initiator. If electron withdrawing groups are present then it is
anionic polymerisation and will be initiated by nucleophile.
Cl Cl
| |
CH = CH 2 (− C H 2 − CH 2−) n
PVC
R R CN CN
| | | |
C H = CH 2 (− C H − CH 2 −) n ; C H = CH 2 (− C H − CH 2 −) n
Acrylonitrile polyacrylonitrile
CH 3 CH 3
| |
CH 2 = C − CH = CH 2 (−CH 2 − C = CH − CH 2 −) n
Isoprene Natural rubber ( polyisoprene ) (1, 4 − addition )
Cl Cl
| |
CH 2 = C− CH = CH 2 (−CH 2 − C = CH − CH 2 −) n
Chlorprene Neoprene
Illustration
125. Describe (a) radical-induced and (b) union-induced polymerization of alkenes. (c) What kinds of alkenes undergo
anion-induced polymerization?
Ans. (a) A radical initiator, RO. from decomposition of ROOR, adds according to Markovnikov’s rule as shown with
MeCH=CH2
H2C = CHMe
RO. + H2C = CHMe H2C – CH H2C–CH–CH2CH
RO Me RO Me Me
This process continues with thousands of monomeric molecules. The polymerization chain terminates when two
long chain intermediate radicals either combine, R. + R. → R — R, or disproportionate.
(b) Anions such as R: –, generated from organometallics or :NH2– (from LiNH2), initiate the polymerization by
adding to one end of the monomer.
–
R:– + H2C = CHX RCH2CH H2C = CHX RCH2CH — CH2CH
X X X
(c) Since ordinary alkenes do not undergo nucleophilic addition, the alkene must have a functional group, such
as —C = N or O=COR, on C=C that can stabilize the negative charge by delocalization
18. Oxidation Reaction

(1) Oxidation without Cleavage:
This oxidation is given by mild oxidising agents. The products of the oxidation without cleavage are either epoxides
or 1,2 diols.
(A) Formation Of Epoxides: Formation of epoxide takes place as follows:
2+
$J2RU
5&22+ +2+
& & &±&
$QWLDGGLWLRQ
2 ULQJRSHQLQJ
HSR[\DONDQH 2+
Hydrocarbon 3.75
(B) Diol Formation:

The most popular reagent used to convert an alkene to 1, 2-diol is a cold alkaline aqueous solution of potassium
permanganate (known as Baeyer’s reagent). Osmium tetra oxide (OsO4) is also used for the same purpose but the
use of this reagent is limited because it is both expensive and toxic. Both of these reagents form cyclic inorganic
esters with alkenes which yield vicinal diol on hydrolysis catalysed by base. Reaction with Bayer’s reagent is
used as a test of unsaturation as purple pink colour of KMnO4 will be disappeared.
.0Q2± +2+2+
±
& & &±& &±& 0Q2.2+
2 2 2+ 2+
0Q
2 2.
This addition comes under syn addition
& & 2 2 1D+62 & 2+
2V2 2V +2+
2V2
& & 2 2 & 2+

Oxidation of alkyne with Bayer’s Reagent.
2+ 2+
%D\HU¶V 2[LGDWLRQ %D\HU¶V5HDJHQW
5±&Ł&+
5HDJHQW
5 & &+ 5 & &++2 5 & &22+
2+ 2+ 2 2 2
Illustrations
126. (a) Give the product of the reaction of a peroxyacid such as peroxybenzoic acid, PhCOOH, with
(i) cyclopentene, (ii) cis-2-butene, and (iii) trans-2-butene. (b) Consider the reaction as an electrophilic
addition.
Ans. (a) The product is a 3-membered ring ether called an epoxide or oxirane. The epoxide has the same geometry
as the alkene reactant. The epoxide can be considered as the oxygen analog of a bromonium ion without a +
charge. However, it is isolable unlike the bromonium ion.
+ +
2 2
0H 0H
+
+ 0H 0H
+
L + 2 LL LLL
(b) The HO of the peroxyacid can be considered as an E+. However, the =Nu– portion, RCOO–, removes the H
from OH as the O bonds to the C=C, giving the epoxide directly.
127. (a) Give the products from the reaction at room temperature of peroxyformic acid (from 35% H2O2
and formic acid, HCOOH) with the same three reactants in (a) of illustration 126. (b) What is the net
addition and the mode? (c) Provide a mechanism using cw-2-butene. (d) Name the overall addition in
part (c).
(a) (i) trans-1,2-Cyclopentanediol, (ii) rac-, and (iii) w«o-CH3CHOHCHOHCH3.
(b) Two OH’s add anti.
(c) HCOOH in the reaction mixture has sufficient acidity to catalyze the opening of the epoxide ring by H2O in
the same anti fashion as does the bromonium ion ring:
3.76 Hydrocarbon
OH
H + H H H Me
O HO H 2 OH
2 Me HCOOH 2 Me H2O Me
1 1 Me +
H H –H
+
H OH
Me Me OH Me
(racemate) (SS)-Glycol (RR)-Glycol
(from attack at C1) (from attack at C2)
(d) Hydroxylation.
128. (a) Give the products from the reactions of the same three reactants in (a) of illustration 126 at room temperature
with basic aqueous KMnO4 or with catalytic amounts of OsO4 (osmium tetroxide) in H2O2. (b) What is the net
addition and the mode? (c) Provide a mechanism using trans-2-butene. (d) Why is KMnO4 preferred to OsO4?
Ans. (a) (i) cis-1,2-Cyclopentanediol, (ii) meso-, and (iii) rac-CH3CHOHCHOHCH3.
(b) Syn hydroxylation.
MnO2– OH
Me
topside OMe O OH
H H
Me attack
H H Me (RR)
C H Me aq. OH
–*
+
(c) H C + Me + [MnO3–]
Me H
Me
H Me H
Me bottomside H
attack
OH
O
OH
O – MnO2– MnO2
(SS)
cyclic intermediates enantiomers
*OH– is used to hydrolyze the Mn complex; H2O2 oxidatively cleaves the Os complex. A similar metal complex is
formed in both cases. When M is Mn, the complex has a – charge delocalized to the lone O’s. There is no charge
on the isolable osmate complex. In the breakdown of the cyclic complexes, the C—O bonds are not broken, their
geometry is not disturbed, and the syn addition is preserved.
(d) OsO4 is expensive and very toxic; it causes blindness. This problem can be minimized by using a catalytic
amount of OsO4 with H2O2 which regenerates the OsO4 by oxidizing the reduced form of Os resulting from
the hydroxylation.
13. The compound most likely to decolourise a solution of potassium permanganate is
CH3
(A) H2C == CH2 (B) (C) (D)
H3C CH3
SOLUTION
13. It is a test for unsaturation. As benzene and naphthalene is also unsaturated, but they are stabilized
due to resonance, and thus does not give Bayer’s test.
\ (A)
Hydrocarbon 3.77
(2) Oxidation with Cleavage: Oxidative Cleavage:

(i) Cleavage with hot basic/Acidic KMnO4:
With hot acidic KMnO4 ;
Products of Oxidation are:
Illustration
129. (a) How does the reaction of a hot acidified KMnO4 (or K2Cr2O7) solution with alkenes differ from hydroxylation?
(b) Summarize the relationship between the R substitution on C = C and the products formed on oxidative cleavage.
(c) Give the expected products formed from hot KMnO4 oxidation of (i) the C4H8 alkenes, (ii) cyclobutene, (iii)
1-methylcyclobutene, and (iv) 1,2-dimethylcyclobutene.
Ans. (a) This vigorous oxidative cleavage converts the C = C to C = O + O = C . Any H on a doubly-bonded
C is further oxidized to OH.
(b) A terminal =CH2 is oxidized to unstable carbonic acid, O = C(OH)2, that decomposes to CO2 and H2O. The
= CHR grouping is converted to HOOCR, a carboxylic acid, while =CR2 and =CRR’ go to ketones, O = CR2
and O = CRR’, respectively. A glycol is likely to be the intermediate that actually undergoes cleavage.
(c) (i) CH3CH2–CH = CH2– CH3CH2C = O + CO2
OH
CH3CH = CHCH3 CH3C = O + O = CCH3
cis or trans
OH OH
(CH3)2C == CH2 → (CH3)2C == O + CO2
(ii) HOOCCH2CH2COOH
(iii) HOOCCH2CH2 C = O
CH3
(iv) O = CCH2CH2C = O
CH3 CH3
Oxidative cleavage of alkenes

This type of reaction is of much less value in synthesis than it is (or was) in degradative structural determination. Oxidative
cleavage of a carbon-carbon double bond leads generally to aldehydes, ketones or carboxylic acids, and it is seldom that
an alkene is the most convenient source of any of these. We have already drawn attention, however, to the value of oxida-
tive cleavage as a ring-opening procedure and there are also occasions when an alkene may be used as a latent carbonyl
function in a multi-stage synthesis.
3.78 Hydrocarbon
There are two principal methods for bringing about this cleavage. The first involves hydroxylation and subsequent
oxidation of the diol using potassium permanganate, lead(IV) acetate or a periodate. The second involves ozonization of
the alkene [reaction)], a sequence of reactions involving a 1,3-dipolar cycloaddition of ozone, a pericyclic ring opening
(‘retro-cyclo addition’) and a second 1,3-dipolar cycloaddition):
O R
3
O O O
+ R O
O O 1 R
1
R
3
R
1
R
3
O3 R
1 3
R R
O 4
2 4 2
R
2 O R
R R R
2
R
4
R
The primary product, the ozonid, is not isolated but is converted directly into the required carbonyl compounds. Re-
ductive work-up (e.g., using zinc and acetic acid or a complex metal hydride or a tervalent phosphorus reagent) produces
aldehydes or ketones (although excess of the reducing agent may react with these, e.g., the use of lithium aluminium
hydride gives alcohols):
H R1 R3
O OH
R1 O+ O + H2O
R3
R2 O R4 R 2
R 4
R3P:
or
O O R1 R3
R1 R3
O+ O + R3PO
R2 O R4 2 4
R R
Oxidative work-up usually involves a peroxy acid and possibly involves hydrolysis as the first step. Under such condi-
tions the products are carboxylic acids or ketones:
R1 O O R3 R3 R1 O OH R1
H2O
21 R4 O+ O + H2O2
R2
OH O H R4 R2 OH R2
(R4 = H) (R2 = H)
R3 CO2H R1 CO2H
(*If the number of carbon atoms per molecule does not change on ozonolysis the dooble bond must be within a ring
and the ring contains only one double bond.)
For example,
HC = O O = CH
HC = O O = CH
H 2C CH2 HC CH2
and 2
CH2 HC = O O = CH
(ring contains more
than one double bond)
(a) What are the experimental conditions for this reaction? (c) What is the main utility of this reaction and why is it supe-
rior to KMnO4 cleavage for this purpose?
(b) Ozone is generated at about 8% concentration in an ozonizer by passing a stream of dry O2 through an electric
discharge. It passes through a solution of alkene in CH2Cl2 or CH3OH. The explosive ozonide is reduced with Me2S
or Zn and HOAc without being isolated.
(c) It locates the position of C=C’s in molecules. KMnO4 cleavage is more vigorous and can oxidize other groups,
i.e., OH.
Hydrocarbon 3.79
Illustrations
130. Write the structures for the products from reductive ozonolysis of: (a) 3,5-Dimethyl-4-octene, and
(b) 1,2-dimethylcyclohexene.
CH3 CH3 CH3 CH3
1. O3
Ans. (a) CH3CH2CHCH = CCH2CH2CH3 CH3CH2CHCH = O + O = CCH2CH2CH3
2. Zn, HOAc
2-methylbutanal 2-pentanone
(an aldehyde) (a ketone)
O O
(b) CH3C(CH2)4CCH3 A cycloalkene gives only a dicarbonyl compound.
131. Give the products formed on oxidative-ozonolysis (ozonide is cleaved with H2O2) from the compounds
OH
Ans. The aldehydic group, —CH=O, is oxidized to the carboxylic acid group, —C = O
(a) CH3CH2CH(CH3)COOH + O = C(CH3)CH2CH2CH3, (b) no change.
132. Write structural formulae for the compounds which yield the following products on reductive ozonolysis:
(a) two moles of O == C(CH3)CH2CH3 (b) H2C == O + O == CHCH(CH3)CH(CH3)2
(c) O == CHCH2CH2CH2CH == O (d) (C2H5)2C == O + O == CHCH == O + O == CHCH2CH3
(e) two moles O == CHCH2CH == O
Ans. (a) The formation of a single carbonyl compound signals a symmetrical alkene. Write twice the structural formula
of the ketone with the C = O groups facing each other. Omit the O’s and join the C’s with a double bond.
CH3 CH3 H3C CH3
CH3CH2C = O O = CCH2 CH3 CH3CH2C = CCH2CH3 (cis or trans)
(b) Two different carbonyl compounds means the alkene is unsymmetrical.
H2C=O O = CHCH(CH3)CH(CH3)2 ← H2C = CHCH(CH3)CH(CH3)2
(c) The presence of two C = O’s in the same product indicates a cycloalkene, in this case cyclopentene.
HC = O O = CH
H2C CH2
CH2
(d) A total of four C=O’s in the products indicates a diene, a compound with two C = C’s.
(C2H5)2C=O + O=CHCH=O + O=CHCH2CH3 ← (C2H5)2C=CHCH = CHCH2CH3 (cis or trans)
(e) Two moles of a dicarbonyl compound signal a symmetrical cycloalkadiene
HC = O O = CH
H2C CH2
HC = O O = CH
14. (i) An Olefines was treated with ozone and the resulting product on reduction (reductive
ozonolysis) gave 2-pentanone and acetaldehyde. What is the structure of olefin? Write the reaction
(ii) How many gm of Br2 will reaction with 5 gm of (a) Pent-1-ene; (b) Pent-1-yne; (c) Pentanes.
3.80 Hydrocarbon
SOLUTION
14. (i) Alkene is H3 C CH2 -CH2 -CH3
C
HC
CH3
(Z)-3-methylhex-2-ene
H3 C-H 2 C-H 2 C
H3 C-H 2 C-H 2 C O
O3
H3 C C CH 3
C CH CH
H3 C CH 3
O O
H2 O/Zn
H3 C-H 2 C-H 2 C CH 3
C O + O HC
H3C
H3C CH2 Br
CH2 CH
+ Br2 CH2 HC
(ii) (a) H3C CH2 CH2
pent-1-ene CH 2
Br
70 gm 160 gm
so 5 gm 11.42 gm
H3 C CH 2 Br Br
CH 2 C
(b) H3 C CH 2 CH + 2Br 2 CH 2 C HC
pent-1-yne
Br Br
68 gm 320 gm
so 5 gm 23.53 gm
H3 C CH 2 CH 3
(c) CH 3 CH 2 CH 2 CH 2 CH 3 + 1/ 2 Br2
CH2HC
pentane
Br
72 gm 80 gm
so 5 gm 5.55 gm
Hydrocarbon 3.81
19. Addition Reaction in Dienes
Illustrations
133. Give the structural formulae and 1UPAC names of the unbranched isomeric dienes, C5H8.
Ans. (i) H2C = C=CHCH2CH3, 1,2-pentadiene; (ii) H2C = CH—CH = CHCH3, 1,3-pentadiene, Z and E; (iii) H2C =
CHCH2CH = CH2, 1,4-pentadiene; (iv) CH3CH=C = CHCH3, 2,3-pentadiene.
134. Categorize the three kinds of dienes in Question 130.

Ans. (i) and (iv) Cumulated dienes (allenes) with two double bonds on the same C. (ii) Conjugated diene with alternating
C=C and C—C bonds, (iii) Isolated diene with at least one sp3 hybridized C between the C=C groupings.
135. Compare the stabilities of the three types of dienes in Question 130 from their heats of hydrogenation, DH,
(in kcal/mol): (i) –70, (ii, E) –54, and (iii) –61. For comparison, for 1-pentene is –30.1 kcal/mol.
136. Draw and give the stereochemical designation for the geometric isomers of 2,4-heptadiene.
Ans. Each double bond can generate geometric isomers.
HH H3C H
H 3C C=C C=C H
C=C C2H5 H C=C
H H H C2H5
Z,Z isomer E,E isomer
H C2H5 H3C H
H 3C C=C C=C C2H5
C=C H H C=C
H H H H
Z,E isomer E,Z isomer
137. Give the industrial synthesis of 1,3-butadiene.

Ans. Industrial syntheses require inexpensive starting materials. In this case, butane, isolated by fractional distillation
of petroleum, is dehydrogenated (— 2H2) with a heterogeneous catalyst.
138. Synthesize 1,3-butadiene from 1-butene.

Ans. H 2 C = CHCH 2 CH 3 
NBS
→ H 2 C = CHCHBrCH 3 
aic. KOH
→ H 2 C = CHCH = CH 2
139. Synthesize 1,3-butadiene from acetylene.

Ans. 2HC ≡ CH 
CuCl
NH 4 Cl
→ H 2 C = CHC ≡ CH 
H 2 / P1
(BaSO4 )
→ H 2 C = CHCH = CH 2
140. Synthesize H2C=CHCH2CH2CH = CH2 (C) from propene.

Ans. Going from a three-carbon to a six-carbon molecule requires a coupling reaction best achieved by a Corey-House
synthesis.
2H 2 C = CHCH 3 (A) →
C12
∆
2H 2 C = CHCH 2 C1 
1. Li
2. Cul
→ (H 2 C = CHCH 2 ) 2 CuLi (B); A + B → C
141. Prepare 1,3-cyclohexadiene from cyclohexane.

Cl2 Cl alc. KOH NBS Br alc. KOH
Ans.
hv
3-Bromo-cyclohexene
3.82 Hydrocarbon
Reaction
Addition reaction of conjugated diene are of two types 1,2 and 1,4-addition. 1,2-Addition kinetically controlled re-
action which depends on stability of intermediate and rate of slowest step the reaction which is also called rate
determining step.
1,4-addition reaction depends on stability of the product formed. These reactions takes place comparatively at high
temperature and their intermediates are comparatively less stable. Product of 1,4-addition are called thermodynamically
controlled products.
Θ Θ Θ ⊕
CH2 = CH − CH = CH2 CH2 − C H CH = CH2 C H2 − CH = CH − CH2
Examples
Addition of Bromine
Br2
CH 2 = CHCH = CH 2 CH2 CHCH = CH 2 + CH 2 CH = CH CH 2
–15°C
1,3−Butadiene
Br Br Br Br
54% 46%
(1,2−addition) (1,4−addition)
Thus extensive delocalization occurs when conjugated dienes are attacked by chemical reagents. Reactions of this type
have been found to be quite general with other conjugated dienes, and 1,4-addition is often the major product of the
reaction. Similarly 1,3-butadiene reacts with one mole of HCl or HBr to produce a mixture of two products due to 1, 2- and
1,4-addition.
Hydrocarbon 3.83
Addition of Hydrogen
⊕ ⊕ ⊕
CH2 = CH – CH = CH2 CH2 – CH – CH = CH2 CH2 – CH – CH = CH2
H2 H2
CH3 – CH2 – CH = CH2 CH3CH2 = CH – CH3

1, 2- addition 1, 4 addition
(Kinetically controlled) (Thermodynamically controlled)
formed at low temperature and will be formed at High temperature
The relative amounts of 1, 2- and 1, 4- addition products are dependent on the temperature of the reaction.
–80° CH3CHCH = CH2 + CH3CH = CHCH2Br
(80%) (20%)
CH2 = CH – CH = CH2 Br
HBr 40°
CH3CHCH = CH2 + CH3CH = CHCH2Br
(20%) (80%)
Br
At low temperature (–80°), the major reaction is 1, 2-addition while at higher temperature (40°), the major reaction is 1,
4-addition. Furthermore, when the product mixture obtained at low temperature is heated to 40°, then the relative amounts
of the two products alter. This behaviour of 1, 3-butadiene towards HBr addition can be understood by saying that the
energy of activation leading to the 1,2-addition is considerably less than that needed for the 1, 4-addition product. At low
temperature more of the 1, 2-addition product is formed than the 1,4-addition product. At higher temperature, both the
products are formed but the 1, 2-addition product though formed faster, is unstable and thus reverts back to the allylic
cation and bromide ion rearranges to give the 1, 4-addition product. The 1,4-aclditipn is thus formed in a larger proportion
at the expense of the 1, 2-addition. It is said to be thermodynamically I controlled reaction as an equilibrium is established
between the products. The formation of the 1, 2-addition product at low temperature is kinetically controlled, i.e., the
yields of products are proportional to the rates at which they are formed.
Illustrations
142. (a) Explain why HBr adds to 1,3-pentadiene at a faster rate than to 1,4-pentadiene. (b) Is this inconsistent with
the conjugated diene being more stable than the isolated diene?
Ans. (a) When an electrophile (H+) adds to the conjugated diene in the rate-controlling step, an allylic carbocation
is formed. Addition to the isolated diene gives an ordinary saturated 2° carbocation, CH3CHCH2CH=CH2. The
allylic carbocation is more stable, the DH+ of its formation is less than the DH+ for the formation of the ordinary
carbocation. Thus, it is formed at a faster rate, (b) No Stability is a thermodynamic property, while reactivity is a
kinetic property.
143. (a) When HBr adds to butadiene at a low temperature (-80 °C), which addendum is the major product? (b) Which
is the major product at higher temperatures (40 °C)? (c) What happens when the 1,2-adduct is warmed to higher
temperatures?
Ans. (a) CH3CHBrCH=CH2, 1,2-adduct (A), (b) BrCH2CH = CHCH3, 1,4-adduct (B). (c) The 1,2-adduct rearranges to
give mainly the 1,4-adduct.
3.84 Hydrocarbon
144. (a) Use an enthalpy diagram to illustrate the results in illustration 143. (b) Explain the results in terms of rate and
thermodynamic control of products. Identify the rate-controlled and thermodynamically-controlled products. (c)
Why is the 1, 4-adduct more stable?
Ans. (a) See Figure. The two products arise from DH++ differences in the second step, the reaction of Br‑ with the
allyl R+.
(b) At -80 °C the 1,2-adduct has the lower DH++ and is formed at the faster rate. It is the rate-controled product, A.
As the temperature rises to 40 °C, the 1,2-adduct is able to reverse back to the intermediate R+, and then can pass
through the higher enthalpy transition state, leading to the more stable thermodynamically-controlled 1,4-adduct,
B. B accumulates at the higher temperature because the DH++ for reversing to the R+ has a higher DH++ than that
of A.
(c) B is a more substituted alkene than A.
DIELS - ALDER REACTION

In 1928, Otto Diels and his research student Kurt Alder presented a convenient route to the formation of six-membered
rings through pericyclic process, categorically a [4 + 2]p-cycloaddition reaction. The reaction is well-known as Diels-Alder
reaction in honour of the inventors. The usefulness of this reaction in synthesis arises from its versatility and also from its
remarkable stereoselectivity. Besides six-membered carbocyclic rings, a variety of six-membered heterocyclic compounds
may also be synthesized by using this reaction. The Diels-Alder reaction involves a concerted step cycloaddition between
a 1,3-conjugated diene (4p-electron system) and an alkene (2p-electron system, usually referred to as dienophile); during
the course of the reaction, two new s-bonds are formed at the cost of two p-bonds. The reaction may be prototypically
represented as:
heat
+
Diene Dienophile Adduct
Diels-Ader reaction takes place simply by mixing the components at room temperature or by gentle warming in
suitable solvent—however, more vigorous conditions may be necessary in some cases where dienes or dienophiles are not
so reactive. Since Diels-Alder reaction is reversible, heating at high temperature is disadvantageous because it facilitates
adduct to decompose into its components; that’s why Diels-Alder reaction is generally carried out at low temperature.
The forward reaction can be facilitated by using an excess of one of the components, or a solvent from which the adduct
separates out readily. It has also been observed that Lewis acid catalysts accelerate many Diels-Alder reactions. By varying
the nature of diene and dienophile different types of ring structures can be built up.
Hydrocarbon 3.85
Illustrations
145. List four chemical tests to distinguish an alkene from an alkane.

Ans. A positive test is indicated by one or more detectable events such as a color change, appearance of an insoluble
solid or liquid, evolution of a gas, uptake of a gas or evolution of heat.
CCl4
C = C + Br2 C C (loss of color)
(red) Br Br
(colorless)
KMnO4
C=C (purple)
C C (+ MnO2) (loss of color
and formation
OH OH brown-black
(colorless) precipitate or precipitate)
C = C + H2SO4 (conc.) C C + HSO4– heat (solubility in

+
H sulfuric acid)
Pt
C=C + H2 C C (uptake of a gas)
H H
Alkanes give none of these tests.

146. Give a simple test to distinguish (a) 1-butene from the 2-butenes and (b) 1,3-dibromopropane from
1,2-dibromopropane.
Ans. (a) Heat with acidified KMnO4 and lead any evolved gas into limewater, Ca(OH)2. If a white precipitate of CaCO3
appears, it comes from 1-butene whose terminal C is emitted as CO2:
CO2 + Ca(OH)2 → CaCO3(s) + H2O
(b) On adding Nal in acetone, the vic-dihalide reacts:
H2CBrCHBrCH3 + 2I– → H2C = CHCH3 + 2Br– + I2 (gives blue-black color with starch.)
147. Three isomeric alkenes A, B, and C, C5H10, are hydrogenated to yield 2-methylbutane. A and B give the same 3°
ROH on oxymercuration-demercuration. B and C give different 1° ROH’s on hydroboration-oxidation. Supply
the structures of A, B, and C.
Ans. The isomers must have the same skeleton as 2-methylbutane and it becomes a question of placing the double
bond. Since A and B give a 3° ROH, they have the =CMe2 or H2C=CMe grouping. Since B and C give 1° ROH’s,
they are terminal alkenes having the H2C= grouping.
A is H2C = C – CHMe2; B is Me – C = C – Me; C is H2C = C – CH2CH3
H Me H Me
148. (a) Two isomers, C7H13Br, are formed when either 1,2- or 2,3-dimethylcyclopentene (A and B) react in the dark
with HBr in the absence of peroxides. What are these isomers? (b) Which isomers are formed when the same two
cyclopentenes in part (a) react with HBr in the presence of peroxides?
Ans. (a) There is a Markovnikov addition to give racemic diastereomers with the Me’s cis or trans:
Br Me
Me Me
Me Br
H H
D C
trans-1,2-Dimethyl -1-bromocyclopentane cis-1,2-Dimethyl-1-bromocyclopentane
3.86 Hydrocarbon
(b) The product is anti-Markovnikov. However, since ROOR catalyzes mainly anti addition of HBr to cycloal-
kenes, the major product from A is D. The bromo products from B have the vicinal Me and Br cis. With three
stereocenters, eight stereoisomers (23), comprising four racemic diastereomers, exist (E-H), of which only
racemic E and F are products.
Br Me Br Me
Me Br Me Br
Me Me Me Me
E G F H
cis-2,3-Dimethyl-cis- cis-2,3-Dimethyl-trans- trans-2,3-Dimethyl-trans- trans-2,3-Dimethyl-cis-
1-bromocyclopentane 1-bromocyclopentane 1-bromocyclopentane 1-bromocyclopentane
The Diene
The diene component in the Diels-Alder reaction may either be open-chain or cyclic; the diene must essentially have cisoid
(or s-cis) confonnation or must be able to adopt it during the reaction before undergoing cycloaddition with dienophiles
— this is required so that the ends can interact with the dienophile simultaneously. No reaction takes place in the transoid
(or s-trans) conformation of the diene. Butadiene itself prefers the transoid conformation with the two double bonds as
far as away from each other for steric reasons; since the rotational energy barrier (about the central s-bond) separating
the two conformations is small (about 3.9 kcal/mole)3, rotation to the less favourable but reactive cisoid conformation
becomes rapid.
COOMe
COOMe
fast (dienophile)
(transoid conformation) (cisoid conformation) (adduct)

favoured; but cannot disfavoured; but undergoes
undergo Diels-Alder reaction Diels-Alder reaction
Cyclic dienes that are permanently in the cisoid conformation are exceptionally good toward Diels-Alder reaction
—cyclopentadiene is a classic example—but cyclic dienes that are frozen into the transoid conformation and cannot
adopt the cisoid form will not undergo the reaction at all. Thus, the cyclic dienes (1 to 5) can undergo the reaction
while 6 and 7 cannot.
1 2 3 4 5
(1,2,3,4,5 --- all are permanently in the cisoid (s-cis) conformation)
(6&7 --- all are permanently in the

transoid (s-trans) conformation)
6 7
It is observed that electron-donating substituents (e.g., –Me, –OMe, –NMe2, etc.) often enhance the reaction-rate while
electron-withdrawing groups have the opposite effect. As expected bulky substituents, which prevent the diene from
adopting the cisoid conformation, retard the reaction. Thus, 2-methyl, 2,3-dimethyl and 2-t-butylbutadienes react normally
with maleic anhydride but 2,3-diphenyl-l,3-butadiene is less reactive while 2,3-di-t-butyl-l,3-butadiene is completely
unreactive.
Hydrocarbon 3.87
(2-methyl-1,3-butadiene) (2,3-dimethy-1,3-butadiene) (2,t-butyl-1,3-butadiene)
Ph The bulky t-butyl groups situated at both the

C-2 and C-6-positions prevent the molecule form
attaining planar cisoid conformaiton by imposing
Ph steric effects.
(2,3-diphenyl-1,3- (2,3-di-t-butyl-1,3-
butadiene) butadiene)
An E-substituted 1,3-tmtadiene reacts with dienophiles much more readily than the Z-isomer because Z-alkyl or aryl sub-
stituents in the C-l position of the diene undergoes non-bonded interaction with a hydrogen atom at C-4, thus, hindering the cis-
oid conformation. It is reflected from the fact that while Z-l-methyl-l,3-butadiene (7) gives only 4 per cent yield of adduct when
heated with maleic anhydride at 100°C, the E-isomer (8) forms an adduct in almost quantitative yield in benzene even at 0°C.
H CH3
CH3 H
H H
H H
(7) (8)
Similarly, E,E-l,4-dimethyl-l,3-butadiene reacts with many dienophiles rapidly, but the Z,E-isomer forms an adduct only
when the components are heated in benzene at 150°C; in an extreme case , i.e., the Z,Z-isomer does not undergo the reaction.
Aromatic compounds can also behave as dienes. Benzene is very unreactive toward dienophiles — very few ones (e.g.,
benzyne) have been reported to give Diels-Alder adduct with it. Naphthalene has been reported to undergo the reaction at
high pressures. However, anthracene and other compounds with at least three linear benzene rings give Diels-Alder reac-
tion readily. For example,
(anthracene) (benzyne) (triptycene)

Very few examples of a variety of diene systems are presented below:
O
N N
N N
N N O O
N N
O S O
3.88 Hydrocarbon
The Dienophile
In Diels-Alder reaction the dienophile component comprises of a large variety of ethylenic and acetylenic derivatives
or reagents in which one or both the reacting atoms is a heteroatom. Dienophiles may vary in reactivity—the reactivity
depends upon the structural pattern. Presence of electron-withdrawing substituents (e.g., CO, COOR, CN, NO2, etc.) on
the double or triple bond of dienophiles enhances the reactivity.
Very few examples of a variety of dieneophile systems are presented below.
COR NO2
O S N O
N
N O
(singlet)
O O
SO2Ph NC OTs
CN H3COOC
N
O O
NC CN CHCCl
3
O O O O CHO
O Me CHO
EtO OEt EtOOC COOEt

Cl CHO
O
A Few Examples of Diels-Alder Reaction

Enormous chemical reactions involving varieties of dienes and dienophiles are known; a very few representative examples
are cited below.
Me COOMe Me
COOMe
150°C
(a) + toluene
COOMe
COOMe 85%
(diene) (dienophile) (adduct)
COOEt
N 10°C
(b) + N COOEt
N ether
N COOEt
EtOOC
(100%)
COOEt O O
MeOOC
O MeOOC COOEt
+
(c)
O COOEt
COOEt (adduct)
MeO2C CO2Et
–CO2
CO2Et
Hydrocarbon 3.89
O
O O
O
(d) + O
O (adduct)
COOEt
O
heat COOEt
(e) O+
COOEt
COOEt
(f) Fulvenes react preferentially as good dienophiles in the Diels-Alder reaction with dienes. However, mode of cycload-
dition varies with the electronic property of dienes—with electron-poor dienes like enones a [4 + 2]p cycloaddition
takes place, whereas a [6 + 4]p cycloaddition occurs with electron-rich dienes like 1-amino-butadiene.
O
O
[4+2]π cycloaddition
H
+ H
(cycloheptatrienone) (6,6-dimethylfulvene)
(adduct)
+
[Ref. 9]
O
O
(66%)
NH2
+
(adduct) NH2
O O
(g)
+ O heat O
MeO O MeO
(h) Diels-Alder reactions may take place in water medium also ; in this case water-soluble dienes are used. Sodium salts
of carboxylic acids and protonated amines both behave well under these conditions. Presumably, the soluble tail is in
the water but the diene itself is inside the oily drops with the dienophile. For example,
3.90 Hydrocarbon
+ H 2N
O H3N O Me N Me
H H
H 2O
+ RT
(98%)
O O H O H
(sterochemistry
(quinone (aminodiene spiro-compound
ascertained by
derivative) salt) (Diels-Alder adduct)
NMR studies)
OMe
O OMe
O
(i) under high pressure
+
(80%)
O O
[Ref. 11]
adduct formation Na-Hg

(j) + (reductive cleavage)
SO2C6H4CH3 SO2C6H4CH3
[Ref. 12]
COOMe Me Me
Me COOMe CO2Me
(k) S + S
COOMe CO2Me
Me
COOMe Me Me [Ref. 13]
(extrucsion of sulphur
under reaction condition)
Mechanism
The rate-determining step in adduct formation is bimolecular and formation of two new s-bonds occurs by overlap of
molecular p-orbitals in a direction corresponding to endwise overlap of atomic p-orbitals. In a concerted mechanism, all
bonds that are to be formed or broken during the reaction are being so formed or broken at the same time; therefore, no
intermediates are involved and it takes place through a cyclic transition state Figure.
slow
+
Stereochemistry
Diels-Alder reaction is stereospecific. The stereochemistry of an adduct can be assumed on the basis of an empirical
rule ‘cis principle’ formulated by Alder and Stein in 1937, according to which the stereochemistry of all the substituents
located at the C-l and C-4 positions on the diene and at the C-l and C-2 positions on the dienophile remains preserved.
Thus,
Hydrocarbon 3.91
R COOMe R
H
COOMe
H Diels - Alder
+
H COOMe
COOMe H R'
R'
(diene) (dienophile)
trans, trans
R H
COOMe COOMe
H Diels - Alder
R
+
H COOMe
H R'
R' COOMe
(diene) (dienophile)
cis, trans
Similarly,
COOMe
COOMe
Diels - Alder
+
COOMe COOMe
(dimethylmaleate)
COOMe COOMe
Diels - Alder
+
COOMe
MeOOC
(dimethylfumarate)
Thus,
Ph H Ph
COOMe COOMe
Diels - Alder
+
Ph COOMe
MeOOC H
(dimethylfumarate) Ph
Diels-Alder reaction maintains regioselectivity during product formation — 1-substituted dienens form ortho-products
while 2-substituted ones give para-products when added to dienophiles with an electron-withdrawing group at one end.
Hence,
X X
Z Z
Z
X = alkyl, aryl, Diels - Alder
+
RO, Me3SiO, X
R3N, etc.
(ortho-relation) ( para-relation)
Z = CHO, COR, major minor
CO2H, COOR, Z
NO2, CN, Z
halogens, etc. + Diels - Alder +
X X X Z
(para-relation) (meta-relation)
major minor
Application of such regioselectivity, as for example, has been used up in the synthesis of limonene (a natural odour
principle found in most citrus plants).
3.92 Hydrocarbon
O O
O
SnCl4
+
heat +
[in presence of SnCl4 (Lewis acid)
regioselectivity is enhanced major (93 : 7) minor
Ph3 P = CH2
Wittig reaction
(Limonene, a citrus constituent)

The stereochemistry of the resultant ring is assigned by the manner in which the diene and dienophile approach each
other—either described as ‘endo’ or ‘exo’. The ‘endo’ approach can be defined as orientation in which the diene and dieno-
phile come to have their ends match up, while achieving maximum ‘overlap’ of their faces. The ‘exo’ approach is, in turn,
described as an orientation in which the two faces have the least interaction, while still maintaining the proper alignment
of the ends of the diene and dienophile. To illustrate the phenomenon let us consider the Diels-Alder reaction between
anhydride and cyclopentadiene—the two possible products (‘endo’ and ‘exo’) may be shown as:
O H O
H
+ O O
H
O H O
O
H
H O
O
O
O
HH
O
(endo-adduct) (exo-adduct)
(two possible products)
Thermodynamically an endo-adduct becomes less stable than exo-adduct, but the interesting fact is that endo-products
normally predominate, often almost to the exclusion of exo-products. In irreversible Diels-Alder reaction endo-adduct must
be kinetic product of the reaction. In case of reversible reactions initially formed endo-adducts may, however, isomerize
to the less sterically hindered more stable exo-adducts by a retro-Diels-Alder reaction followed by recombination, as
observed in:
O
O O O
H retro-Diels- H recombi-
HO nation
Alder
O O O
O H HO
O H
O (exo-adduct)
(endo-adduct)
(less stable; kinetically (more stable;
controlled product) thermodynamically
controlled product)
ALKYNE
Introduction: Unsaturated hydrocarbons having a carbon-carbon triple bond are called alkynes. They correspond to
general formula CnH2n–2, i.e., they have smaller proportion of hydrogen than alkene. Alkynes are isomeric with cycloal-
kenes and alkadienes.
Hydrocarbon 3.93
Illustration
149. (a) Explain why cyclohexyne does not exist. (b) What is the smallest size ring that can accommodate a triple
bond?
Ans. (a) The linear structural unit —C—C=C—C— cannot be bridged with only two C’s. (b) This unit can be bridged
with four C’s; hence, cyclooctyne is the simplest cycloalkyne.
Nomenclature
HC ≡ C — CH 2 — CH = CH 2
1−Penten− 4 −yne
CH3 Cl
4 2 2 4 CH3
H3C 3 CH H3C 3 5 6
5 1 1
4-methylpent-1-yne 2-chlorohex-3-yne
CH3
CH CH
H3C
Pentylethyne
5-methylhex-1-yne
Nomenclature of Alkynes
Illustrations
150. Name the structures below by the IUPAC system:

(a) CH3C ≡ CCH3 (d) HC ≡ C – CH2CH = CH2
(b) CH3C ≡ CCH2CH3 (e) HC ≡ C – CH2CH2Cl
&+ &+
(c) &+±&±&Ł&±&±&+
+ &+
Ans. (a) 2-Butyne
(b) 2-Pentyne
(c) 2,2,5-Trimethyl-3-hexyne
(d) 1-Penten-4-yne
C == C has priority over C ≡≡ C and gets the smaller number.
(e) 4-Chloro-1-butyne
151. Give the structural formulae for each of the following compounds: (a) 1,3-butadiyne, (b) 4-methyl-1-nitro-2-
pentyne, (c) (E)-3-penten-1-yne (not 2-penten-4-yne; numbers as low as possible are given to double and triple
bonds although this may give the yne a lower number than the ene.), (d) (Z)-5-hepten-1,3-diyne.
Ans. (a) HC ≡ C – C ≡ CH (b) (NO2)CH2C ≡ CCH(CH3)2
CH3 H CH3 C = C – C ≡ CH
(c) C=C and (d) C=C
H C ≡ CH H H
3.94 Hydrocarbon
152. Name the following radicals: (a) — C=CH, (b) — CH2C=CH, (c) — C=CCH3, and (d) — C=CCH2CH3.
Ans. (a) Ethynyl, (b) propargyl or 2-propynyl, (c) 1-propynyl, and (d) 1-butynyl.
153. (a) Give the structural formulae for the seven alkynes of the formula C6H10. (b) Give the IUPAC and derived name
for each isomer. (c) Which isomers in (a) are terminal alkynes?
Ans. (a) First insert the triple bond into different positions of the six-carbon chain:
HC=CCH2CH2CH2CH3 (A), H3CC=CCH2CH2CH3 (B), CH3CH2C=CCH2CH3 (C)
Then insert the triple bond into the two possible methyl-branched chains, noting that the triple bond cannot be
on a branched C:
(CH3)2CHC=CCH3 (D), (CH3)2CHCH2C=CH (E), CH3CH2CH(CH3)C=CH (F)
Finally, work with a dimethyl branched chain:
(CH3)3CC=CH (G)
(b) (A) 1-Hexyne, butylacetylene; (B) 2-hexyne, methylpropylacetylene; (C) 3-hexyne, diethylacetylene; (D)
4-methyl-2-pentyne, methylisopropylacetylene; (E) 4-methyl-l-pentyne, isobutylacetylene; (F) 3-methyl-1-
pentyne, sec-butylacetylene; and (G) 3,3-dimethyl-1-butyne, tert-butylacetylene.
(c) Terminal alkynes have the triple bond at the end of a carbon chain; A, E, F, and G. The other alkynes are called
internal alkynes.
154. Give the IUPAC names for each of the following:
CH3
(a) C≡CH (b) H C≡CCH3
H
(c) C≡C (d) CH2C≡CH
Ans. (a) Cyclopentylethyne
(b) cis- 1-Methyl-2-(1 –propynyl) cyclohexane
(c) Cyclobutylcyclopropylethyne (note that numbers are not necessary.)
(d) 5-(2-Propynyl)-1,3-cyclohexediene
Physical Properties
(i) Lower members (C2 to C4) are gases; middle ones (C5 to C12) are liquids; highers are solids.
(ii) The boiling point, melting point and specific gravity of alkynes show a regular increase with increase in molecular
weight; however less volatile than alkene. The order of boiling point in hydrocarbons has been explained in terms of
polarity. Alkynes possess more polarity and thus have higher boiling points.
Boiling point: alkyne > alkene > alkane
(iii) All are colourless and possess no characteristic odour; however C2H2 has garlic odour due to the impurities of PH3,
H2S etc. Pure C2H2 has ethereal odour.
(iv) Soluble in organic solvents like acetone, alcohol and sparingly soluble in water.
(v) The boiling point of acetylene is –84°C. Liquid acetylene is dangerously explosive and therefore storage and
transportation of liquid acetylene is prohibited by law. That is why acetylene is stored and transported by dissolving
it in acetone soaked on porous material like asbestos packed in steel cylinders, under high pressure.
Preparation
1. Dehydrohalogenation of vicinal dihalides: Vicinal dihalides having hydrogens on carbon give alkynes with strong
base.
R — CH — CH — R R —C≡C—R
X X
Hydrocarbon 3.95
2. Kolbe hydrocarbon synthesis: Potassium salt of maleic acid and its alkyl derivatives give alkynes on electrolysis.
R — C — COOK
electrolysis
R — C ≡ C — R + 2CO2 + 2KOH + H2
R — C — COOK
Individual Member
Acetylene: It can be prepared by metal carbide.
CaC 2 H
2O
→ C2 H 2 + Ca (OH) 2
Preparation
Illustrations
155. (a) Write the reactions for the industrial preparation of acetylene from CaO (lime), C (coke) and water, writing
the Lewis structure for CaC2. (b) Formulate the reaction of CaC2 and water as a Bronsted acid-base reaction.
(a) CaO + 3C → CaC2 + CO; CaC2 + 2H2O → HC = CH + Ca(OH)2
(b) (: C ≡ C :) 2 − + 2H 2 O → HC ≡ CH + 2OH −
base1 aicd 2 acid1 base2
(Ca2+ is the spectator ion and is omitted.)

156. Give the major industrial synthesis of acetylene.
Ans. 2CH 4 1500
 °C
→ C 2 H 2 + 3H 2
157. Prepare propyne from propene.

+
→ CH 3 CHBrCH 2 Br 3
Ans. CH 3 CH = CH 2 + Br2  NaNH 2
−2 HBr
→ [CH 3 C ≡ C− ] +
H

→ CH 3 C ≡ CH
vic-Dihalides undergo a double dehydrohalogenation, requiring two moles of NaNH2. The terminal alkyne is
converted to the alkynyl an ion as soon as it forms; thus three moles of the base are used in the overall reaction.
158. Account for the fact that a much stronger base (NaNH2) is used in the double dehydrohalogenation in Question
154 than in alkene formation from alkyl halides (ale. KOH).
Ans. Double dehydrohalogenation of vic-dihalides occurs by two discrete steps:
R − CHBrCHBr − R −
HBr
→ R − CBr = CH − R (a vinyl halide) −
HBr
→ R −C ≡ C−R
It is more difficult to dehydrohalogenate the intermediate vinyl bromide than an alkyl bromide.
159. Explain why CH3CHBrCH2Br reacts with one equivalent of alcoholic KOH to give mainly CH3CH = CHBr
(A) rather than CH2 = CHCH2Br (B) or CH3CBr = CH2 (C).
Ans. In E2 eliminations the more acidic H is removed preferentially. The inductive effect of the Br’s increases the
acidity of the H’s on the C’s to which the Br’s are bonded. B is not obtained because its formation would require
removal of H from the CH3 group which has the least acidic H’s. A little C is formed because its formation
requires removal of H from C2. Since R groups on a C decrease the acidity of its H’s, C2 — H is less acidic than
the Cl—H’s. In addition there is the statistical effect (two H’s available on Cl versus one on C2). A, the major
product, requires loss of H from Cl.
160. What other kind of dihalide can undergo a double dehydrohalogenation to give an alkyne?
Ans. A gem-dihalide as shown:
−CH 2 − CBr2 − NaNH
 2
→ −C ≡ C−
3.96 Hydrocarbon
161. From 1, 1-dibromopentane synthesize (a) 2-pentyne and (b) 1-pentyne.

Ans. (a) CH 3 CH 2 CH 2 CH 2 CHBr2 KOH
 (s )
200° C
→ CH 3 CH 2 C ≡ CCH 3
+
(b) CH 3 CH 2 CH 2 CH 2 CHBr2 NaNH
 2
→ CH 3 CH 2 CH 2 C ≡ C− H
3O
→ CH 3 CH 2 CH 2 C ≡ CH
Br
H3C
NaNH2
15. (a) A. Identify A
(Excess)
H3C
CH3
Br
CH3
CH3
NaNH2
(b) H3C C HC B , Identify B
(Excess)
Br Br
16. Aqueous solution of the following compounds are electrolysed. Acetylene gas is obtained from.
(a) Sodium fumarate
(b) Sopdium maleate
(c) Sodium succinate
(d) Both (a) and (b)
SOLUTIONS
CH3 H3C
15. (a) H3C C C CH (b) C C CH2
CH3 H3 C
(B)
(A)
– –
CH – COO CH – COO
16. || || + 2Na
+
– –
CH – COO CH – COO
–
CH – COO CH
|| || + 2CO 2 + 2C at cathode
CH – COO
–
CH
\ (d)
Hydrocarbon 3.97
Chemical Nature
(A) Reactions due to acidic hydrogen
Relative acidities of some compounds are as follows in decreasing order
HOH > ROH > CH ≡ CH > NH 3 > CH 2 = CH 2
Alkynes are very weak acid. Reaction due to acidic hydrogen will be given by acetylene and terminal alkynes.
(i) Salt formation
1
R − C ≡ C − H NH NaNH 2
 → R − C ≡ CNa + H 2
3 ()
2
(ii) Formation of metal alkynide
R —C≡C—H

1. Reaction with Grignard reagent: These two reagent react with terminal alkyne to form hydrocarbon and new
organometallic compound respectively.
R —C≡C—H

2. Electrophilic substitution with X 2 / OH or NaOX
R — C≡ C — H 
NaOCl
→ R — C≡ C — Cl
H — C≡C — H 
NaOCl
→ Cl — C≡ C — Cl
Illustrations
162. Compare the C—H bond lengths and bond dissociation enthalpies of an alkyne, alkene, and alkane.
Ans. As a rule, ‘the more s character in the HO used by an atom, the closer are the bonding e-s to the atom, and the
shorter and stronger is any of its s bonds." The decreasing order of C—H bond lengths is
−C −3 H > = C −
2
H > ≡ C−H
sp sp sp
The decreasing order of bond enthalpies is

≡ C−H > = C− 2
H > −C −3 H
sp sp sp
163. List alkanes, alkenes, and terminal alkynes in order of decreasing acidity of their terminal C—H.
Ans. The order of decreasing acidities is: alkyne > alkene > alkane.
164. Give the products of each of the following acid-base reactions using the approximate pKa values given in
parentheses: H2 (> 35), CH4 (> 40), CH3OH (17), C2H2 (25), HCN (9), CH3CO2H (5). Write NR if no reaction
occurs.
(a) HC = CNa + CH3OH, (b) HC = CH + CH3Li, (c) HC = CH + NaH, (d) HC = CH + NaCN, (e) HCs = CNa +
CH3CO2H
Ans. Acid-base reactions always go from the stronger acids and bases to the weaker ones. Therefore acetylene will
only react with bases that are converted to acids weaker than acetylene, and acetylide ion will only react with
acids that are converted to bases weaker than acetylide ion. Thus,
3.98 Hydrocarbon
(a) HC=CH + CH3ONa,

(b) HC=CLi + CH4,
(c) HC=CNa + H2,
(d) NR,
(e) HC=CH + CH3CO2Na
165. Write equations for the preparation of (a) HC = CD and (b) DC=CD.
Ans. (a) HC ≡ CH NaNH
 2
→ HC ≡ C− D
2O
→ HC ≡ CD
(b) HC ≡ CH + 2 Na 
→ −: C ≡ C :− D
2O
→ DC ≡ CD
166. From an appropriate alkynide salt and alkyl halide, synthesize (a) 4-methyl-2-hexyne, (b) 5-methyl-2-hexyne, (c)
5,5-dimethyl-3-hexyne.
Ans. In each case select the combination with an unhindered 1° RX.
(a) CH3CH2CHC ≡ C– + I CH3C ≡ CCHCH2 CH3
CH3 CH3
(not CH3C ≡ C + BrCH(CH3)CH2CH3)
–
(b) (CH3)2CHCH2C = C– + CH3I → (CH3)2CHCH2C = CCH3

(c) (CH3)3CC = C‑ + CH3CH2Br → CH3CH2C = CC(CH3)3
CH3I is used in syntheses (caution — it is carcinogenic!) because it is a liquid and therefore more easily
handled than the gaseous chloride or bromide.
167. Show the steps in the preparation of 2-hexyne, starting with acetylene and any alkyl halides.
Ans. A cetylene is dialkylated. The derived name for this alkyne is methylpropylacetylene from which we conclude
that the RX’s needed for dialkylation are n-C3H7Br and CH3I.
168. Discuss the suggested synthesis of cyclodecyne from HC = CH and 1,8-dibromooctane:

Ans. The first alkylation of acetylide (from C2H2) occurs with little difficulty.
HC = C– + Br(CH2)8Br → HC==C(CH2)8Br
Problems arise in the attempted second alkylation to give the ring.
CH2 – C ≡ C – CH2
C≡C(CH2)8Br CH2
CH2 CH2 CH2
CH2 CH2
Intramolecular cyclizations leading to rings with more than six C’s are difficult, and intermolecular reactions pre-
dominate. Intramolecular cyclization are encouraged by using very dilute solutions, thereby making it difficult
for two molecules to collide to give the intermolecular alkylation.
169. Synthesize CH3CH2CH(CH3)C = CH from 1-pentyne.
Ans. First form the dianion. Then one mole of RX is added to the dianion, alkylating the more basic propargylic
carbanion.
Hydrocarbon 3.99
(B) Reactions due to Pi bonds

Alkyne gives addition as well as oxidation reactions due to the presence of pi bonds.
Addition Reactions of Alkynes

(1) Alkyne gives electrophilic addition reactions and the reaction intermediate is vinyl carbocation.
(2) Alkene is more reactive than alkyne for electrophilic addition reactions. The reason can be explained as follows:
⊕ ⊕
H
R – CH = CH2 R – CH – CH3
Alkene (I)
Alkylcarbocation
more stable than (II)
⊕ ⊕
H
R – C ≡ CH R – C – CH2
(II)
Vinyl carbocation
less stable than(I)
We known that reactivity of substrate depends on the stability of reaction intermediate. Higher is the stability of RI,
more will be the reactivity of the substrate. Therefore, alkene is more reactive than alkyne.
CH ≡CH −CH 2 −CH =CH 2  → CH ≡C−CH 2 −CHBr −CH 2 Br

Br2 / CCl4
− 80 ° C
The above reaction also confirms that alkene is more reactive than alkyne for electrophilic addition reaction.
(3) Alkyne also gives nucleophilic addition reaction but only with HOH, HCN, ROH and RCOOH. Reaction intermediate
of this reaction is vinyl carbanion.
(4) Alkyne can react with one mole as well as with two moles of the reagent. This depends on the reaction condition and
number of moles of substrate and reagent.
Another explanation for the greater reactivity of alkyne is given as follows.
πy
Py Py π’s
Pz Pz
πz H C σ C H
H sp C sp sp C sp H or H σ
C σ σ
H or (depicts combined
Pz Pz P py and pz π-electron
Py y
cloud)
Alkenes are absorbed on the surface of the catalyst only when the plane of the p bond approaches perpendicularly
(‘head on’). Because of the cylindrical nature of the p bonds of alkynes, any approach along the axis of the cylinder
can be successful (see fig above). These less constrained transition states cause alkynes to have more positive DS val-
ues. Consequently, in this reaction alkynes react at a faster rate than alkenes.
Electrophilic addition reactions

1. Addition of Hydrogen: Alkynes are more reactive than alkenes towards hydrogenation, because
sp hybrid carbon of alkyne is less hindered than sp2 hybrid carbon of alkene.
2. (a) Syn Addition of Hydrogen (cis-Alkenes):
Hydrogenation of alkynes in the presence of P-2 catalyst causes syn addition of hydrogen.
H2/Ni2 B(P-2) H3CH2C CH2CH3

CH3CH2C ≡ CCH2CH3
(3–Hexyne) Syn Addition C=C
H H
(Cis-3-hexene)
97%
3.100 Hydrocarbon
(b) Lindlar’s catalyst:

Metallic palladium deposited on calcium. carbonate and is poisoned with lead acetate and quinoline
H2/Ni2 B(P-2) H3CH2C CH2CH3
CH3CH2C ≡ CCH2CH3
(3-Hexyne) Syn Addition C=C
H H
(cis-3-hexene)
97%
3. Na and liq. NH3 or Li (liq. NH3) converts non-terminal alkyne to trans-alkene. This reaction takes place via formation
of radical anion. This is called anti addition.
(CH2)2CH3 H
1. Li
CH3(CH2)2 – C ≡ C – (CH2)2CH3 C=C
2. NH3
H (CH2)2CH3
Probable Mechanism
The Dissolving Metal Reduction of an Alkyne

R R H
Na C = C C=C
NH3
R R
A sodium atom donates an electron to

the π bond of the alkyne. An electron
pair shifts to one carbon as the
hybridization states change to sp2
R H R H R H
NH3
C≡C C ≡ C C ≡ C
Na R
R – H R
Terminal alkynes on reaction with Na/liq. NH3 give sodium salt due to presence of acidic terminal hydrogen of
C ≡ C-H.
Θ + 1
CH3 – C ≡ C-H  Na
→ CH 3 − C ≡ C N a + H 2
liq. NH3 2
4. Birch Reduction: Reduction of terminal alkene with Na and liq. NH3 to give alkane via formation of radical anion.
R − CH = CH 2 Na
/ liq . NH3
→ RCH 2 − CH 3
1,4- Reduction of benzene under same condition is also known as Birch Reduction
Na (liq. NH3)
This reaction takes place via formation of radical anion. Electron withdrawing groups favours formation of carbanion.
COOH COOH CH3 CH3

H H
Na Na (liq. NH3) H
(liq. NH3) H
H H H
Hydrocarbon 3.101
Illustrations
170. Write equations for the stepwise reaction of 2-butyne with two moles of H2/Pt.
H2/Pt H2/Pt
Ans. CH3C ≡ CCH3 CH3C = CCH3 CH3CH2CH2CH3
H H
(Z)-2-butene
171. The DH's of hydrogenation of the two steps in Question 167 are -42 kcal/mol and -33 kcal/mol, respectively. Why
can the reaction be stopped after the alkene is formed?
Ans. Since the first hydrogenation step is more exothermic, most of the alkyne will react before any alkene reacts. The
Lindlar’s catalyst, Pd on solid CaCO3 or BaSO4, deactivated (poisoned) with quinoline (a heterocyclic amine) or
Ni/B, is used to ensure getting the alkene.
172. Give a mechanism for the active metal (Na) reduction of an alkyne in a protic solvent (C2H5OH).
Ans. An Na. atom transfers an e– to the C = C group to give a vinyl radical carbanion intermediate, whose HO’s
containing the unshared pair of e–'s and odd electron are as far away from each other as possible. The R’s are
now fixed trans. The radical anion picks up an H+ from the protic solvent to give a trans vinyl radical. Another
sequence of e‑/H+ transfers occur to give the trans-alkene and EtO–Na+.
(A) Addition of X2(Cl2, Br2 and I2): Addition occur once or twice depending on the number of molar equivalents of halo-
gen

Both addition follow Markovnikov’s Rule
Reactivity Cl2 > Br2 > I 2
Both additions follow Markovnikov’s rule.
(a) It is usually possible to prepare a dihalo alkene by simply adding one molar equivalent of the halogen at 0°C.

(b) The reactivity order of halogen is Cl2 > Br2 > I2.
(c) Chlorine and bromine forms di as well as tetra halo derivatives but iodine forms only di iodo derivative.

3.102 Hydrocarbon
Illustrations
173. Explain why alkynes are less reactive than alkenes toward addition of Br2.
Ans. The three membered ring bromonium ion formed from the alkyne (A) has a full double bond causing it to be more
strained and less stable than the one from the alkene (B).
HC = CH (A) less stable than H2C — CH2 (B)
+ +
Br Br
Also, the C’s of A that are part of the bromonium ion have more s-character than those of B, further making A
less stable than B
174. Prepare (a) (E)-2-butene and (b) (Z)-2-butene from 2-bromobutane.

Ans. By retrosynthetic analysis the target compounds are each prepared from the alkyne which in turn is made from
the corresponding alkene.
(a)
The double dehydrogenation is effected with hot solid KOH, rather than NaNH2, to prevent isomerization to
1-butyne.
H3C CH3
(b) CH3C≡CCH3 C≡C

H H
(B) Addition of HX: The product of the reaction is halo alkene or gem dihalide.
R X X
R —C≡C—R HX HX
R CH2 R
H R X

(a) Order of reactivity of HX is HI > HBr > HCl.
O
(b) The addition of HX (HC1 and HBr) can be facilitated by using R—C—Xand Al2O3.
C6H13
HBr
C6H13C≡CH C = CH2
O Br
CH3–C–Br/Al2O2/CH2Cl2

Hydrocarbon 3.103
(c) It is possible to prepare vinyl halides by simply adding one mole of HX at 10°C or below this temperature.
Br
HBr
CH3 – CH2 – CH2 – C ≡ CH CH3 – CH2 – CH2 – C = CH2

CH3
DBr D
CH3 – C ≡ C – H C=C
Br H
(d) In the presence of free radical initiators such as peroxides, anti Markownikoff addition of HBr to alkynes is
observed.
Illustrations
175. List the products formed when 1-butyne reacts with one equivalent of (a) HBr, (b) HBr with peroxides, and (c)
Br2. Characterize each reaction.
Ans. (a) CH3CH2CBr=CH2 a Markovnikov electrophilic addition
(b) CH3CH2CH=CHBr an anti-Markovnikov radical addition
(c) CH3CH2CBr = CHBr an electrophilic addition
176. Give the products formed when a second equivalent of reagent is added to the products formed in Question 175.
(Same as adding two equivalents to 1-butyne.)
Ans. (a) CH3CH2CBr2CH3, (b) CH3CH2CH2CHBr2, and (c) CH3CH2CBr2CHBr2.
177. What additional factor, not present in hydrocarbon alkenes, is responsible for the orientation in the electrophilic
addition to vinyl bromides leading to the product in Question 176(a)?
Ans. The Markovnikov addition of H+ to CH3CH2CBr = CH2 gives a carbocation that is stabilized by the inductive
effect of the R groups, as was the case with alkenes. But a much more significant stabilization occurs by extended
p bonding with Br.
+
CH3CH2C = CH2 + H+ [CH3CH2C – CH3 Br–
CH3CH2CCH3] CH3CH2CBr2CH3
Br Br Br
+
178. What additional factor, not present in hydrocarbon alkenes, is responsible for the orientation in the radical addition
of HBr to vinyl bromides leading to the product in Question 176(b)?
Ans. A halogen atom destabilizes a carbon radical to which it is bonded. Hence, Br- adds as shown:
Br HBr
CH3CH2CH = CHBr CH3CH2CHCHBr2 CH3CH2CH2 CHBr2 + Br.
Br
CH3CH2CHBrCHBr (no reaction)
3.104 Hydrocarbon
(C) Addition of HOX: Alkyne reacts with HOX to give haloenol. This compound undergoes tautomerisation to give
a-halocarbonyl compound.
NOTE:
We can make a rule for obtaining product for this reaction and rule may be as follows : add oxygen on triply bonded carbon
of unsymmetrical alkyne having no hydrogen and H and X on other triply bonded carbon.
Nucleophilic addition reactions

H2O (Hydration to Carbonyl Compounds)
When passed into dilute sulphuric acid at 60oC in the presence of mercuric sulphate as catalyst, acetylene adds on one
molecule of water to form acetaldehyde. The mechanism of this hydration takes place via the formation of vinyl alcohol
as an intermediate.
+ 62
&+ Ł&++2 >&+ &+2+@ &+ &+2
+J
The homologues of acetylene form ketone when hydrated, example, propyne gives acetone.
2+ 2
+ 62
&+ & Ł&++ 2 +J62 &+ & &+ &+ &&+ 0DUNRYQLNRYDGGLWLRQ
+
DYLQ\ODOFRKRO$FHWRQH XQVWDEOH
+
2 &+
+ 62
+2 +J62
SKHQ\OHWKDQRQH
NOTE:
(1) Only acetylene gives aldehyde and aldehyde is acetaldehyde.
(2) Terminal alkynes and symmetrical internal alkynes form single ketone.
2
+2+J62+62
&+±&Ł&±&+ D &+±&±&+±&+
D 2+ ,
E +2
2 2
+2+J62+62
&+±&Ł&+ &+±&±&+ (b) &+±&+±&±&+
Hydrocarbon 3.105
(3) Unsymmetrical internal alkyne gives two isomeric ketones. Both are positional isomers and metamers.
2 2
+2+
&+±&+±&Ł&±&+ D &+±&+±&±&+±&+ E &+±&+±&+±&±&+
+J62+62
D 2+ 3HQWDQRQH 3HQWDQRQH
E +2 , ,,
Illustrations
179. (a) Explain why acetylene, unlike ethylene, does not dissolve in concentrated H2SO4. (b) Why do other alkynes
such as 2-butyne dissolve in cone. H2SO4?
Ans. (a) Ethylene gives an alkyl carbocation salt, (H3CCH2+)(HSO4-). If HC=CH were to dissolve in H2SO4, a bisulfate
salt of a vinyl carbocation, (H2C=C—H)(HSO4-), would be formed. The more s-character in the positively-
charged C, the less stable is the carbocation and the less likely it is to form, (b) Vinyl carbocations from other
alkynes have electron-repelling R substituents, i.e, CH3C=CH — CH3, and thus they are more stable than the
vinyl carbocation from acetylene.
180. Write an equation for the reaction of propyne with water in the presence of H2SO4 and HgSO4. Show the
intermediate.
+J62+62
Ans. &+ &Ł&++ 2 >&+& &+@ &+&&+

2+ 2
DYLQ\ODOFRKRO HQRO $FHWRQH DNHWRQH
XQVWDEOH VWDEOH
The Markovnikov addition of H2O gives an unstable vinyl alcohol that rearranges, as shown, to the more stable
ketone.
181. Use general equations to give the kinds of alkynes that are hydrated to (a) a single ketone, (b) a mixture of
ketones, and (c) an aldehyde, by the reaction in Question 180.
Ans. (a) Terminal: 5&Ł&+ 5&&+ and symmetrical internal: 5&Ł&5 5&&+5
2 2
(b) Unsymmetrical internal: 5&Ł&5c 5&&+5c5&+&5c
2 2
(c) Only HC=CH → CH3CHO, the only aldehyde that can be prepared this way.
182. Give the structures of the products formed from the reaction of 2-hexyne with HgSO4 and dilute H2SO4. Show the
intermediate enols.
Ans.
183. List the alkynes needed to synthesize the following ketones in the best possible yields:
(a) (CH3)2CHCCH3, (b) CH3CH2CCH2CH2CH3, (c) CCH2
O O
O
3.106 Hydrocarbon
Ans. (a) Methyl ketones, CH C = O, are best made from terminal alkynes; use (CH3)2CHC=CH.
3
R
(b) Use the symmetrical internal alkyne CH3CH2C ≡ CCH2CH3 rather than the unsymmetrical CH3C = CCH2
CH2CH3, which also gives CH3CCH2CH2CH2CH3
O
(c) C≡C
Hydroboration
Addition reaction of alkyne with boron hydride is known as hydroboration. Reaction takes place as follows :
3R — C ≡ C — H + BH3

This trivinylborane is very useful compound but this cannot be isolated because it still has pi bond and reacts Further
with BH3 to give gem-diborane.
BH3 B — (CH — CH2 — R)2
(R — CH ≡ CH2)3B R — CH2 — CH
B — (CH — CH2 — R)2

Because of this, it becomes quite difficult to make vinyl boranes in this manner. Vinyl boranes are prepared by selective
hydroborating agent known as disiamyl borane (abreviated as Sia2BH). This sterically hindered dialkyl borane reacts with
alkyne to give only vinyl boranes.
R H
R—C≡C—H C=C
H Syn addition
R R
R—C≡C—R C=C
H

(a) Vinyl borane on oxidation with H2O2/OH gives carbonyl compound. Thus alkyne can be converted into carbonyl
compound and the sequence of reaction is known as Hydroboration-oxidation.
R H R H
Sia2BH H2O2/OH
R—C≡C—H C=C C=C
H BSia2 H OH
enol
Tautomerisation
O
R — CH2 — C — H
The overall reaction can be represented as follows:
R — C ≡ CH R — CH2 — C — H

Hydrocarbon 3.107
We can formulate a rule for this reaction:

Rule 1. Add oxygen on one triply bonded carbon and 2H’s on other triply bonded carbon. In case of terminal alkyne add
oxygen on trminal carbon.
Rule 2. Terminal alkyne always gives aldehyde.
Rule 3. Symmetrical internal alkyne gives only one ketone.
Rule 4. Unsymmetrical internal alkyne gives two ketones which are isomers (positional and metamers).
(b) CH3 – CH2 – C – CH3

(II)
Both (I) and (II) are same ketone

O O
(i) Sia2BH
CH3– CH2 – C ≡ C – CH3 (a) CH3– CH2 – C – CH2 – CH3 (b) CH3– CH2 – CH2 – C – CH3
(a) O H2 (ii) H2O2/OH 3-Pentanone 2-Pentanone
(b) H2 O (II) (II)
(b) Vinylborane on acidification with organic acids give alkene (cis alkene if geometrical isomerism is possible)
(i) Sia2BH CH3 CH3
CH3– C ≡ C – CH3 C=C
(i) Sia2BH R D (ii) CH3COOH H H
R–C≡C–D C=C cis alkane
(ii) CH3COOH H H CH – C ≡ C – H (i) Sia2BH
3
CH3– CH = CH2
(ii) CH3COOH

Illustrations
184. Give the equation for the reaction of 2-butyne with BH3 complexed with tetrahydrofuran (BH3-THF).
Ans. A trivinylborane is formed which results from a syn addition.
 CH3 CH3 
BH3.THF  | | 

H — C == C — 
B
 3
 
cis isomer
185. (a) Give the equation for the reaction of 1-butyne with BH3-THF. (b) What method is employed for ensuring the
addition of only one mole of borane?
Ans. (a) Two moles of BH3 add to terminal alkynes, the reaction being difficult to stop after one mole has
reacted:
%
%+7+) %+7+)
&+&+&{&+ >&+&+&+ &+%+@ &+&+&+&+
DJHPGLERUDQH
3.108 Hydrocarbon
&+
(b) A sterically hindered dialkylborane, di-sec-isoamylborane or > &+ &+&±@%+ (abbreviated Sia2BH), is
+
used instead of BH3.
6LD%+
&+&+&Ł&+ &+&+&+ &+%6LD
Like all boranes, Sia2BH gives anti-Markovnikov products when adding to triple bonds as well as to double
bonds.
186. Give the structural formulae for the products formed on the oxidation in alkaline H2O2 of the product in (a)
Question 184(b) and 185(b).
(a) The +& &±%± grouping is converted to +& &±2+, a vinyl alcohol, which rearranges to a carbonyl
compound.
(a) Internal alkynes give ketones on oxidative-hydroboration.
§ &+ &+ ·
¨ _ _ ¸¸ + 2
& ² ¸¸ % 2+± >&+&+ &&+@ &+&+&&+
¨¨
¨+ ² &
© ¹
2+ 2
XQVWDEOHHQRO DNHWRQH
(b) Terminal alkynes give aldehydes

+2
&+&+&+ &+%6LD >&+&+&+ &+2+@ &+&+&+&+2
2+±
DQDOGHK\GH
187. (a) What is the product obtained from the reaction of a vinylborane with acetic acid (CH3COOH)? (b) Give the
structural formulae and IUPAC names for the products formed from the reaction with CH3COOH of the product
in (i) Question 184 and (ii) Question 184(b)
&+&22+
Ans. (a) 5&+ &% 5&+ &+ as H replaces the B.
 CH3 CH3  CH3 CH3



| |  CH3 COOH
(b) H — C == C —  3 B

 
C=C
H H
(Z)-2-Butene
The net reaction is a syn addition of two H’s to give a cis alkene.
(ii) CH3CH2CH=CHBSia2 
CH3 COOH
→ CH3CH2CH=CH2
1-Butene
188. Use two methods to convert 2-butyne to (Z)-2,3-dideutero-2-butene.
H3C CH3
D2/Lindlar’s catalyst 1. BD3
Ans. CH3C ≡ CCH3 C=C CH3C ≡ CCH3
2. CH3COOD
D D
189. Use two methods to convert 2-butyne to (Z)-2-deutero-2-butene.

H3C CH3
1. BD3 .THF 1. BH3.THF
Ans. CH3C ≡ CCH3 C=C CH3C ≡ CCH3
2. CH3COOH 2. CH3COOD
D H
Hydrocarbon 3.109
190. From 1-butyne, synthesize (a) (E)-1-deutero-1-butene and (b) 2-deutero-l-butene.

CH3CH2 H CH3CH2 H
Sia2 BH CH3COOD
Ans. (a) CH3CH2C ≡ CH C=C C=C
H BSia2 H D
CH3CH2 H CH3CH2 H
Sia2 BD CH3COOH
(b) CH3CH2C ≡ CH C=C C=C
D BSia2 D H
191. Show the steps in the oxidative-deuteroboration with Sia2BD of (a) 2-butyne and (b) 1-hexyne.
Sia2 BD H2O2·OH–
Ans. (a) CH3C ≡ CCH3 CH3C = CCH3 [CH3C = CCH3] CH3CHDCCH3
D BSia2 D OH O
Sia2 BD H2O2·OH–
(b) CH3(CH2)3C ≡ CH CH3(CH2)3CD = CHBSia2
[CH3(CH2)3CD = CH (OH)] CH3(CH2)3CHDCH = O
Addition of hydrogen (See preparation of alkene from alkyne)

Alkynes are more reactive than alkenes towards hydrogenation. It is because
(a) sp-hybrid carbon of alkyne is less hindered than sp2-hybrid carbon of alkene.
In transition state formation;
Reactivity ∝ 1/Steric hindrance
(b) Alkyne can be easily absorbed on the surface of catalyst due to cylindrical nature of pi bonds (or linear structure
of —C ≡ C—).
Oxidation of Alkynes
Like alkenes, these also give two types of oxidation reactions:
(1) Oxidation without cleavage: The product of oxidation is vie dicarbonyl compound.
(a) Oxidation by Baeyer Reagent:

In case of acetylene product is oxalic acid
(b) Oxidation by SeO2: SeO2 converts alkyne into vie dicarbonyl compound:

3.110 Hydrocarbon

(2) Oxidative cleavage: Alkynes undergo oxidative cleavage with hot basic KMnO4. In this oxidation triple bond breaks
and both triply bonded carbon converts into carboxylic group.

KMnO4/OH/∆
CH3 — C ≡ C — C6H5 CH3COOH + C6H5COOH

NOTE:
Terminal alkynes give formic acid as one of the oxidation products which further oxidises into CO2. Thus loss of a carbon
in this reaction indicates that alkyne is terminal.
Ozonolysis
20. Ozonolysis-Hydrolysis
Acetylene and its homologues form ozonides with ozone, and these compounds are decomposed by water to form diketones,
which are then oxidised to acids by the hydrogen peroxide formed in the reaction.
Acetylene is exceptional in that it gives glyoxal as well as formic acid.

Hydrocarbon 3.111
Illustrations
192. Give the products formed from the reaction of each of the following compounds with KMnO4 in warm acid,
(a) 2-Methyl-3-heptyne, (b) 3-hexyne, (c) 1-pentyne, and (d) 2,6-nonadiyne.
Ans. (a) (CH3)2CHC ≡ CCH2CH2CH3 → (CH3)2CHCOOH + HOOCCH2CH2CH3
(b) CH3CH2C ≡ CCH2CH3 → 2CH3CH2COOH. Symmetrical internal alkynes give one acid.
(c) HC ≡ CCH2CH2CH3 → CO2 + HOOCCH2CH2CH3. C1 of a terminal alkyne is oxidized to CO2.
(d) CH3C ≡ CCH2CH2C ≡ CCH2CH3 → CH3COOH + HOOCCH2CH2COOH + HOOCCH2CH3
The central portion of a diyne gives a dicarboxylic acid.
193. What is the structural formula of an alkyne that undergoes oxidative cleavage to give two moles of CH3COOH
and one mole of HOOC(CH2)3COOH?
Ans. Write the products in a line so that the COOH groups point toward each other keeping the dicarboxylic acid in the
middle. Then erase the OOH’s and join the C’s of the COOH’s by triple bonds. Thus
CH3COOH, HOOC(CH2)3COOH, HOOCCH3 ← CH3C=C(CH2)3C=CCH3
The number of C atoms in the proposed structure must be the same as the total in the oxidation products, includ-
ing CO2 if formed.
194. Deduce the structural formula of a compound, Cl0H10 (A) that gives as the only organic compound,
HOOCCH2CHCH2COOH (B) on oxidative cleavage.
Ans. A has an index of unsaturation of 6 which is attributed to the presence of three triple bonds because of the
isolation of the tricarboxylic acid B. Since B has three less C’s than A, the three triple bonds must be terminal so
that three moles of CO2 are lost in the oxidation. Compound A is
17. Identify the compound ‘Y’ in the following sequence of reaction
)i)O3 Zn / CH3 COOH
HC CH X Y
)ii) H2O/ Zn
OH OH
(a) HO (b) O
OAc
(c) H3C (d) CH3COOH
OAc
SOLUTION
O OH
Ozonolysis Reduction
17. HC CH O HO
3.112 Hydrocarbon
21. Nucleophiles
When acetylene is passed into dilute hydrochloric acid at 65oC in the presence of mercuric ions as catalyst, vinyl chloride
is formed :
2+
CH ≡ CH + HCl 
Hg
→ CH2 = CHCl
Acetylene adds on hydrogen cyanide in the presence of cuprous chloride in hydrochloric acid as catalyst to form vinyl
cyanide :
CH ≡ CH + HCN → CH2=CHCN
Vinyl cyanide is used in the manufacture of Buna-N-synthetic rubber, which is a copolymer of vinyl cyanide and
butadiene.
17. When acetylene is passed into warm acetic acid in the presence of mercuric ions as catalyst, vinyl acetate and
ethylidene diacetate are formed:
2+
CH≡CH + CH3CO2H 
Hg
→ CH2=CHOOCCH3
2+
CH2=CHOOCCH3 + CH3CO2H 
Hg
→ CH3CH(OOCCH3)2
Vinyl acetate (liquid) is used in the plastics industry. Ethylidene diacetate (liquid), when heated rapidly to 300-4000C,
gives acetic anhydride and acetaldehyde.
18. Acetylene reacts with nitric acid in the presence of mercuric ions to form nitroform, CH(NO3)3, and combines with
arsenic trichloride to form Lewisite.
19. When acetylene is passed into methanol at 160-200oC in the presence of small amount (1-2 per cent) of potassium
methoxide and under pressure just high enough to prevent boiling, methyl vinyl ether is formed. The mechanism is
believed to involve nucleophilic attack in the first step.
CH≡CH + CH3O- → CH=CHOCH3  CH3 OH
→ CH2=CHOCH3 + CH3O-
Methyl vinyl ether is used for making the polyvinyl ether plastics.
20. Acetylene and formaldehyde interact in the presence of sodium alkoxide as catalyst to form butynediol, together with
smaller amounts of propargyl alcohol:
HC≡CH + CH3O– HC≡C— + CH3OH
– — CH 3 OH
O = CH2 C ≡ CH O — CH2 — C ≡ CH
−
HO − CH 2 − C ≡ CH CH
 3O
→ HOCH 2 C ≡ CCH 2 OH
CH 2 O
This reaction in which acetylene (or any compound containing the ≡ CH group, i.e., a methine hydrogen atom) adds
on to certain unsaturated links (such as in the carbonyl group), is known as ethinylation. Thus the above reactions with
formaldehyde are examples of ethinylation.
21. When acetylene is passed into hypochlorous acid solution, dichloroacetaldehyde is formed:
HOCl
CH ≡ CH + HOCl → [CHCl = CHOH] → [Cl2CHCH(OH)2] → Cl2CHCHO + H2O
Dichloroacetic acid, Cl2CHCO2H, is also formed by the oxidation of dichloroacetaldehyde by the hypochlorous acid.
Isomerisation
Alkyne undergoes isomerisation either in the presence of ale KOH or NaNH2
(a) Non-terminal alkyne converts into terminal alkyne.

Hydrocarbon 3.113
(b) Terminal alkyne having a—CH2 group isomerises into non-terminal alkyne as well as into conjugated diene.
Coupling of Alkynes
(1) Coupling in mild acid conditions: Terminal alkyne undergoes coupling reaction in the presence of midly acid con-
dition to give alkeneyne. The reaction is simply addition reaction between two molecule of alkyne. One molecule
behaves as substrate and other behaves as reagent and addition takes place according to anti Markovnikov’s rule.

(2) Oxidative coupling: Oxidative coupling takes place by shaking terminal alkyne in a solution of Cu2Cl2 in methanol/
pyridine (a base) in the presence of oxygen or air. The product of the reaction is alkadiyne.

(3) Addition of carbenes: Alkynes react with CH2 and other carbenes. However, since alkyne have two pi bonds, this
addition can occur twice.
H H
C
CH2 CH2
R–C≡C–R R–C=C–R R–C–C–R
C C
H H H H

When passed through a heated tube acetylene polymerises, to a small extent, to benzene.
3C2H2 ∆ ∆

Homologues of acetylene behave in a similar manner, e.g., propyne polymerises to 1,3,5-trimethylbenzene, and
but-2-yne to hexamethylbenzene:

3.114 Hydrocarbon
Under suitable conditions acetylene polymerises to cyclooctatetraene:
4C2 H2

18. An unsaturated hydrocarbon A (C6H10) readily gives B on treatment with NaNH2 in liquid
NH3. When B is allowed to react with 1-chloropropane a compound C is obtained. On partial
hydrocarbon in the presence of Lindlar catalyst, compound C gives D (C9H18). On ozonolysis D
gives 2, 2-dimethyl propanal and 1-butanal. With proper reasoning give the structures of A, B, C
and D.
19. When gas (A) is passed through dry KOH at low temperature, a deep red coloured compound, (B)
and a gas (C) are obtained. The gas (A), on reaction with but –2- ene, followed by treatment with
Zn/H2O yields acetaldehyde. Identify (A), (B) and (C)
20. 1,4 – Pentadiene reacts with excess of HCl in the presence or benzoyl peroxide to give
compound (X) which upon reaction with excess of Mg in dry ether forms (Y). Compound (Y) on
treatment ethyl acetate followed by dilute acid yields (Z). Identify the structures compound (X),
(Y) and (Z).
21. There are six different alkane A, B, C, D, E and F. Each on addition of one mole of hydrogen
gives G which is the lowest molecular wt. Hydrocarbon containing only one asymmetric carbon
atom. None of the above alkene give acetone as a product on ozonolysis. Give the structures of A
to F. Identity the alkenes that is likely to give a ketone containing more than five carbon atoms on
treatment with a warm con solution of alkaline KMnO4. Show various configurations of G in fisher
projection.
SOLUTIONS
CH 3 CH3
H3 C
– +
18. A = B = H3 C C Na
H3 C H CH3
CH 3 CH3
H3C
C = H3 C D=
CH 3
CH 3 CH 3 H3C
19. (A) O3, (B) KO3, (C) O2

Hydrocarbon 3.115
HO
CH 3
20. H C H3 C
3 CH 3
Cl Cl
H3 C
(X) (Z)
MgCl MgCl CH 2
H3 C CH 3 H3 C CH 3
(Y)
CH 3
(Z)
21. The 6 different alkenes (A) to (F) are
CH 3 CH3
A= B=
CH3 CH3
H2C H3C
CH3 CH2
C= D=
CH3 CH3
H3C
H3C
CH3 CH3
E= F=
CH3 CH2
H3C H3C
H3C
G=
H
H3C
CH3
3.116 Hydrocarbon
SOLVED CONCEPTUAL EXAMPLES CH3
1. Chlorination of optically active 2-chlorobutane yields

(iv)
a mixture of isomers with the formula C4H8Cl2.
(a) How many different isomers would YOU expect
to be produced? What are their structures?
(b) Which of these fractions would be optically ac- CH3
tive?
Sol. (a) (v) H3C
CH 3 CH2 Cl CH3 CH3
CH3
CCl 2 CHCl CHCl
H––C––Cl + Cl 2 + + + CHCl
CH2 CH2 CHCl CH2 CH2
CH 2 CH 3
CH3 CH3 CH3 CH3
4 possible isomers Sol.
(i) (4Z)-4-(1-methylbutyl)hexa-1,4-diene
(b) T
he compounds which are having chiral centers
(ii) (4E)-4-isopropyl-6-methyldec-4-ene
(asymetric carbon) will be optically active
(iii) Allylcyclopropane
CH3 CH3 (iv) (2Z,4Z)-hexa-2,4-diene
CH 2 Cl
H ––C—Cl (v) (3E)-penta-1,3-diene
Cl ––C—H H ––C—Cl
&
H ––C—Cl CH2 3. Identify (a) the chiral compound C, C10 H14 , that is
C 2 H5
oxidized with alk. KMnO 4 to PhCOOH, and (b) the
CH CH2 Cl achiral compound D, C10 H14 , inert to oxidation under
3
(i) (ii) (iii)

the same condition.
Sol. Given
Three fractions are optically active
2. Write the IUPAC name of the following compounds COOH
CH2
(i) H3 C
C10 H14 alk. KMnO4
chiral
(C)
H3C CH3 C10 H14 Inert to oxidation
(D)
H3C achiral
CH3
Since benzoilic acid is the product `C’ should be
monosubstituted benzene.
C4 H 9 CH3
CH3
H5C2 C CH3
(ii) H3C H 5 C2 CH CH3
CH3
(iii) (C) (D)

CH2 Achiral and resistant to oxidation
Hydrocarbon 3.117
4. Calculate the relative ratio of iso and t-butyl bromides CH3 CH3 H3C CH3
formed by the bromination of isobutane. The relative Potassium
tertbutoride
rates of bromination of tertiary, secondary and primary H Cl C C +
H-atoms are 1600: 82: 1.
Sol. CH3 CH3 H3C CH3
(Y)
H3 C CH 3
H3 C H3C CH3
Br 2
(i) CH CH3 C + CH C
H3 C Br H3C CH2
H3 C
t-butyl bromide (Z)
H3 C H3C CH3
Hydrogenation
Y&Z CH HC
CH CH2 Br
H3C CH3
H3 C (Z)
isobutyl bromide
6. The final step is the proof of structure of an unknown
(ii) Relative rates of bromination products for t-butyl alkane was its synthesis by the coupling of lithium di-
and isobutyl bromide is 1600: 1. tert-butyl copper with n-butyl bromide. What was the
(iii) Isobutane has 9 hydrogen atom of 1° and 1 hydro- alkane?
gen atom of 3°.
Sol. The alkane was 2,2 dimethyl hexane
So reactivity of 3° H atom = 1≡ 1600 = 1600
and total reactivity of 1° H atom = 9 ≡ 1 = 9 CH 3
Total reactivity of isobutane = 1600 + 9 = 1609
CH 3 —CH 2 —CH 2 —CH 2 —Br + CH 3 —C— CuLi
As Q 1609 gm isobutane gives 1600 gm 3° n-Butyl bromide
isomers CH 3 2
1600 Lithium di-tert-butyl copper

∴ 58 gm isobutane gives = × 58
1609 CH 3
= 57.68 gm 3° isomer
CH 2 CH 2 CH 2 CH 2 —C—CH 3
9
Similarly 58 gm isobutane gives = × 50
1609 CH 3
= 0.325 gm 2.2 Dimethyl hexane
3° isomer product 57.68

= = 177.48 Ph H
1° isomer product 0.325
7. (a) + Br2 (A)
5. An alkyl halide, (X), of formula C6 H13Cl on H CH3
treatment with potassium tertiary butoxide gives two
isomeric alkenes Y and Z (C6 H12 ). Both alkenes on HBr/peroxide
hydrogenation gives 2, 3-dimethylbutane. Predict the
structures of X, Y and Z.
Sol. An alkyl halide X (C6 H13Cl) gives two isomeric (B)
alkenes Y and Z. Since it is forming two isomeric Identify A and B
alkane on dehydrohalogenation reaction, Cl should
(b) Write the product(s) of the following reactions:
not be at the terminal alkyl group. The reaction
are CH 3CH = CH 2 + BrCCl3 →
Peroxide
?
3.118 Hydrocarbon
Sol. In the above reaction acetylene is the only organic re-

H3C Br agent used.
(a) CHHC (Trans Addition) 11. Complete the following equation:
Br CH3 (a) CH 3C ≡ CCH 3 

H2
Pt
→
(A) (A) 
H2
Pt
→ CH 3CH 2 CH 2 CH 3
Ph CH 2 CH CH3
(b) CH 3 − C ≡ CCH 3 
Na +C2 H5OH
→ (B) + NaOC2 H 5
Br
Sol.
(B)
(b) CH 3 — CH — CH 2CCl 3 H 3C CH 3
(a) C C
Br
H H
8. Write the major products of the hydroboration and
oxidation of: H3C H
(a) 1-Ethyl cyclopentene (b) C C
(b) Methylene cyclopentene.
H CH3
Sol.
C2H5
Ph H
(i) BH3 , THF
(a) C2H5 H
(ii) H 2 O2 , OH
H 12. C C + Br2 (A)
OH
(Trans and racemic) H CH3
(b) OH HBr/peroxide
9. Give the missing compounds in the following: (B)

BH 3.THF CH 3COOH
(a) ? ? Sol.
BH3 .THF CH3 COOH H3 C Br
(b) ? ?
BH3 .THF CH3 COOH CH HC (Trans Addition)
(c) ? ?
(i) BH3 .THF
(d) ? Br CH3
(ii) CH 3COOH
(A)
Sol.
Ph CH 2 CH CH3
(a) (CH 3CH 2 )3 B, CH 3 — CH 3
(b) (CH 3CH 2 CH 2 )3 B, CH 3CH 2 CH 3 Br
(c) [CH 3CH 2 CH — CH 3 ]3 B, CH 3CH 2 CH 2 CH 3 (B)
(d) 13. (a) Complete the following reactions:

+
CH 3COCH 3 
NaNH 2
→ A 
C2 H 2
→ B 
H
→
10. Use HC ≡ CH as the only organic reagent to prepare Al2 O3 , ∆
(a) (E) –3– hexene and (b) (Z) –3– hexene C →
H 2 (1 equiv)
Pd
D 
400° C
→E
Sol. HC ≡ CH  Na
→ HC ≡ C– Na+ (1) (b) Complete the following reactions:
HC ≡ CH → CH2 = CH2
H2
CH 3 − C ≡ CH 
i) NaNH 2
→ A  H2
→
HCl
→ CH3 – CH2Cl (2) ii) CH3CH 2 Br Lindlar 's catalyst
B 
CH 2 I2
→C
Combine (1) and (2) Zn (Cu )
Hydrocarbon 3.119
ONa Sol.
CH3
Sol. (a) A = H3C
CH2 X=
OH
H3C
ONa triple bond is not affected
B= by HCO3H
OH
HC CH3 O
H3C O
OH Y= CH3
C=
CH3 OH
HC KMnO4 hydroxylates
H3C C = C bond and
OH C ≡ C bond
OH
D=
CH3 O OH
Z=
CH2
O
CH2 OH + CH3COOH; C = C,
H2C and C ≡ C bonds are
E= O affected due to
CH3
isoprene OH ozonolysis
(b) A = H 3C CH3 15. (a) Give reasons fwor the following:

When 1-penten -4-yne is treated with HBr in equi-
H H
molecular proportion, the addition takes place on
double bond and not on triple bond yielding there-
B= by the product CH3CH(Br)CH2OCH.
H 3C (b) Provide a suitable mechanism for the following
reaction.
H3C
OH CH3
H CH3
C=
H
CH3 CH3
CH3 Sol. (a) Electrophilic addition of HBr on carbon - car-

bon double leads to the formation of 2° – carbocation
HCO3 H while that on carbon - carbon triple bond leads to the
X formation of vinylic carbocation as the intermedi-
KMnO 4 , Δ ate. Vinylic carbocation being most unstable whereas
Y
14. 2°-carbocation being relatively more stable, addition
O3 , H 2 O
Z (mix) is favoured on ethylenic linkage more stable, addition
is favoured on ethylenic linkage rather than on acety-
Identify X, Y and Z lenic.
3.120 Hydrocarbon
Addition on carbon - carbon double bond:

⊕ H OH
CH 2=CH—CH 2—C≡CH + HBr CH 3CHCH 2C≡CH (c)
2° - carbocation HO H
17. Deduce the structural formula of a compound,

CH 3CHCH 2C≡CH C10H10(A), that gives as the only organic compound,
HOOCCH2CHCH2COOH (B) on oxidative cleavage,
Br
(Actual product)
CH2COOH
Addition on carbon - carbon triple bond.
C10H10 is the molecular formula of the organic
⊕
CH 2=CH—CH2 — C≡CH + HBr CH2 =CH—CH2 —C=CH2 compound
(Vinylic carbocation) Sol. The degree of unsaturation in the compound is =
Br – (number of carbon)
CH 2=CH—CH2—C=CH 2 Number of hydrogen 10
– + 1 = (10 + 1) – = 11 – 5 = 6
2 2
Br
+ This compound contains 6 bonds on oxidative cleav-
OH OH2 age it is producing only one compound, so all the mul-
tiple bonds should be at the terminal atom.
H+ − H2O
(b) KMnO4 /H+
HC ≡ CH — CH2 — CH — C ≡ CH
H
CH3 (A) CH2 — C ≡ CH
+
HOOC — CH 2 — CH — CH 2 COOH
(B) CH 2 COOH
16. Predict the product of the following
conc. H2SO4/∆ 18. What happens when:
A
(a) (a) Dry sodium propionate is heated with soda-lime?
HCl
OH B (b) Water is added to aluminium carbide?
CH3 H2O/H+ (c) Ethyl iodide is treated with phosphorus and hy-
A drogen iodide?
(i) B2H6
CH2 – B (d) Ethyl iodide dissolved in dry ether is treated with
(b) H3C (ii) H2O2 (OH )
sodium metal?
CH3 (i) Hg(OAc)2
(e) Methane is treated with iodine in presence of an
C
(ii) NaBH4
oxidizing agent?
OH (f) n-Hexane is treated with Cr2O3 supported over
H+ RCO3H H 2O
(c) J alumina at 600°C?
(g) Ethane is treated with cone, nitric acid at 450°C?
Sol. (h) Lithium dimethyl cuprate is treated with ethyl
CH3 CH3 bromide?
Cl Sol.
(a)
CH3 CH3 (a) C2H5COONa + NaOH  CaO
→ C2H6 + Na2CO3
(A) (B) (b) Al4C3 + 12H2O → 3CH4 + 4Al(OH)3
CH3 150° C
(c) (i) 3C2H5I + 3HI  → 3C2H6 + 3I2
(b) CH3 (CH3 )3 C — CH2 — CH2 — OH
H3C (B) (ii) 2P + 3I2 → 2PI3
OH
3,3–dimethylbutanol –1 (d) 2C2H5I + 2Na → C4H10 + 2NaI
CH3 CH3
(e) (i) CH 4 + I 2  CH 3 I + HI
CH3
(ii) 2HI + O → H2O + HI
H3C
CH3 (f) C6H14 →
Cr2 O3 /Al2 O3
C6H6 + 4H2
OH 600° C
Hydrocarbon 3.121
(g) C2H6 + HNO3 450° C

→ C2H5NO2 + CH3NO2 O
(h) Li(CH3)2Cu + C2H5Br → C3H8 + CH3Cu + LiBr (ii) (A) CH3 – C ≡ CH (B) H3C
19. How will you prepare the following: CH3

(a) n-Butane from ethyl bromide OH
(b) Ethane from acetic acid
(C) H3C (D) CH3 – CH = CH2
(c) Ethane from ethene
(d) Methane from acetic acid CH3
(e) Ethane from methane in two steps
Br
(f) Ethane from ethanol in one step
(g) Methyl chloride from aluminium carbide in two (E) H3C (F) CH3 – C ≡ CH
steps
CH2
(h) Propane from methane
Sol. Br
(a) C2H5Br + 2Na + BrC2H5 → C2H5.C2H5 + 2NaBr
Br
(b) CH 3 COOH + KOH CH 3 COOK + 2NaBr
Electrolysis
(iii) A = B =
H3C CH3
CH 3 – CH3 H3C CH3
(c) C2H4 + H2 
Ni
→ C2H6 %U %U
300° C
(d) CH 3COOH + NaOH 

→ C= D = +& &+
CH 3COONa 
→ CH 4 NaOH
+& &+
CaO
(e) CH 4 → CH 3Cl → CH 3 − CH 3

Cl2 Na
E = CH3COOH (2 mol)
hν Ether
(f) C 2 H 5OH 

→ C2 H 6 P/HI
21. Identify the unknown alkene in the following
(g) Al4 C3 
→ CH 4 → CH 3Cl
H 2O Cl2 reactions.
hν
(h) CH 4 + Cl2 
hν (a) (A)  (i) O3
→ CH3COCH3 + CH3CH(CH3)
→ CH 3Cl 
Na
→ (ii) Zn/CH3COOH
CHO
CH 3 − CH 3 
Cl2
→
(b) (B)  → CH3COCH2CH2CH2CH2
–
hν (i) KMnO 4 /OH
(ii) H3O+
CH 3 CH 2 Cl → Li(CH 3 CH 2 ) 2 Cu
Cul
COOH
Li

→ CH 3 CH 2 CH 3
CH3 Cl
(c) (C) →
(i) O3
(ii) H 2 O
2CH 3CH 2 CO 2 H
–
20. Identify the missing compound in the following (d) (D) 
(i) KMnO 4 /OH
(ii) H3O+
→ CH3CH2COOH + CH3 CH2
sequence of reaction: CH2 CH2 COOH
(i) CaC 2 
H 2O
→(A)  H2
→(B) 
Br2
→ CH3
H+ Lindlar 's catalyst
(C) 
KOH (alc.)
→ (D) 
NaNH 2
∆
→ (E) Sol. A =
+ 2+
H3C CH3
(ii) Mg 2 C3 
4H 2 O
→ (A) 
H /Hg
H 2O
→ (B) 
LiAlH 4
→ CH3
(C) →
Conc. H 2SO 4
∆
(D) 
Br2
→ (E) 
NaNH 2
∆
→ (F) CH3
(iii) CH 3CH 2 CH 2 CH 3 

Br2 /hν
→ A 
alcoholic KOH
→ B=
B 
→ C 
1 mol
→ D → E
Br2 /CCl4 alcoholic KOH KMnO 4
H+
Sol. CH3
C= H3C
(i) (a) CH ≡ CH (b) CH2CH2
(c) CH2BrCH2Br (d) CH2 = CHBr CH3
D= H3C
(E) CH ≡ CH
3.122 Hydrocarbon
22. (a) Suggest appropriate structures for the missing

compounds. (The no. of carbon atoms remains the (c) O C≡C NO2
same throughout the reactions) H3C
CH3 O C = HC NO 2
dil. H2SO4 HlO4 OH
–
A B C
H3C OH
CH3
(d) E = CH2
(b) l-isopropyl-4-methyl ← excess H 2 /Pd
 Limonene

Br2 /CCl4
→ decolourised solution cyclohexane
23. Complete the following reaction
O3 / Zn / H 2O
CH3
O O eq. H2 1
(i) Major Product
Lindlar catalyst (A)
H3C CH3
CH 2 O + H
(1 mole) (1 mole)
CH3
O
(ii) Peroxide
Identify the structure of Limonene. + HBr B
(c) H3C
O H 3O +
A. Identify A. Br2 Zn
(iii) (C ) ( D)
CH 2 (Cl2) CH 3 COOH
NO2 B 2 H6 H+
−
(E) (F )
+ H2 O 2 / OH
O
CH3
(i) O3 + CH 2O Sol. A =
(d) (E)
(ii) Zn / AcOH
CH3 Br
Sol.
H3C O B= C=
HO O
Br
(a) Br
HO CH3
CH3 OH
H3C O OH
(A) (B) (C) D= E=
(b) D
ecolourisation of Br2/CCl4 shows limonene to be
an alkene is the skeleton of alkene and one double
bond is a terminal double bond and other is inside
the ring. The above clues suggest the following F=
structure for limonene.
CH3 CH2 O
H 3C H 3C
CH3 NaNH 2
24. (a) A B.
H+
CH3 (Limonene)
CH3

Hydrocarbon 3.123
(b) Show the products of these reactions: ∴ The reactions are

Br H3C
Hydrogenation CH3
H3C →
CH2 CH2 CH3
NaNH 2 /∆
(i) HCl(excess)
Ozonolysis
→ CH 3COCHO + 2HCHO
CH2
26. Complete the following reaction.

CH3
CH3 CH2 1 2 3
EtOK/Δ (i)
(ii) EtOH
Br
[IIT 1999]
Br &+
Sol.
Cl (ii)
CH3 +
0DMRUSURGXFW
/LQGODU FDWDO\VW
(a) A = Cl [IIT 2001]
&+
CH3 CH (iii) + & & + 2+
0DMRUSURGXFW
'
B= &+ %U
[IIT 2001]
CH 2 + 2 /L$O+
Sol. (i) 2
+ 62
(b) (i) 2+
± + 2
+
&
CH3 & + +
(ii)
&+ /LQGODU FDWDO\VW
CH3 +&
CH (iii) (CH 3 )3 CCH 2 Br 
C2 H5OH
∆
→
(ii)
(CH 3 ) 2 C = CH — CH 3
25. An organic compound E (C5H8) on hydrogenation 27. Give the structures of two major products from
gives compound F(C5H12). Compound (E) on 3-ethylpent-2-ene under each of the following
ozonolysis gives formaldehyde and 2-ketopropanal. reaction conditions
Deduce the structures of compound (E) (a) HBr in presence of peroxide
(b) Br2/H2O.
[IIT 1995]
Sol.
Sol. (i) Compound (E) gives (F) on hydrogenation.
Also (E) on ozonolysis gives HCHO and 2-ketopropa- +& &+ +%U 3HUR[LGH
nal. Thus (E) (C5H8) having two double bonds may be $QWL 0DUNRZQLNRII
CH2 = O + CH3 — C — CHO + O = CH 2 +& %U

HWK\OSHQWHQH
O +& &+
E is CH3 — C — CH = CH 2
+&
CH 2 EURPRHWK\OSHQWDQH
3.124 Hydrocarbon
%U + 2 Due to contribution of structure II and III, the cen-

+& &+ tral C—C bond acquires some doublebond character.
+2%U
& +
0DUNRZQLNRII $GGLWLRQ Hence it is smaller than that in butane.
HWK\OSHQWHQH %U CH 2 — CH — CH — CH2
& + Buta – 1, 3 – diene
CH3 — CH2 — CH 2 — CH3
+& &+ Butane
2+
29. In alkyl halide X of formula C6H13Cl on treatment
with potassium tertiary butoxide gives two isomeric
28. (a) Explain briefly as to why alkynes are generally
isomeric alkenes Y and Z (C6H12). Both alkenes on
less reactive than alkenes towards electrophilic
hydrogenation gives 2-3-dimethyl butane. Predict the
reagents such as H+.
(b) Explain why the central carbon-carbon bond in
1-2-butadiene is shorter than in butane. CH3 CH3
Sol. (CH 3 ) 3 COK
H3 C C C CH3
(a) Alkynes are less reactive than alkene to- – HCl
Sol. (Elimination occurs)
wards electrophilic additions due to following Cl H
reasons:
(i) The triple bonded carbons are sp-hybridised which 2-Chloro-2, 3-dimethylbutane
are relatively more electronegative. Consequently, (X)
they hold the π electrons more firmly.
H3C CH3 H3C CH3
(ii) Electrophilic attack on ethylenic bond gives alkyl
carbocation while that on acetylenic bond gives C C + C HC
vinylic carbocation which is less stable than alkyl
H3C CH3 H2C CH3
carbocation.
2, 3-dimethylbut-2-ene 2, 3-Dimethylbut-1-ene
⊕ +
CH 2 = CH 2 + E 
→ E — CH 2 — C H 2 (More stable) (Y) (Z)
+
CH ≡ CH + E + 
→ E — CH = C H (Less stable)
(b) B
uta-1, 3-diene is a hybrid of the following rea- CH3
sonating forms
CH3
+ H3C
[CH 2 = CH — CH = CH 2 ←
→ C H 2 — CH = CH —
I II
– – +
CH3
C H 2 ←
→ C H 2 — CH = CH — C H 2 ] 2,3-dimethylbutane
III
2. Ammonical AgNO3 reacts with acetylene to

STEP–I CHECK YOUR CONCEPT
form:
1. Which of the following will have least hindered (a) Silver acetate (b) Silver acetylide
rotation about carbon-carbon bond ? (c) Silver formate (d) Silver metal
(a) Ethane 3. On heating CH3COONa with soda lime the gas
(b) Ethylene evolved will be
(c) Acetylene (a) C2H2 (b) CH4
(d) hexachloro ethane. (c) C2H6 (d) C2H4.
Hydrocarbon 3.125
4. If 20cc of methane burnt using 50cc of oxygen 11. What is the chief product obtained when n-butane
the volume of the gases left after cooling to room is treated with bromine in the presence of light at
temperature: 130°C?
(a) 60cc (b) 70cc
(a) H3C Br
(c) 30cc (d) 50cc
CH3
5. A sample of 1.79 mg of a compound of molar mass
90 g mol–1 when treated with CH3Mgl releases (b) H3C
1.34 ml of a gas at STP. The number of active Br
hydrogen in the molecule is
(c) H3C
(a) 1 (b) 2 Br
(c) 3 (d) 4.
6. The product obtained via oxymercuration (HgSO4 + CH3
H2SO4) of 1-butyne would be CH3
(a) H3C
CH3 (d) H3C C CH 2 Br
CH3
O
(b) H3C O 12. Which of the following will have least hindered
rotation about carbon-carbon bond?
O (a) Ethane (b) Ethylene
(c) H3C + CH2 O
(c) Acetylene (d) Hexachloro ethane
O
+ HCO2 H 13. The olefin, which on ozonolysis gives CH3CH2CHO
(d) H3 C
and CH3CHO.
OH (a) But-1-ene (b) But-2-ene
(c) Pent-1-ene (d) Pent-2-ene.
7. The addition of Br2 to trans-2-butene produces
(a) (+) 2, 3-dibromobutane 14. Addition of one equivalent of bromine to 1, 3–
(b) (–) 2, 3-dibromobutane pentadiene produces
(c) rac –2, 3-dibromobutane (a) 1, 3–pentadiene produces
(d) meso-2, 3-dibromobutane (b) 4, 5–dibromo–2–pentene
8. On heating CH3COONa with sodalime the gas (c) 3, 4–dibromopentene
evolved will be (d) 3, 4–dibromo–2–pentene
(a) C2H2 (b) CH4 15. What is the chief product obtained when n–butane
(c) C2H6 (d) C2H4 is treated with bromine in the presence of light at
9. The treatment of CH3C(CH3) = CHCH3 with NalO4 or 130°C?
boiling KMnO4 produces (a) CH3 – CH2 – CH2 – CH2 – Br
(a) CH 3COCH 3 + CH 2 O (b) CH3 – CH2 – CH – Br
(b) CH 3CHO + CH 3CHO |
CH3
(c) CH 3COCH 3 + CO 2
(c) CH3 – CH – CH – Br
(d) CH 3COCH 3 + HCOOH . |
CH3
10. A mixture of methane, ethylene, ethyne gases is passed
through a Woulfe’s bottle containing ammonical CH3
AgNO3. The gas not coming out from bottle is |
(d) H3C – C – CH 2Br
(a) Methane (b) Ethyne |
(c) Ethelene (d) All CH3
3.126 Hydrocarbon
16. Addition of halogen acid (HX) is least in

(a) CH 2 = CHCl (b) CH 2 = CH 2
(c) CH 3 — CH = CH 2 (d) (CH 3 ) 2 C = CH 2. 1. End product of the following sequence is:
17. Bromination of an-alkane as compared to chlorination CaO + C 
Heat
→ (A) 
H 2O
→ (C) 
Hg 2+
→(C)
H 2SO4
proceeds
(a) at a slower rate (a) Ethanol
(b) at a faster rate (b) Ethyl hydrogen sulphate
(c) with equal rates (c) Ethanal
(d) with equal or different rates depending upon the (d) Ethylene glycol.
temperature
2. 10 mL of a certain hydrocarbon require 25 mL of
18. Which of the following alkene will react fastest with oxygen for complete combustion and the volume
H2 under catalytic hydrogenation condition? of CO2 product is 20 mL. What is the formula of
R R R H hydrocarbon.
(a) (b) (a) C2H2 (b) C2H4
(c) CH4 (d) C2H6
H H H R
R R 3. Point out (A) in the given reaction sequence:
R R
(c) (d) (a) (b)
R H R R
(c) (d)
19. The product obtained on heating n-heptane with
Cr2O3– Al2O3 at 600°C is
4. Hydrogenation of the compound:
(a) Cyalohexane (b) Cyclohexane
(c) Benzene (d) Toluene Me
20. Products of the reaction,
Me Me
CH3
D2 O / D+
H3C CH2
H
CH3 H
CH3 H
(a) H3C CH2D In the presence of poisoned palladium catalyst gives:

(a) An optically active compound
CH3 OD (b) An optically inactive compound
CH3 CH3 (c) A racemic mixture
(d) A diastereomeric mixture
(b) H3C CH2D
5. The treatment of C2H5Mgl with water produces
OD (a) Methane (b) Ethane
CH3 H (c) Ethanal (d) Ethanol.
(c) H3C CH3 6. When isobutene is brominated, the percentage of
Br
OD D
CH3 H3C CH3 would be
CH3
(d) H3C CH2
(a) 0% (b) 83%
CH3 D OD (c) 10% (d) 100%
Hydrocarbon 3.127
11. Identify (B) in the following sequence of reactions.

7. Ozonolysis of will give Cu 2 Cl2 + NH 4 Cl
CH ≡ CH  → (A) →
HCl
(B)
(a) CH3CH2Cl
(b) CH2 = CH – CH2CH2Cl
O (c) HC CH3
(a) 2 (b) O
Cl
Cl
O
O (d) H2C C CH2
(c) (d) 12. The treatment of C2H5MgI with water produces

(a) Methane (b) Ethane
2
(c) Ethanal (d) Ethanol
13. Propene can be converted into 1-propanol by
8. Stability of oxidation. Which set of the reagents is used to effect
(i) CH3 – CH = CH – CH3 the conversion?
(ii) CH 3 – C = C – CH3 (a) OsO4 – CHCl3
| | (b) O3/Zn – H2O
CH3 CH3 (c) Alkaline and cold KMnO4
(iii) CH3 – C = CH2 (d) B2H6 and alk. H2O2.
|
CH3 14. CH3 CH3
|
(iv) CH3 – C = CH—CH3 H–C H Br
| || Br2 H Br
CH3 C–H
| CH3
In the increasing order is CH3
(a) I < III < IV < II (b) I < II < III < IV
(c) IV < III < II < I (d) II < III < IV = I Which is true statement?
(a) A is formed by anti addition and is meso
9. Which of the following is used for aromatization of (b) A is formed by syn addition and is meso
n-hexane? (c) A is formed by anti addition and is racemic
(a) AlCl3 (d) A is formed by syn addition and is racemic
(b) Na in liquid NH3
(c) Cr2O3/Al2O3 with heat 15. In the following sequence of reactions, identify the
(d) Wilkinson’s catalyst product (D).
CH3 CH ≡ CH →
HBr
(A) →
HBr
(B)
|
H–C 
alk. KOH
→ (C) 
NaNH 2
→ (D)
10. || alkaline KMnO4 A
H–C (a) Ethanol (b) Ethyne
| (c) Ethanal (d) Ethene
CH3
CH3
Which is true about this reaction? H Br
16. 2-butene + Br2 Br and
(a) A is meso 1, 2-butan-di-ol formed by syn addition H
(b) A is meso 1, 2-butan-di-ol formed by anti addition CH3
(c) A is a racemic mixture of d and l, 1, 2-butan-di-ol (by anti addition)
formed by anti addition enantiomer. 2-butene is
(d) A is a racemic mixture of d and l 1, 2-butan-di-ol (a) cis (b) trans
formed by syn addition. (c) both (d) none
3.128 Hydrocarbon
BH3 / THF H3 O +
The correct order of reactivity of I, II and III towards
17. B CH 2 A addition reactions is:
H2 O 2 / OH
(a) I > III > II (b) I > II > III
A and B are (c) III > II > I (d) III > I > II
(a) both CH 2 OH
?
3.
(b) both CH3
OH Select the suitable reagent for above conversion,
(a) CH2N2/∆ (b) CBr4/RLi
(c) CH 2 OH, CH3 (c) H2C = CH2 (d) t - BuOK
OH
O
(d) CH3 CH 2 OH,
OH , ∆ Zn (Hg)/HCl
4. (A) (B)
O
18. (A) cis-2-butene 
HCO3H
→I H–O
(B) trans-2-butene → II HCO3H
In the above reaction, product (b) is
Correct statements are
(a) (b)
(a) is racemic mixture by anti addition
(b) II is meso compound by anti addition
OH
(c) I is meso compound by syn addition (c) (d)
(d) II is racemic compound by syn addition
19. CH3 – CH – CH = CH2 + HBr A (predominant), Na/Dry ether

| 5. Cl Br (A)
CH3 97%
A is
(a) CH 3 – CH – CH – CH3 (a) (b)
| |
CH3 Br
(b) CH3 – CH – CH 2 – CH2Br (c) (d)
|
CH3
CH3 – CH2 CH3
Br H2/Pt
| 6. C=C
(c) CH3 – C – CH2 – CH3 D
| D
CH3 Product of the above reaction will be:
(d) None is correct (a) Racemic mixture (b) Diastereomers
(c) Meso (d) Constitutional isomers
STEP–III CHECK YOUR EXPERTISE CH2 – Cl

Na (Dry ether)
CONFRONT THE CONCEPTUAL QUESTIONS AS 7.
PRESENT JEE PATTERN CH3
CH2 – Cl
1. Calcium carbide + heavy water → ?
The product of the above reaction is: Product obtained in above Wurtz reaction is:
(a) C2H2 (b) CaD2
(c) Ca(OD)2 (d) CD4
(a)
2.
(I) (II) (III) CH3 CH3
Hydrocarbon 3.129
CH3 (a) 3 transition states and 3 intermediates

(b) 4 transition states and 3 intermediates
(c) 3 transition states and 2 intermediates
(b)
(d) 5 transition states and 4 intermediates
O
CH3 Br
11. Reaction (1) alc. KOH (A) (major)
(c) O
Reaction (2) alc. KOH (B) (major)

CH3 CH3
Br
(d) Both (a) and (b) O
8. Which of the following bromides is the major product
of the reaction shown below, assuming that there are Reaction (3) alc. KOH (C) (major)
no carbocation rearrangement?
Br
Product obtained in above reactions (1), (2) and (3) is
(a) A = B but C is different
+ HBr C13H17Br (b) A = C, but (B) is different
(1 equivalent)
(c) B = C, but A is different
Br (d) A = B = C all product are identical
Br
Cl
(a) (b) Cl Cl
3 mol alc. KOH
12. Reaction (1) (A)
Cl Cl
(c) (d) Cl
Cl
Br Br Cl Cl
3 mol alc. KOH
Reaction (2) (B)
9. Which of the following reactions results in the
formation of a pair of diastereomers? Cl Cl
HC H Cl
(a) 3 Cl
HBr
Cl Cl
H3C H 3 mol alc. KOH
(b) (C)
HBr Reaction (3)
H3C H Cl Cl
(c) HBr Cl
ROOR, UV Product obtained in above reactions (l), (2) and (3) is
H 3C H (a) A = B, C is different (b) A = C, B is different
1. BH3, THF
(d) (c) B = C, A is different (d) A = B = C is same
2. H2O2, OH–, H2O
13. Taking into account the stability of various carboca-
10. How many transition states and intermediates will be tions and, as well as the rules governing mechanisms
formed during the course of following reaction? of carbocation rearrangements, which reaction is most
OH likely to occur during the given reaction?
⊕ Br
H2O, H+ (a) ⊕ Br
3.130 Hydrocarbon
Br
⊕ (a) (b)
(b) Br
⊕ (c) (d) CH3–CH–CH2–CH=CH2

⊕ H CH3
Br
(c) Br
⊕
(d) None 18. Case A Heat (a) (major)
+ CH2N2
14. 2, 4-hexadiyne (C6H6) is allowed to react with Li
in NH3 (liq). The product obtained is treated with 1
equivalent of C12 in CC14, Which of the following
constitutional isomers are possible products? Heat
Case B + CH2l2 (b) (major)
Cl Cl Zn
(I) (II)
In the above reaction difference in reagents results in
Cl Cl
the different product mixtures. Find relation between
Cl Cl Cl a and b.
(III) (IV) (a) a = b (b) a > b
(c) b > a (d) cannot predict
Cl
Cl
19. HCl ; major product of the reaction is
CH3
(V)
Cl (a) (b)
(a) I and II (b) II and III Cl
Cl
(c) I and V (d) I and III
15. How many products will be formed in this reaction? (c) (d)
Cl Cl
1. OsO4
2. NaHSO3 20. Predict the product of the following reaction:
(a) 1 (b) 2 (c) 3 (d) 4

H+
A
∆
2HCl
16. A .
Cl Cl (a) (b)
Reactant (A) can be
(c) (d)
(a) (b)
OH
H+ A
21. ∆ (Major) Major – product A is
(c) (d) all
HO (a) (b)
CH3
17. CH – CH + H C = CH HF
3 2 2 2 – 5°C
; (A) is (c) (d)
CH3
Hydrocarbon 3.131
OH OMe O
H2SO4
22. A (Major) (b)
∆
Major product A is
O
(a) (b) OMe
(c)
(c) (d)
O O
O
CH2N2
(d) None of these
Hv
23. (A) (B)
∆
O H+
Product (B) is: 26.
Major product of the reaction is:

(a) (b) OH
(a)
(c) (d)
HO
(b)
s)
xces (c)
H 2(e OH
Pt
24. A KM
nO
4
CO2H CO2H (d)
+
CO2H CO2H OH
Compound (A) is 27. Rank in the order of increasing rate in a Diels-Alder

reaction.
(a) (b) O
(a) (b) O
(c) (d)
(c)
OMe
(a) B < A < C (b) B < C < A
25. MCPBA
P ; Product (P) is: (c) C <A < B (d) C < B < A
75%
O–H
O Br2
28. (lactone)
OMe NaHCO3 Cyclic ester
O
(Bromolactonization)
(a)
O (a)
HO O
O O
3.132 Hydrocarbon
CH2 — CH3
(b) O (c) CH3 (d)
O
Br CH3
Br
(c) CH3 H H CH3
CO2H
Br 32. (I) (II)
OH
(c)
O O Rate of reaction towards reduction using (H2/Pt):
(a) I > II
(b) I = II
O3 LiAlH4 H+ (c) II > I
29. A B (c);
Zn ∆ (d) Reduction of given molecule is not possible
33. What is the major product expected from the following

reaction?
Product (c) of the reaction is:
OH O
(a) (b) CH3 D – Cl Product
CH3 CH3
(c) (d) H D
(a) (b)
Cl Cl
OH H
H2SO4, 0°C H
30. (A) (B);
H2O –HCl
D D
Cl
H Cl
Product (B) of above reaction (c) (d)
CH3 CH3
(a) (b) O Cl H
O
O O O
(c) O (d) CF3CO3H
O 34. CH = CH2 +
A
O
31. An optically active compound A with molecular
formula C8H14 undergoes catalytic hydrogenation to
give Meso compound, the structure of (A) is:
CH3 CH3 B O
(Only one enantiomer is taken)

(a) (b) (a) A and B are mixture of diastereomers
(b) A and B are mixture of enantiomers
(c) A and B are optically active
CH3 CH3 (d) B is optically active and A is optically inactive
Hydrocarbon 3.133
(a) 39. + H2C = CH2 ∆

(d)
(b)
35. End product (C) in above reaction is:
Product of the above reaction is:
(c) OH
Which (π-bond) will reduce first, when above com- (a) (b) O
pound undergoes catalytic hydrogenation?
(a) a (b) b OH
(c) c (d) d
OH Br
36. In which of following reaction, Markownikoff’s rule
is violated. (c) (d)
(a) CH3 – O – CH = CH2 HBr
→ OH OH
CCl 4
(b) CH3 – NH – CH = CH2 HBr

→
CCl 4 O
(c) CH3 – S – CH = CH2 HBr

→ 40. ∆
CCl 4 Product
(Retro Diels Alder reaction)
(d) O2N – CH = CH2 HBr
→
CCl 4
37. Decreasing order of rate of reaction of molecules ;

(a) (b)
towards electrophilic addition reaction is:
CH = CH2 CH = CH2
(c) both (d) No reaction
(i) (ii)
41. Which is incorrect statement about heats of
combustion
NO2 OH
CH = CH2 CH = CH2
(a)
(iii) (iv) > >
CH3 NH2 (b) > >

(a) i > ii > iii > iv (b) ii > iii > i > iv
(c) Iso-butene > trans – 2 – butene > 1 – butene
(c) iv > ii > iii > i (d) ii > iv > iii > i
(d) n-Hexane < n – Heptane < n – Octane
38. List the following dienes in decreasing order of their
reactivity in Diels-Alder reaction. O
42. + HBr Product
(i) (ii)
(1 mole)
Addition of a mineral acid to an olefin bond leads to
(iii) (iv) major product, identify it.
O
(a) i > ii > iv > iii
(b) iv > i > iii > ii (a)
(c) iv > i > ii > iii
(d) iv > iii > i > ii Br
3.134 Hydrocarbon
O
(b) Br H2 (One mole)
45. Product
PtO2
O
(c) Br
In polyenes that contain differently substituted (C = C)
Br double bonds, it is possible to hydrogenate chemese-
(d) O lectively one (C = C) double bond. Product is:
O (a) (b)
43. Conc. H2SO4

P
O (c) (d)
(a) (b) O
HOOC COOH BD – THF H O , OD–

46. C=C 3 2 2
Product
H H
The product is
(c) (d) COOH COOD
O H D H D
O (a) (b)
H OD H OD
COOH COOD
COOH COOH
H2SO4 H D H D
44. B (c) (d)
H OH DO H
COOH COOH
A
Identify product (P) B A
47.
A isomerise to B on addition of traces of acid H2SO4.
Compound (b) is
HO
CH2OH
(a) (b)
The most appropriate reagents for corresponding

reactions are
(a) A = BH3 – THF; H2O2, OH– B = H+, H2O
(b) A = CH3 – CH – CH – B – CH – CH – CH3 ;
(c) (d) H
CH3 CH3 CH3 CH3
B = Hg(OAc)2; H2O; NaBH4
Hydrocarbon 3.135
(c) A = B = BH3 – THF; H2O2; OH– CH3OH

(d) A = BH3 – THF; H2O2; OH–
B = Hg(OAc)2; H2O, NaBH4 (a) CH3 – C – CH – CH3
CH3
CH3
48. 1. O3
CH3 2. (CH)3S2 (b) CH3 – C – CH2 – CH3
CH3
Product. The ozonolysis product is
CH3 – CH – CH – CH3
(c)
CH3 CH3
(a) CH3 Cl
CH3 C CHO
O (d) CH3 – C – CH – CH3
CH3
O
(b) CH3 C CHO 51. A ←
NaNH 2
150° C
CH3 – CH2 – CH2 – CCl2 – CH3
KOH, 200° C

(fused)
→ B Products ‘A’ and ‘B’ are
O (a) same, CH3CH2 – C ≡ C – CH3
(b) A = CH3 – CH2 – C ≡ C – CH3
(c) CH3 C CH = O B = CH3 – CH2 – CH2 – C ≡ CH
(c) same, CH3 – CH2 – CH2 – C ≡ CH
(d) A = CH3 – CH2 – CH2 – C ≡ CH;
O O B= CH3 – CH2 – C ≡ C – CH3
(d) CH3 C C OH 52. An organic compound ‘X’ on treatment with hydrogen
and platinum catalyst, absorbs 5 equivalents of hydro-
gen to give n-butyl cyclohexane. When ‘X’ is treated
with silver nitrate in ethanol, a white precipitate forms.
49. Three isomeric alkenes, A, B and C, C5H10, are The precipitate is found to be soluble in dilute acid.
hydrogenated to yield 2-methylbutane. A and B give Treatment of ‘X’ with an excess of ozone, followed by
the same 3° ROH on oxymercuration - demercuration. dimethyl sulphide and water, gives following products:
B and C give different 1° ROH on hydroboration- O O O O O
oxida-tion. Some of the possible isomeric structures
for C5H10 are as follows: HCCH2 – CH2 – C – CH HC – CH
I CH3 – CH2 – CH2 – CH = CH2 O O O
II CH2 = CH – CH(CH3)2 HC – C – OH HC – OH
III (CH3)2 – C = CHCH3 Hence, compound ‘X’ is
IV CH2 = C(CH3) – CH2CH3
CH = CH – C ≡ CH
Mark out the correct combination of isomeric, A, B (a)
and C with structures (I to IV).
(a) I-A, II-B, III-C (b) II-A, III-B, IV-C CH = CH – C ≡ CH
(c) III-A; IV-B; II-C (d) III-A; II-B; IV-C (b)
CH3O CH = CH – C ≡ CH
(c)
Zn – Hg, conc. HCl
50. CH3 – C – C – CH3 Product
CH3 CH ≡ C – CH = CH2
(d)
The main product is
3.136 Hydrocarbon
53. Choose the correct comparison of heat of hydrogena- CHO COCH3

tion for the following alkenes. COCH3 CHO
I II (c) (d)
III IV CHO COCH3
HOOC COOH
C=C BD3, – THF H2O2, OD, D2O
V 57.
H H
(a) II < IV < III < V < I Product
(b) III < IV < I < V < II COOH COOD
(c) V < IV < III < I < II H D H D
(d) IV < V < I < III < II (a) (b)
H OD H OD
54. Which of the following reaction gives the non-
resolvable product? COOH COOD
CH3 I. OsO4 pyridine COOH COOH

(a) H D
CH3
II. NaHSO3 H D
(c) (d)
H OH DO H
CH2 CH3 I. OsO4 pyridine
(b) COOH COOH
II. NaHSO3
Br2 , H2 O ?
(c) 58. R — C ≡ CMgX  → R — C ≡ CH
Which of the following is not the suitable reagent to
HCO3H perform the conversion?
(d) (a) 2, 4, 6-trinitrophenol
CH2 CH3 (b) Trifluoroacetic acid
(c) t-butyl chloride
55. 1-Pentyne → Pentanal (d) DMF
Which of the following is most suitable reagent for 59. Which of the following is/are not the possible product
this conversion? on the electrolysis of CH3 – CH – COONa
(a) BH3 –THF; H2O2, OH–
(b) H+. H2O CH3
(c) HgSO4, H2SO4 (a) CH3 – CH2 – CH3
(d) Sia2BH; H2O2, OH– (b) (CH3)2 CH – CH – (CH3)2
(c) CH3 – CH – CH3
I. CH2 = CHCOCH3 CH3
56. Product
II. O3/Zn, H2O
O
Predominant product is: (d) (CH3)2 – CH – O – C – CH – (CH3)2
CHO COCH3
CHO CHO O
(a) (b) 60. ∆
+ CCl3 – C – ONa
CHO CHO The predominant product is

Hydrocarbon 3.137
O OH
(a) OCH2CH3
– O – C – CH3
(a)
Cl O
(b)
(b) OCH2CH3
Cl
O
(c)
C – OCH2CH3
(c) Cl
Cl OH
OCH2CH3
(d)
(d) Br
Cl
Cl 63. Give the major product of the following sequence:
61. Identify product Z in the following reaction sequence: (1) O3 H+

H2
HO
(2) (CH3)2S
HOCH 2 – C ≡ C – CH2 – CH2 – OH X
Lindlars Pd
O (Major Product)
||
H2SO4 CH3 − C − O − O − H H OH
Y Z (a)
Heat
O O
HO
O
OH
(a) (b) H
O
O
HO
O OH
O (c)
(b) O O
H
O O
(d)
(c) CH3 – C – O – CH2 CH2 –CH2–O–C–CH3 O
C=C O OH
H H
O 64. How many different products (including stereomers)
are obtained in the following reaction?
(d) CH3 – C – O – CH2 CH2– CH2– O – C – CH3
H3C CH2CH3
C=C O CH3
H H Light/ NBS
O
H3C CH3
62. NBS, CCl4 CH3CH2ONa
Peroxide CH3CH2OH
(a) 3 (b) 4
Product. The major product is: (c) 5 (d) more than 5
3.138 Hydrocarbon
65. Arrange the following reaction in decreasing order of OH

reactivity with NBS/heat: (a)
1. 2.
(b)
OH
O
3. 4.
(c)
(a) l > 2 > 3 > 4 (b) 2 > l > 3 > 4
(c) 1 > 2 > 4 > 3 (d) 4 > 3 > 2 > 1
OH
(d)
66. Give the major products in the following reaction:
NBS/Light
Major product
69. Give the reagent that would best accomplish the
following transformation:
Br
1. 2. Best reagent
Br
O
Br Br
3. 4. (a) MCPBA
(b) CH3COOH
(c) (CH3)3COOC(CH3)3
(a) 1, 2 and 3 (b) 1, 2 and 4 (d) Br2/NAOH
(c) 1 and 3 (d) 2, 3 and 4
70. Give the major product of the following reaction:
67. Give the major product of the following reaction:
O3/CH2Cl2
Major product
BH Zn/CH3COOH
2
–
H2O2, OH
H H
(a)
(a) C≡C O O
H CH3
(b)
(b) O O
(c) HO OH
(c)
O O
OH
(d)
CHO
H
(d)
68. Predict major product of the following reaction OH and enantiomer
sequence:
H
O
Li 71. Give the starting compound that when reacted as
Major
shown belo, gives the indicated product:
Hydrocarbon 3.139
Starting material? 74. What is the product of the following sequence of

reaction?
O
O3/Zn, NaNH2/NH3 H2/Pd/BaSO4 BH3/H2O/NaOH
CH3COOH
+
O
(a) (b)
HO OH
HO OH
(a)
(c) (d)
HO OH
HO
(b)
72. What is the major product obtained from the following
reaction?
HO HO OH
Br (c)
O N O
HO HO OH OH
(d)
Trace peroxide
Br Br 75. Which of the following compounds was the starting

material for the oxidation shown below?
(a) (b)
O
O
KMnO4/H+
? HO OH + CO2
OH
(c) (d)
Br
Br O
73.
(a) (b)
H2SO4
∆
A;
OH (c) (d)
76. Which radical is responsible for the observed

(a) (b) selectivity in the following chain reaction
Cl
Cl – Br
hv
+
(c) (d)
Cl
2% 98%
3.140 Hydrocarbon
(a) Cl• (b) Br• 80. Consider the following reaction:

(c) H• (d) A 2• radical
Br
77. What is the most likely product of the following HBr + Br
reaction?
(A) (B)
Cl2
hv The incorrect statement about this reaction is:
(a) In the intermediate, the positive charge on the sec-
ondary carbon is larger than on primary carbon,
resulting in the more rapid formation of A,
(a) (b)
(b) In B the double bond is more stabilized by hyper-
Cl Cl conjugation than in A.
Cl (c) At higher temperature B is major product.
(d) Under the kinetically controlled conditions, A and
(c) (d) B can easily interconvert.
Cl
81. Protonation of 1, 2-butadiene gives carbocation (a)
78. Consider the following reaction of 1-methyl and protonation of 2-butene gives carbocation (b). In
cyclohexene with NBS. Four likely products of the both case the most stable carbocation possible is pro
reaction are shown below. One of the likely products duced but no carbocation rearrangements take place.
is not shown, however. Which of the two carbocation is more stable and why?
(a) A is more stable because it is a terminal carboca-
Br tion, according to Markovnikov’s rule.
(b) A is more stable because it is stabilised by reso
NBS nance and hyperconjugation.
+
CCl4 (c) A is more stable because cationic carbon is sp hy-
bridized.
Br (d) B is more stable because it has two alkyl groups
Br that can provide extra stabilisation by hyperconju-
Br gation and inductive effect.
+ +
82. How many stereoisomers of the main product will
Which of the following is the missing product? form in the following reaction?
Br Br BH3/H2O2
(a) (b) NaOH
(a) 1 (b) 2
Br (c) 3 (d) 4
(c) (d)
83. Vinyl cylcopropane on reaction with HBR yields – as
Br Br major product:
Br
79. Which is the least likely protonation site in the Br
conjugated alkene shown below? (a) (b)
(III) (I)
(II) Br
Br
(IV)
(c) (d)
(a) I (b) II
(c) III (d) IV
Hydrocarbon 3.141
84. Arrange the following alkene in increasing order of

their enthalpy of hydrogenation (–∆H):
(a)
I II III IV
(b)
(a) III < IV < II C=C 88. Arrange in decreasing order of reactivity with HC1
H H H CH3
CH3 Cl CH3 H
(b) C=C > C=C
H H H Cl
Cl Cl
NO2 OCH3
Cl
(c) >
(a) II > III > I
(b) III > II > I
Cl (c) III > I > II
CH3 CH3 (d) none of the above
Cl H CH3
(d) >
89. Br2 X
(stereoisomer) X may be
Cl C2H5 CCl4
(±)
(Z)
86. Which order is/are correct regarding stability?
Br
(a) (Trans) < (Cis) Br Br
(a) (b)
(b) <
H Br Br Br
CH3 H CH3 H H5C2 Br H5C2 H
(c) C=C > C=C
CH3 CH3 CH3
H H CH3
Br Br
&+ &+ &+ +
(d) & & ! & &
(c) (d)
+ + + &+
Br H H 3C Br
/L1+ O H5C2 Br H5C2 Br
87. &Ł&í&Ł& ;;LV
CH3 H
3.142 Hydrocarbon
CH2 – CH2 – OH Identify the product?

A
(a) C≡C
OH (b) H – C ≡ C – H
CH = CH2
B (c)
90.
(d) C≡C–H
OH
C
O
A, B, C are 94. (i) CF3 – C – O – O – H (1 eq.)
(a) Simple hydration reaction C ≡ C – CH3
(ii) H3O+
(b) Hydroboration, hydration and oxymercuration de-
mercuration
C ≡ C – CH3
(c) Hydroboration oxidation, oxymercuration demer- (a)
curation and hydration HO OH
(d) Oxymercuration demercuration hydroboration
and hydration HO C ≡ C – CH3
(b)
CHBr3
91. CH2 OH
t–BuO K – +
H–O
Br
(c) C ≡ C – CH3
(a) Br (b)
Br OH
Br OH
Br
Br (d) C ≡ C – CH3
(c) (d) OH
Br 95. In the following series of reactions the major products
Br
P and S are respectively.
92. An unknown compound decolourises bromine in
carbon tetrachloride, and it undergoes catalytic
reduction to give decalin. When treated with warm,
cone, potassium permangate, this compound give cis-
cyclohex-ane-l,2-dicaboxylic acid and oxalic acid.
Propose a structure for the unknown compound.
(a) (b) (a) ;

Br
(c) (d) (b) ;

Br
Cl (c) ;
KOC(CH3)3, DMSO Br
93. CCH3 heat
Cl (d) Br ;
Hydrocarbon 3.143
96. End product D of the following reaction will be Me

Cl H 2O ZnCl2HCl Et DH
A B
(b)
Mg/ether D2O D H (±)
C D
CH3
(a) D (b) OD Me
Et OH
D (c)
(c) D (d) H D (±)
OD
Me
97. Consider the following reactions CH3
H5C2 C2H5 CH3CH2 DH
C=C (d)
H H H OD
R1 R H C2H5
2 CH3
C=C
H5C2— C C — C2H5 H5C2 H
R3 99. Compound ‘P’ of the following reaction sequence can
H5C2 — C — CH2— C2H5 be
R4 ⊕
O O
2CH3 — CH2— COOH O O H2O
(P) [C8H6O3] COOH
The correct set of reagents for these reactions is B–H
R1 R2 R3 R4 [C16H21B]
HOO
(a) H2/Lindlar Na/liq.NH3 (i) O3, H2O, CrO3/Acetone/H2O
catalyst (ii) H2O H2SO4, [C8H8O] CH2 – COOH
HgSO4
(b) H2/Lindlar Na/liq.NH3 H2O, (i) O3, (a) C≡C
catalyst H2SO4, (ii) H2O
HgSO4 (b) CH2 – C ≡ CH
(c) (i) O3, H2O, Na/liq. H2/Lindlar (c) C ≡ CH
(ii) H2O H2SO4, NH3 catalyst
HgSO4 (d) CH = CH2
(d) H2O, H2/Lindlar (i) O3, Na/liq. 100. The alkene limonene has the following structure,
H2SO4, catalyst (ii) H2O NH3
HgSO4
The product results from the reaction of limonene and
98. The most appropriate major product of the following
1 molar equivalent chlorine water?
sequence of reactions would be
OH OH
O
CH3CH2 CH3 (a) (b)
CH3 – C – O – O – H OH Cl
C C Cl Cl
Cl
H3C H LiAlD4 H 3O + Cl
Me (c) OH (d) HO
Cl
Et D
(a)
H OH (±) 101. The end product ‘W’ in the following sequence of
Me reactions is
3.144 Hydrocarbon
CH2CH3 alc. KOH (b) CH3 – C – CH2 – CH2OH

Y
NBS Hg(OAc)2 O
(X) W
aq. KOH NaBH4 CH3
Z
(c) CH3 – C – CH – C – CH3
CH3
O O
(a) Ph – CH2 – CH2 – O – CH – Ph OH
CH3 CH3
(d)
(b) Ph – CH – O – CH – Ph
(c) Ph – CH2 – O – CH2 – CH2 –Ph COOC2H5
CH = CH2
105. The best yiest of product ‘X’ can be obtained by using
which one of the following sequence of reagents and
(d)
reactants
Ph – CH – CH3 OH
102. The most stable conformation of the product of X = CH3 – C ≡ C – CH – CH (CH3)2

following reaction
NaNH2 (CH3)2CHCHO H 3O +
(a) CH3 – C ≡ CH
HBr / R2O2 HBr / dark
C ≡ CH
(1 eqivalent) OH
H Ph NaNH2 CH3l
(b) (CH3)2 CH – CH – C ≡ C – H
Ph Br H Br NaNH2 CH3l
(a) (b) (c) CH3 – C ≡ C – CH – CH2 – CH3
H H H H
Br Br OH
Ph H OH
H Br Br H (d) (CH3)2CH – CH – C ≡ C – H
CH3Mgl CH3l
(c) (d)
H Br Ph Br
Br H CH3
103. In the given reaction, H3C – C – CH2 – CH3

CH3
B2H6, THF H2O2, NaOH TSCl 106. H3C – CH2 – CH2 – N
t–BuO–K+ O
(Y) H3C – C – CH3
CH3 – C – Cl
The product ‘Y’ is CH3 X, X is
AlCl3
(a) A positional isomer of X
(b) Identical to X In the above reaction the product will be –
(c) Chain isomer of X (a) CH3 – CH – CH2 – Cl
(d) An oxidation product of X.
COCH3
104. Which of the following compounds would liberate (b) CH3 – CH – CH2 – C – CH3
two moles of methane when treated with methyl
magnesium bromide? Cl O
(a) CH3 – CH – CH2 – C ≡ CH (c) CH3 – CH – C – CH2 – CH3
OH Cl O
Hydrocarbon 3.145
CH3 Ph Ph
H Cl H Br
(d) CH – CH – CH – C – CH (a) Me (b) Me
3 2 3 Br Cl
Ph Ph
Cl O
107. Fastest rate of electrophilic addition will take place in Ph Ph
H Cl H Br
(a) HO CH = CH2 (c) Br Me (d) Br Me
Ph Ph
(b) ON CH = CH2
(c) CH3O CH = CH2 MCQS WITH ONE OR MORE THAN

ONE CORRECT ANSWERS
(d) CH = CH2
1. Which of the following alkanes will give a single
108. Which of the following will be the correct product (P) product with a methylene insertion?
for the given reaction ? (a) (CH3)2CHCH(CH3)2
(b) CH3CH3
(c) (CH3)4C
(d) CH3CH2C(CH3)2CH2CH3
OH 2. Which of the following alkanes cannot be synthesized

by the Wurtz reaction in a good yield?
(a) (b) (a) (CH3)2CH – CH2 – CH(CH3)2
(b) (CH3)2CH – CH2 – CH2 – CH(CH3)2
OH
(c) CH3 – CH2C(CH3)2CH2CH3
(d) (CH3)3C – CH2 – CH2 – CH3
(c) (d)
CH2 H+, H2O
3. Product
HBr aq NaOH
109. CH2 X (major)
R2O2
Product(s) is/are
H SO /∆
Y (major) 2 4 Z (major) CH3 CH3
identify the correct option (a) (b)
OH OH
X Y Z
HOCH2
(A) &+ &+ &+ (c) (d)
%U 2+ OH CH3
(B) &+ &+ &+
%U 2+
4. CH = CH2 CH2 – CH2 – OH
(C) &+ &+ &+
The conversion can be performed suitably by
%U 2+
(a) I. C12, H2O II. LiAIH4
(D) &+ &+ &+ (b) I. HBr II. OH–
(c) I. BH3 – THF II. H2O2, OH–
%U 2+
(d) I. HBr-peroxide II. OH–
110. The final product of the following reaction is
5. Some alkanes may be prepared by adding an alkyl
Ph iodide (iodoalkane) dropwise to sodium in a suitable
H o–COCH3 inert solvent e.g., 2CH3I + 2Na → C2H6 + 2NaI. If a
BrCl/CCl4
H Me ∆
mixture of iodomethane and 2-iodopropane is used as
Ph starting material the product will contain:
3.146 Hydrocarbon
(a) 2-methyl propane 9. Which statement is correct about the end product of
(b) methane, propene and propane the following reaction series,
(c) ethane and 2, 3-dimethyl butane
HOCl (excess)
(d) all of above C ≡ CH
(1) (2)
1. Hg 2+
6. CH ≡ CH + 2CH3COOH → Products2. D, 300 − 400° C (a) It is optically inactive hydroxy denote
Product is/are (b) It is a resolvable hydroxy acid
(a) CH3–CH(OCOCH3)2 (c) It is a non resolvable aldehyde
(b) CH3CHO (d) It is an optically inactive hydroxy acid
O 10. The following synthesis can not be carried out be:
||
(c) CH 3 − C − OCH 3 I
CH = CH2
O O CH = CH2
|| ||
(d) CH 3 − C − O − C − CH 3
Cl I
7. Choose the correct statement regarding the following
Cl2 ICl/CH3COOH ICl/CH3COOH Zn dust
reaction. (a)
(1) (2) (3) (4)
Conc. H2SO4
CD.CH3 – CH – CH3 . HOCl/H Cl2/Fe ICl/ZnCl2(excess) NaOH, ∆
140°C (b)
(1) (2) (3) (4)
OH HOBr/H Cl2/Fe ICl/ZnCl2(excess) Zn dust, CH3COOH
(c)
(a) reaction is regioselective (1) (2) (3) (4)
(b) reaction is stereospecific (d)
Br2/CH3COOH Cl2/Fe ICl/CH3COOH(excess) NaNH2
(c) reaction is stereoselective (1) (2) (3) (4)
(d) reaction predominant product is
C6H5 CH3 11. Bu − C ≡ CH 
LiNH 2
→ A 
(i) PhCHO
(ii) H 2 O
→ B 
MnO3
→C
C=C
Compound C of the above reaction can not be:
CH3 H
CHO
CHO
8. Which order/s are correct regarding boiling point.
(a) C ≡ CBu (b)
CH3 CH3 CH3 H
(a) C=C > C=C C ≡ CBu
H H H CH3
CHO
CH3 Cl CH3 Cl O
(b) C=C < C=C
H H H H (c) (d) C – C ≡ CBu
Cl Cl
Cl C ≡ CBu
(c) >
12. Acetone (CH3COCH3) is the major product in:
⊕
I CH 2 = C = CH 2 
Cl
H 3C
→
CH3 CH3 II CH 3C CH →

H 2SO4 /HgSO 4 /H 2O
Cl
(d) > III CH 3C CH 
BH3− THF
H O /OH○−
→
2 2
(a) I (b) II
Cl (c) III (d) none
Hydrocarbon 3.147
3. Mark out the incorrect match.

COMPREHENSION TYPE
(a) CH3 – CH = CH – CH3 + Br2 – intermediate:
COMPREHENSION-I (2) – stereospecific
(b) CH3 – CH = CH – Ph + Br2 – intermediate:
Electrophilic addition: In this mechanism a positive (1) –non–stereospecific
species approaches the double or triple bond and in the first (c) CH3 – CH = CH – CH3 + HOCl – intermediate:
step forms a bond by converting the π pair of electrons into (1) – non-stereospecific
a σ pair (d) CH3 – C ≡ C – CH3 + Br2 – intermediate:
Step I (2) -non-stereospecific
X
+ Slow + COMPREHENSION-II
–C=C–+X –C–C–
In the Diels-Alder reaction a double bond adds to 1, 4 to a
Step II conjugated diene (a 2 + 4 cycloaddition), so the product is
always a six-membered ring.
X Y X
⊕ –
–C–C–+Y –C–C–
+
In the reaction, X need not actually be a positive ion but Z Z

can be the positive end of a dipole or an induced dipole,
with the negative part breaking off either during the first • T
he double bond compound is called a dienophile.
step or shortly after. Most dienophiles are of the form − C = C− Z , where
Not all electrophilic additions follow the simple mecha | |
nism. In many cases, if (1) forms, it very rapidly cyclises Z is strong e– withdrawing group. Benzyne acts as
giving cyclic intermediate (2) dienophile
+
X
–C–C–
cis trans–oid
Whether intermediate is (1) or (2), the mechanism is
called electrophilic addition bimolecular. Stability of inter- • I f diene is frozen into transoid conformations,
mediate (1) or the formation of (2) controls the stereochem- Diels-Alder reaction is not possible. Some aromatic
istry of the reaction. As the stability of (1) increases, rotation compounds can behave as dienes but benzene is
along C–C is possible, reaction may be non-stereospecific. highly unreactive.
• With respect to the dienophile, the addition is stereo
1. CH3 – CH = CH – CH3  X 2 ,CCl4
→ Product (X2 = C12, specifically syn.
Br2, l2)
In the reaction, which X is having maximum tendency 4. Mark out the correct decreasing reactivity of diene in
to form intermediate like (2)? a Diels-Alder reaction.
(a) Cl (b) Br
(c) I (d) CI >> Br >> I (a)
CH3 H W2
2. C=C Product
H CH2CH3 (b)
W2 is an electrophilic reagent. The addition of W2 to
the alkene ‘A’ proceeds through intermediate like (2).
Which of the following is correct about the reaction? (c)
(a) Reaction is non-stereospecific
(b) Products are meso compounds
(c) Products are threo dl pairs (d)
(d) Products are erhythro dl pairs
3.148 Hydrocarbon
Acidic KMnO
CHCO 8. C3H2O2     
4 → Product
5. Reaction:–I: Product is:
+ ‘A’ (major product)
CHO
(a) |
CH = O CHO
Reaction: II + ‘B’ (major product) COOH
(b) |
COOH
For the reactions I and II, major products (c) CHC –CH2 – COOH
CH = O (d) CH3 − C − COOH
||
(a) A = B= O
CH = O
9. In the sequential reaction, if instead of CO2, (CH3)3 Br
CH = O is used. Product will be:
CH = O
(b) A = and B = (a) HC ≡ CH (b) (CH3)3CH
(c) HC ≡ C – C(CH3)3 (d) BrCH = CH – C(CH3)3
CH = O COMPREHENSION-IV
(c) A = and B =
O
CH = O
N – Br
(d) A = and B =
CH = O O (CH3)3C – OK+
CH = O A(C8H10) B(C8H9Br)
I II
6. Which of the following is the most reactive diene?
(a) Naphthalene (b) Anthracene VI reduction III ozonolysis
N2H4 + NaOH 1. O3, 2.Zn/H3O+
(c) Phenanthrene (d) Benzene
COMPREHENSION-III 1. CH2MgBr
E +
D(C7H6O) + HCHO↑
Acetylene + CH3MgBr A+B 2. H3O
IV
oxidation pyridinium
+
H CO2 Cl2, hv chloro chromate
C3H2O2 C Pyrene F(C8H8O)
(PCC)
V
H2O, H2SO4
C3H4O3
10. Which of the following pair of molecules can be dis
KMnO4 tinguished by using Br2, H2O?
CH2(COOH)2
(a) A and F (b) D and E
7. The molecule C3H4O3, in sequential reaction is: (c) D and F (d) C and D
(a) HO – CH = CH – COOH 11. Compound ‘B’ is
(b) CH2 = C − COOH CH2 – CH2Br
| (a)
OH
(c) CH3 – C − C − OH Br
|| ||
OH OH
(b) CH2 – CH3
(d) H – C − CH2 − C − OH
|| ||
OH OH
Hydrocarbon 3.149
CH2 – CH3 (a) CH3 – CH − CH

|
(c) H
CH3
CH2 – H
CH2 Br (b)
(d)
CH3 CH3 – CH – CH3
(c)
12. Which of the following is incorrect?
1. BH3− YHF 1. BH3 − THF H
(a) C A (b) C E
2. CH 3COOH 2. H 2 O 2 OH −
1. Hg ( OAc) 2 H2 O LiAlH4 (d) CH – CH3

(c) C F (d) B A
2. pcc
COMPREHENSION-V
Alkanes may be prepared from alkyl halides by the Wurtz
method where alkyl halides are reacted with Na in the pres- COMPREHENSION-VI
ence of ether An unknown compound ‘X’ (C10H16) absorbs two moles of
2R – X 
→ R – R + 2NaX
Na H2 to give ‘Y’ (C10H20). Permanganate oxidation of X lead
ether
COCH3
The mechanism may be ionic in nature to the formation of CH3 – C – (CH2)2 – CH .
CH2COOH
i.e. R – X + 2Na → R–Na+ + NaX
O
R– + R – X → R – R + X– Addition of 1 mole of H2O to ‘X’ lead to the formation
X– + Na+ → NaX of ‘Y’. Addition of 1 mole of H2O to ‘Y’ gives ‘Z’. Answer
the following questions on the basis of the above.
13. If CH3CH2C1 is reacted with Na in the presence of
ether then which of the following compounds may not 16. Which of the following cannot be a possible structure
be formed? for ‘X’.
(a) CH3CH3 (b) CH3CH2CH2CH3
(c) CH4 (d) CH2 = CH2
(a) (b)
I
14. When is reacted with copper at 180°C
I
then which of the following compounds is formed? (c) (d)
(a) (b)
17. If it is given that a particular ‘Y’ contains

six-membered ring, then which of the following
cannot be ‘Y’
(c) Both of these (d)
(a) (b)
15. The reactivity of which H-atom is maximum for OH

HO
halogenation by free radical mechanism?
3.150 Hydrocarbon
OH 21. Dimerization product of cyclohexene under acidic

conditions is
(a) (b)
(c) (d)
18. Which of the following is true about ‘Z’ which is
obtained from the particular ‘Y’ in the previous ques
tion?
COMPREHENSION-VIII
(a) Z contains at least one double bond in its struc-
ture. Alkenes undergo electrophilic addition reaction, while car-
(b) ‘Z’ on treatment with CrO3/H+ leads to an alde- bonyl compounds undergo nucleophilic addition reaction
hyde. and also various type of rearrangement and condensation
(c) ‘Z’ on treatment with LiAlH4 remains unaffected reaction due to presence of active hydrogen.
(d) ‘Z’ gives positive idoform test. Consider the following information:
Molecular formula of (A) is C7H12, it can decolourise
COMPREHENSION-VII bromine water and forms the following chair of reaction
when treated with various reagents.
It a reaction proceeds via carbocation formation then
product obtained will be the one corresponding to more (A) 
Br2 / H 2 O
→ (B)(A) →
AgNO2 (aq)
(C)(A) 
NH 2 / OH
→
pH(3 − 4)
stable carbocation. Within the same molecule more stable (I) (II)
(III)
carbocation will be formed either by (1) hydride shifting (D) 
conc. H 2 SO4
→(E) + (F)
or (2) alkyl group shifting or (3) phenyl group shifting or (IV)
(4) bond migration.

22. At which step ring expansion takes place?
19. X (C4H8O) does not decolourise bromine water solu
(a) I, II (b) I, IV
tion water solution X with HBr followed by aqueous
(c) I, II (d) II, IV
alkali hydrolysis and heating with copper gives a
compound Y. Y forms oxime. Structure of X and Y 23. Select the wrong statement:
are respectively. (i) E and F are isomer
OH (ii)F can show tautomerism
(a) , (iii) On reductive ozonolysis of A, product gives posi
CH = O tive Tollen’s test
OH O (iv) A is an alkyne
(b) (a) (i), (iiii) (b) (i), (iv)
, (c) (iii), (iv) (d) (ii), (iii)
O
24. How many compounds are cycloketone among (A) to
(c) CH2 — OH, (F)?
O (a) 2 (b) 3
OH (c) 1 (d) 4
(d) , CH3
CH3 Comprehension - IX
Demercuration allows Mardownikoffs addition of H, OH
20. Which alkene when treated with benzene in the pres without rearrangement. The net result is the addition of
ence of H+ ion will give 1,1-diphenylethane. H2O. Answer the following question.
(a) CH3 – CH = CH2
(b) C 6H5 – C = CH2 = CH 2 CH3
|
i) Hg(OAc)2. THF
C6 H 5 25. CH – C – CH = CH A
3 2
ii) CH3OH, NaBH4 NaOH
(c) C6H5 – CH = CH2
CH3 HI (Conc.)
(d) C6H5 – CH = CH – C6H5 B, Product B is:
Hydrocarbon 3.151
(a) (CH3)3CCH – CH3 (b) CH3I R: A

lkene is less reactive towards hydrogenation in
comparison to alkyne.
OH
3. A: Addition of two equivalents of HBr to alkyne
(c) CH3CH2I (d) (CH3)3CCH – CH3
produces gem dihalide in the presence as well as
I in the absence of peroxide.
R: Halogen atom reduces the stability of radical and
O increase the stability of carbocation.
4. A: Addition of Br2 to 2-butene is stereospecific and
N–Br
addition of Br2 to 2-butyne is non-stereospecific.
1) Hg (OAc)2, THF R: 2-butyne has no stereoisomers.
26. CH3CH = CH2 O 2) H2O
A B 5. A: 2-methylbutane on treatment with Br2, hv gives
3) NaBH4, NaOH
2-bromo-2-methylbutane exclusively while Cl2,
OH hv to that gives 2-chloro-3-methylbutane as
C.
significant product.
The product ‘C’ formation from B occurs through R: Cl2 reactivity towards 3° –H is less in comparison
(a) enol formation to 2° –H.
(b) SN1 mechanism
(c) Neighboring group participation 6. A: Cyclopropane has the highest heat of combustion
(d) SNAR mechanism per methylene group.
R: Its potential energy is raised by angle strain.
OH
i) Hg(OAC)2. THF 7. Statement-1:
27. A, Product ‛A’ is:
ii) NaBH4. NaOH HBr Br
40ºC CH2
OH
CH2 CH3 +
(a) HO (b)
OH CH2 Minor
CH2
OH OH CH2 Br
Major Br
(c) (d)
CH2
OH CH3 +
–20ºC Major
CH2
ASSERTION AND REASON TYPE CH3 Br
Minor
Each of the following questions contain two statements:
Statement-2:
Assertion (A) and Reason (R).
Each question has four choices: +
CH2
(a) A is true, R is true; R is the correct explanation of A. CH3
H+ Allylic
(b) A is true, R is true; R is NOT the correct explanation of CH2 cation
A. CH2 Br
(c) A is true, R is false. Br
(d) A is false, R is true. Select the correct choice. CH2
CH3
major at low temp
1. A: Electrophilic addition of Br2 to alkyne proceeds +
faster than that of alkene. CH2
R: Bromonium ion intermediate of alkene is more CH3
Br
stable than that of alkyne.
CH2
2. A: With limited amount of hydrogen, alkyne can be CH3 Br
reduced to alkene deliberately. major at of high temp
3.152 Hydrocarbon
(a) S tatement-1 is True, Statement-2 is True; State- MATRIX MATCH TYPE

(b) Statement-1 is True, Statement-2 is True; 1. Match the column (I) and (II)
Statement-2 is NOT a correct explanation for Column-I Column-II
Statement-1.
(c) Satement-1 is True, Statement-2 is False.
(d) Statement-1 is False, Statement-2 is True. (a) (p) Di-carboxylic acid will be
formed when reacts with
8. Statement–1: hot alk. KMnO4
Me NBS Me Me
+
Me Me Me (b) (q) Decolurises Br2/H2O
Br
Br
Statement–2:
(c) (r) Dicarboxylic acid will be
O formed when reacts with
Me Me Me
Br O3/H2O2
–HBr
Me Me Me
(d) (s) Number of ally lie hydro
Br2 Br2 gens is odd
Br 2. Match the following

Me
Column-I
Me
Me CH3 H
Br (a) CH3 – C ≡ C – CH3 C=C
Me H CH3
CH3 CH3
(a) S tatement-1 is True, Statement-2 is True; State- (b) CH3 – C ≡ C – CH3 C=C
ment-2 is a correct explanation for Statement-1. H H
(b) Statement-1 is True, Statement-2 is True; State- (c) C
H2 = CH – CH2 – NO2 –→ CH3 – CH2 – CH2 –
ment-2 is NOT a correct explanation for State- NO2
ment-1. CH3 CH3
(c) Satement-1 is True, Statement-2 is False. (d) C=C
CH3 CH = CHCH3
(d) Statement-1 is False, Statement-2 is True.
CH3 CH3
9. Statement-1: But-1-ene gives 2-Bromobutane with C=C
CH3 CH2CH2CH3
HBr/Peroxide
Column-II
Statement-2: The reaction involves forma-
(p) NH2 – NH2, H2O2
tion of more stable free radical and in that re-
(q) Li–liq. NH3
spect the addition is Markovnik of although the
(r) H2, Lindlars catalyst
product obtained appears as anti Markovnik of
(s) SiA2BH; CH3COOH
product.
(a) Statement-1 is True, Statement-2 is True; State- 3. Match the following
ment-2 is a correct explanation for Statement-1. Column-I
(b) Statement-1 is True, Statement-2 is True; State- CH3
ment-2 is NOT a correct explanation for State- Br
H
ment-1. (a) Zn, CH3OH
H Br
(d) Statement-1 is False, Statement-2 is True. CH3
Hydrocarbon 3.153
CH3 5. Match the following:

Column-I
H Br
(b) (a) CH3– CH = CH2 → CH3 – CH – CH2CCl3
Br Br Nal, acetone
∆
CH3 Br
+ +
OH (b) R3N – CH = CH2 → R3N – CH2 – CH2 – Br
Ph
O
(c) (c) CH3– C ≡ CH → CH3 – C – CH3
CH3
∆
(d) CH3 – CH = CH – CH3 → CH3 – CH – CH2 – CH3
CH3
Br
Br
EtONa
Column-II
EtOH, ∆
H (p) Markownikoffs Addition
(d) (q) Anti-Markownikoff’s addition
CH3
(r) Electrophilic addition
CH3 (s) Radical addition
Column-II 6. Match the following
(p) Ant-elimination Column-I
(q) Rearrangement
(a)
(r) Stereoselective
(s) Stereospecific 2CH3 – CH – X → CH3 – CH – CH – CH3 +
4. CH3 CH3 CH3

Column-I CH2 = CH + CH3 – CH2
CH3 CH3 CH3
Ph CH3
(a) Ph – C – CH – CH3 C=C CH 2 − X CH 2
CH3 CH3 (b) | ||
CH3 OH CH 2 − X CH 2
CH3 (c) CH 3 − C H − X → CH 3 − CH2
CH3 H | |
(b) Ph – C – CH2 – CH3 C=C CH3 CH 2
CH3 CH3
OH (d) CH3 – C ≡ CMgX → CH3 – C ≡ CH
(c) CH3 – CH2 – CH – CH3 CH3 – CH – CH – CH3 Column-II
(p) Protonation
Br (q) Na, dry ether
(r) Mg, dry ether
O
(s) Dehalogenation
(d) CH – C – O – CH – CH CH2 = CH2 +
3 2 3 7. Match the following
O Column-I (Reaction)
CH3 – C – OH CH2 – CH3Cl CH = CH2
(a)
–
conc. OH
Column-II
(p) Elimination
(q) Rearrangement CH2 – CHCl2 CH = CH2
(r) Unimolecular (b) Zn, CH3OH
(s) Biomolecular
3.154 Hydrocarbon
Column-I
F dil. H2SO4
(a) CH3
(c) Mg, THF
C 1. B2H6
(b) CH3
Cl OCH2CH3 2. NaOH + H2O2
CH3CH2ONa
(d) Br2
O2N (c) CH3
O 2N CH3OH
Column-II (Intermediate) CH3 Hg(OAc)2 in H2O

(d)
(p) Carbene NaBH4
(q) Radical Column-II
(r) Carbanion OH
(s) Benzyne (p)
8. (q) product contains at least one chiral carbon

Column-I (r) a positive ion participates in the mechanism
(s) Net reaction follows Markovnikov’s rule
H
CH2
11. Match the column I with column II
C
(a) Column-I
HgSO4
(a) C ≡ CD
D2SO4, D2O
CH3
CH2 – H CH2 – H
(b) > (b)
*14 H2SO4
(c) CH3CH2CH2CH3 with Br2 H 2O
CH3
Br2
(d)
(c)
COOAg *14 B2H6/THF
Column-II OH /H2O2
(p) Optically active compound both treated within B2D6/THF
(d) C ≡ CD
(q) Ph3 C > Ph2 C H stable due to resonance OD /H2O2
(r) Hunsdiecker reaction Column-II

(s) Bond dissociation energy CH3
9. (p) CH3
Column-I Column-II OH
*14
(a) But-1-yne (p) R
eacts with KMnO4/
CH3
KOH to give acetic acid
(b) But-2-yne (q) W ith Hg2+/H2SO4 gives CH2OH
(q) H
butane-2-one *14
(c) Propene (r) Reacts with CH3Cl to
form but-2-yne
(d) CH3C ≡ CNa (s) Reacts with Cl2 at 500°C (r) CD2CDO
to give allyl chloride.
(s) C − CD3
10. Match the reactions given in Column-I with the most
likely facts given in Column-II. O
Hydrocarbon 3.155
other (J) gives an alkene that is reductively ozonized

INTEGER TYPE
to Me2C = O. Give the structures of (l) and (J) and
explain the formation of the latter.
1. (a) CH3—CH—C C—CH—CH3
(X) 3. A hydrocarbon (A) containing 90% carbon reacts
OH OH with dil. H2SO4 in presence of HgSO4 to give
Total no. of stereoisomers of the product when (B). Compound (B) is reduced by LiA1H4 to (C)
above compound which on heating with H2SO4 gives (D) directly by
(b) Total no. of stereoisomers of the product when hydrogenation in presence of deactivated Pd-CaCO3
above compound (X) is reduced by lindlar cata- catalyst. Outline the reactions.
lyst.
(c) Total no. of stereoisomers of the product when (X) 4. An hydrocarbon (A), C8H14, decolourises Br2/CCl4
is reduced by Na/liq NH3 (Birch reduction) and cold dil. neutral KMnO4 solution, but does not
(d) No. of products that we will get when optically react with ammonical AgNO3 and Cu2C12 solutions.
inactive form formed in part (B) reacts with It on ozonolysis produced two molecules of the same
PhCOOH followed by hydrolysis. acid (B), C4H8O2, which on heating with sodalime
gave propane. What are (A) and (B) ?
2. CH3 – CH = CH – CH3 reacts with Cl2 at 500°C. Find
out total no. of possible products. 5. A hydrocarbon (A) is treated with excess of HCl to
give a dihalogen compound (B), which on treatment
CHClBr2 with alc. KOH and aq. KOH separately gives (A) and
3. (CH3)3CO–K⊕ m no. of products. (C) respectively. (C) can also be obtained by heating
calcium salt of 2-methyl propanoic acid with calcium
Et acetate. What are (A), (B) and (C)?
CH3 CH3 6. Compound A (C6H12) is treated with Br2 to form
4. C=C + CH2N2 Uυ m Total compound B (C6H12Br2). On treating B with
H H
alcoholic KOH followed by NaNH2 the compound
no. of products. C(C6H10) is formed C on treatment with H2/Pt forms
CH3 NH2OH
2-methylpentane. The compound ‛C’ does not react
Cold Dil
5. KMnO4
HIO4
(excess)
with ammoniacal Cu2C12 or AgNO3. When A is treated
KMnO4 with cold KMnO4 solution, a diol D is formed which
gives two acids E and F when heated with KMnO4
Total no. of isomers (including stereo) are formed in
solution. Compound E is found to be ethanoic acid.
the products.
Deduce the structures from A to F.
SUBJECTIVE TYPE QUESTIONS 7. An alkane (A) with M.F. C6H14 reacts with chlorine
in the presence of U.V light to yield three isomeric
1. (a) Give reasons for the following: monochloro derivatives (B), (C) and (D). Of these
When 1-penten -4-yne is treated with HBr in equi- only (C) and (D) undergo dehydrohalogenation with
molecular proportion, the addition takes place on sodium ethoxide in ethanol to produce an alkene.
double bond and not on triple bond yielding there- Moreover (C) and (D) yields the same alkene
by the product CH3CH(Br)CH2C≡CH. (E) (C6H12). Hydrogenation of (E) produces (A).
(b) Provide a suitable mechanism for the following Treating (E) with HCl produces a compound (F) that
reaction. is an isomer of (B), (C) and (D). Treating (F) with
OH CH3 Zn and acetic acid gives a compound (G), which is
CH3 isomeric with (A). Propose structures for (A) to (G).
8. There are six different alkenes A, B, C, D, E and
F. Each on addition of one mole of hydrogen gives
G which is the lowest molecular wt. hydrocarbon
2. 3, 3-dimethyl-1-butene and Hl react to give two containing only one asymmetric carbon atom. None
products, C6H13l. On reaction with alc. KOH one of the above alkene give acetone as a product on
isomer, (I) gives back 3, 3-dimethyl-1-butene the ozonolysis. Give the structure of A to F.
3.156 Hydrocarbon
9. The hydrocarbon (A), adds one mole of hydrogen in 1-butanal. With proper reasoning give the structures
the presence of a platinum catalyst to form n-hexane. of A, B, C and D.
When (A) is oxidized vigorously with KMnO4, a
single carboxylic acid, containing three carbon atoms, 13. 1,4 – Pentadiene reacts with excess of HCl in the
is isolated. Give the structure of A and explain. presence or benzoyl peroxide to give compound
(X) which upon reaction with excess of Mg in dry
[IIT 1997]
ether forms (Y). Compound (Y) on treatment ethyl
10. Complete the following reaction. acetate followed by dilute acid yields (Z). Identify the
structures compound (X), (Y) and (Z).
i) CH2 1 2 3
14. 2-Butyne undergoes following reactions in steps as
indicated. Identify A to H.
[IIT 1999]
H2 D2 / Pt
CH3 CH 3C ≡ CCH 3 Ni 2 B(P–2)
A B
ii) H2 D2 / Pt
Major product Na / EtOH C D
Lindlar catalyst
H2 Br2
[IIT 2001] E F
Ni 2 B(P–2)
CH3 Br2 H2
G H
Ni
iii) H3C C 2 H 5OH
Major product
Δ 15. An unsaturated hydrocarbon A C6H10 readily gives B
CH3 Br on treatment with NaNH2 in liquid NH3. When B is
allowed to react with 1-chloropropane a compound C
[IIT 2001] is obtained. On partial hydrogenation in the presence
11. In alkyl halide X of formula C6H13C1 on treatment of Lindlar catalyst, compound C gives D C9H10.
with potassium tertiary butoxide gives two On ozonolysis D gives 2, 2-dimethyl propanal and
isomeric alkenes Y and Z (C6H12). Both alkenes on 1-butanal. With proper reasoning give the structures of
hydrogenation gives 2-3-dimethyl butane. Predict the A, B, C and D.
16. Identify (A), (B) and (C) in the following reactions
12. An unsaturated hydrocarbon A (C6H10) readily gives HCO3H
B on treatment with NaNH2 in liquid NH3. When B 1 eqv. (A)
is allowed to react with 1-chloropropane a compound CrO3
C is obtained. On partial hydrocarbon in the presence CH3 (B)
in AcOH
of Lindlar catalyst, compound C gives D (C9H18). aq. KMnO4
On ozonolysis D gives 2, 2-dimethyl propanal and excess (C)
ANSWER KEYS
STEP- I
1. (d) 2. (b) 3. (b) 4. (c) 5. (c) 6. (a) 7. (c) 8. (b) 9. (c) 10. (b)
11. (b) 12. (d) 13. (d) 14. (b) 15. (b) 16. (b) 17. (a) 18. (d) 19. (d) 20. (b)
STEP - II
1. (c) 2. (a) 3. (c) 4. (b) 5. (b) 6. (d) 7. (b) 8. (a) 9. (c) 10. (a)
11. (d) 12. (b) 13. (d) 14. (a) 15. (b) 16. (a) 17. (d) 18 (c, d) 19. (c)
Hydrocarbon 3.157
SOLUTIONS
1. (c) CaC2 + D2O → Ca(OD)2 + D – C ≡ C – D O OH

2. (b) Cyclopropane is most unstable therefore more
reactive toward addition reaction. Cyclopentene is (C)
most stable. ∴ less reactive.
3. (a) Carbene will form 3-member ring with alkane.
Cl
4. (b) Reactant in β-keto acid easily undergo decarbox-
ylation.
12. (d) A = B = C
H OH
O O Cl Cl
C = CH2
C – CH2 – C = O ∆ 13. (d) Reaction is exothermic because of formation of
stable alkene.
(Clemmensen reduction) 14. (d) 1, 2 and 1, 4-addition take place
O
15. (b) Two products will be obtained by addition reaction
Zn (Hg)/HCl above and below the plane of ring.
16. (d)
5. (b) It is an example of intramolecular Wurtz reaction. CH3 CH3
Na → NA+ + eQ H–F ⊕
17. (b) CH CH H CH3 C + H2C = CH2
3
e + Cl Br Cl Θ CH3 CH3
6. (a) CH3
⊕ 1, 2 H shaft
7. (d) Wurtz reaction CH3 C CH2 CH2
CH3 CH3
8. (d) HBr ⊕
⊕ C CH
CH3 CH3
(Stable carbocation)
CH3
9. (b) CH3 CH3
Θ
CH3 H CH3 H Br CH3 H Br 1, 2, CH3shaft
CH3 C CH CH3
HBr + ⊕ α
(Diastereomers)
18. (c) Zinc stabilized the transition state
10. (b) Transition state = Intermediate + 1
19. (c) Ring expansion takes place.
O OH
⊕
11. (d) (A) H – Cl Ring
exp.
(Phenol will obtained)

O OH Cl
⊕
(B)
Cl
3.158 Hydrocarbon
27. (b) Dienes is nucleophile in Diels-Alder reaction

⊕
⊕ Θ
28. (b)
Br2 O
20. (d) H
+
Ring expansion
O
NaHCO3 ⊕
Br O
(3° Carbocation stable)
Θ
Br – CH2
1, 2 CH3 O
Shift
⊕
O
O–H ⊕
H+ CH2 O OH
21. (b)
∆ 29. (c) O3 LiAlH4 H+
1, 2, H shift
Zn ∆
⊕ H ⊕ ⊕
⊕
⊕
1, 2 – H shift CH2
∆ OH ⊕ OH
(7α – H Major) 30. (b) H+
O–H Cl Cl
⊕ Ring
H+ expansion ⊕ Cl H 2O OH
22. (c)
Cl
H (Unstable)
HSO4
O
⊕
CH3 CH3
HV CH2N2 H2 H
23. (c) H2C = CH – CH3 ∆ 31. (c) Pt H
CH2 – CH – CH3 CH3 CH3
(meso)
CH2 32. (a) less steric hindrance
24. (b) Conjugated Dienes on KmnO4/D give oxalic acid. 33. (b) Markonikov addition
25. (b) More substituted alkene will undergo epoxide for- 34. (a) Diastereomers
mation
35. (d) Unstable alkene will readily undergo reduction
⊕
O O–H O–H H – Br ⊕ Br
36. (d) H2C = CH – NO2 CH2 – CH2 – NO2
(Stable)
+ ⊕
26. (b) H
⊕ Br – CH2 – CH2 – NO2 CH3 – CH – NO2
(unstable)
⊕
OH OH CH – CH3
Ring H 37. (c) (most stable)

expansion ⊕ because of (+R) of NH2
NH2
Hydrocarbon 3.159
(a) is least stable due to (–R) of –NO2 ⊕

(b) +R (–OH) ⊕
(c) –CH3 (hyper conjunction)
38. (b) (iv) is most reactive because dienes is locked in 44. (c)
1, 2 H shift
cis-conformation, dials alder favourable in cis form
(ii) is least reactive
(i) is more than (iii)
(ii) is least reactive
⊕
H Br
39. (b) (A) (B) (C) O
HO H Η
40. (c) Above is the reverse of Diels-Alder reaction Isomerization of less stable diene into a more stable
41. (c) Iso-butane is most stable isomer of butene ∴ It is diene.
least heat of combustion. 45. (b) less stable alkene (less a-hydrogen) will reduction
42. (b) r.d.s of the reaction is formation of carbocation. first.
∴ formation of 3° carbocation is more favourable. HOOC COOH
46. (b) C=C HOOCCH – CHCOOH
O O O H H
D BD2
D – BD2
Br 2HOOCH = CHCOOH
H – Br
(HOOCCHD – CH – )3B
COOH
⊕ H2O2, OD–
(3)° Br O O
DO – CHD – CH – COD
⊕ OD
43. (b) O O–H
– OH from – COOH is displaced by – OD.
+
H
47. (b) Less reactive towards
(A) E+ (Hg+ OAC) less sterically
hindered more favourable
Η−Ο
More substituted for SiA2BH
⊕ Ο more reactive
Η−Ο
towards E⊕ (Hg+ OAC)
(B) but sterically hindered
The decrease of ring strain can provide a driving force 48. (c) O3(CH3)2S – reductive ozonolysis
strong enough to overcompensate for the conversion
of a more stable into less stable cationic centre, the CH3
carboxonium ion. A rearranges into the carbonium
ion B because of the release of cyclo butene strain CO
(26 kcal/mol) in the formation of the cyclopentane
CH = O
(ring strain of about 5 cal/mol) cation B stabiliser
O
itself by way of another 1, 2 rearrangement. The
resulting action (c) has comparably little ring strain CH3 C CH = O
but is an electronically favourable carboxonium
ion.
3.160 Hydrocarbon
49. (c) 52. (a)

CH3 5H2, cat. CH2 – CH2 – CH2 – CH3
Hydrogenated ‘X’
C5H10 CH3 – CH – CH2 – CH3 Sliver nitrate
Isomers A, B and C in ethanol
CH3 CH3
OM/DM White ppt.
CH3 – C = CH – CH3 CH3 – C – CH2 – CH3
A (It suggests terminal triple bond)
OH Hence,
3º alcohol
O O
CH2
CH O O CH C OH HO CH
CH2
O
CH O O
CH2 = C – CH2 – CH3
B O CH
Hydroborational
oxidation CH
HO – CH2 – CH – CH2 – CH3 CH = CH – C ≡ CH
CH3
1° alcohol 53. (c) Greater the stability of alkene, lower the heat of
CH3 Hydro- CH3 hydrogenation.
borational
oxidation ∆H = 114 kJ/mol (cis)
CH3 – CH – CH = CH2 CH3 – CH – CH2 – CH2 ∆H = 105 kJ/mol ∆H = 111 kJ/mol (trans) ∆H =
122 kJ/mol
1º alcohol
OH
Different for R – OH
obtained from B III < IV
cistrans
7–hyperconjugative HS 3 – hyperconjugative HS
Zn → Zn2+ + 2e– 2 – hyperconjugative HS
50. (c)
∆H = 151 kJ/mol
+
CH3OH CH3 OH2 No hyperconjugative HS
+
2H
CH3 – C – C – CH3 CH3 – C – CH – CH3 CH3
⊕ CH3 OsO4 pyridine OH
CH3 CH3 54. (a)
CH3 NaHSO3 OH
CH3 CH3
1, 2–methyl
+ shift
meso form
– H 2O
CH3 – C – CH – CH3 non-resolvable
CH3 55. (d)
Sia2BH
CH3CH3 CH3CH3 CH3 – CH2 – CH2 – C ≡ CH
–
2e CH3 – CH2 – CH2 – HC = CH – BSia2
CH3 – C – CH – CH3 CH3– C – CH – CH3
+ Η+
O –
H2O2, OH
51. (d) NaNH2 is a strong base, that gives kinetic product,
terminal alkyne as the major product while KOH CH3 – CH2 – CH2 – CH
gives thermodynamic product internal alkyne, the
CH3CH2 – CH2 – HC = CH – OH
more stable product.
Hydrocarbon 3.161
CH2
58. (c) R – C ≡ CMgZ any
 protic
→ R – C ≡ CH
COCH3 solvent
56. (c) CH
OH
C – CH3 O2N NO2
diene
O 2, 4, 6 – trinitrophenol
dienophile
NO2
O3, Zn, H2O OHC
COCH3 Triflu oroacetic acid CF3 – COOH
OHC O
CH3
DMF dimethyl formamide H – C – N
CHO CH3
It has no acidic hydrogen so, protonation is not pos-
CH3
OHC COCH3 |
sible. R – C ≡ MgX CH3 − C − Cl
COOH HOOC
|
HOOC COOH
57. (b) C–C
CH3
C=C
Nucleophilic substitution is not possible at 3° halide
H H H H +
D BD2 hence, alkylide R – C ≡ C– Mg X acts as base abstracts

D – BD2 hydrogen from β– carbon cause elimination thus
HOOC COOH products are R – C ≡ C – H + CH2 = C − CH3 + MgXCl
2 C=C |
H H CH3
59. (c) At node:
O O
HOOC COOH
H C–C H CH3 CH C O– (CH3)2 CH – C – O + e–
D
CH3
3
B O
H2O2,OD– OD–, D2O 2(CH3)2 – CH – C – O 2(CH3)2 – CH

B O – CH – CHDCOOH
(CH3)2 – CH – CH – (CH3)2 (Coupling)
COOH 3
CH3 – CH + CH3 – CH CH3 – CH – CH2 = CH
DO — CH — CHD OD , D2O– DO — CH — CHD
CH3 CH3 CH3 CH3
COOH COOH COOD COOD (disproportionation)
O
Hydrolysis starts that remain in equilibrium •
OH (CH3)2CH + (CH3)2 – CH – C – O →
O
R – C – O– R–C=O (CH3)2 – CH – C – O – CH – (CH3)2
O
OD OD
60. (c) CH3 – C – O– ∆ +
CCl3 + CO2 + Na
cis + syn addition → meso form or erythro
COOD :CCl2 + NaCl
5
H D Cl 4
Hence, H OD C
3
Cl 2 1 Cl
COOD Cl
3.162 Hydrocarbon
6 DOF.2+¨ 7K2¨
5 1
Cl Cl ,,, ,,
+2
Cl 5
4 2 Cl %U
3 , +2%U+

4
61. (b)
,, 7K2¨ ,,, DOF.2+¨
±+2 ±+%U
6
96. (c)
+
HOCH2 – CH = CH – CH2 – CH2 – OH2 Cl H 2O ZnCl2/HCl
Cl
1 2 3 4 5 6
OH
O CH3CO3H O Mg/ether D 2O
O MgCl D
Epoxidation
97. (b)
98. (c) Trans additions of – OH and ‘D’ at C=C is
62. (c) O O ctaking place.
NBS CH3CH2O
O CH3CH2 O
Br
–CH3CH2OH CH3 CH3
C
C C D
OCH2CH3
H CH3
O O CH3 D
CH3CH2OH OH
O CH3 Et Me
Br C H3O⊕ C C + enantion
CH3 D H
DH
⊕
OCH2CH3 CH3CH2OH O O
99. (c) O O
C ≡ CH C–C–H
O
OCH2CH3 O–O
C B–H (9-BBN)
H 2O
O [C16H21B]
Favorski rearrangement COOH + H2O +CO2
HOO (Hydroboration oxidation)
63. (d) 64. (a) 65. (c) 66. (b) 67. (d)
CrO3/Acetone/H2O
68. (d) 69. (a) 70. (a) 71. (c) 72. (a) CH2 – CHO
73. (b) 74. (c) 75. (b) 76. (b) 77. (d)
CH2 – COOH
78. (d) 79. (a) 80. (d) 81. (b) 82. (b)
83. (c) 84. (a) 85. (d) 86. (a) 87. (b) 100. (d) The least stable alkene has highest value of heat of
hydrogenation
88. (b) 89. (c) 90. (c) 91. (a) 92. (d)
Br
93. (d) 94. (a)
CH2 – CH3 CH – CH3
⊕
Br2/hυ (CH3)3CO K NBS
95. (A) 101. (b)
(P) Br
(X)
Hydrocarbon 3.163
CH = CH2 106. (b)
alc. KOH CH3
(X)
Hg(OAc)2 H3C – C – CH2 – CH3
HO – CH – CH3 NaBH4
aq. KOH
CH3 – CH2 – CH2 – N
H3C – C – CH3
CH3 CH3
Ph – CH – O – CH – Ph CH3
CH3
102. (d)
H3C – C – CH2 – CH3
HBr/R2O2 HBr/dark
Ph – C ≡ CH Ph – CH = CHBr
CH3 – CH = CH2 + N – CH3
H
Br H C(CH3)3
Ph – CH CH2 ≡
Ph Br O
Br Br H
CH2C – Cl / AlCl3
(Elect. Add.)
103. (a) +
O (CH3C AlCl4–)
CH3 CH3 O
(1) B2H6, THF H TsCl CH3 – CH – CH2 – C – CH3
(2) H2O2 / NaOH H
OH Cl
CH3 CH3
H t-BuO H + t-BuOH + TsOH 107. (a) +M group stabilizers carbocation effectively
H therefore fast rate of electrophilic addition.
OTs
H H
⊕
104. (a)
⊕
2CH3MgBr
CH3 – CH – CH2 – C ≡ CH
⊕
–H
⊕ ∆
OH
CH3 – CH – CH2 – C ≡ C – MgBr + 2 CH4↑ 108. (c)
OMgBr
109. (d)
105. (a)
CH3
CH3 – CH ≡ CΘ + CH3 – C – C – H
H O 110. (c)
H CH3
CH3 – C ≡ C – C – CH3
OΘ H
3.164 Hydrocarbon
MCQS WITH ONE OR MORE THAN ONE CH3 – CH + CH3 – CH – I CH3 – CH – CH – CH3
CORRECT ANSWERS CH3 CH3 CH3 CH3
(nuclcophilic action)
1. (b, c) Alkane having same kind of hydrogen will give
same products on methylene insertion. + CH3 – CH2 + CH2 = CH
CH3 CH3 (basic action)
2. (a, c, d) These molecules are unsymmetrical and
having odd number of C – atoms.
Hg2 +
3. (b, c) 6. (b, d) CH ≡ CH + CH3COOH
O
&+ &+

+ CH2 = CH – O – C – CH3
Vinyl acetate
&+
O
Hg2+
2+ CH2 = CH – O – C – CH3 + CH3COOH

&+ &+ CH3 – CH(–OCOCH3)2
ethylidene diacetate
&+ + 2 &+

2+
&\FORSURS\OPHWK\O
FDUERQLXPLRQ
4. (c, d)
%+±7+)
&+ &+ &+±&+±2+
$QWL0DUNRZQLNRII¶V O = C – CH3
DGGLWLRQ O – C – CH3
2+±
+%U±SHUR[LGH CH3 – CH CH3 – CH + O
&+±&+±%U O
O – C – CH3 O
O = C – CH3
5. (a, b, c, d) &+ &+ ±&+±, 1D

3URGXFW O
&+
CD.CH3 – CH – CH3
2Na → 2Na +2e + – 7. (a, c) E1
CH31 + 2e– → CH⊝3 + I⊝ + OH
CH31 + CH⊝ → CH3 – CH3 + I–
1, 2–D–Shift
2Na + 2I– → 2NaI CDCH3 – CH – CH3
⊕
CH3 + CH3 – CH – I CH3 – CH – CH3 + I–
CH3 CH3 CH3
Abstraction of hydrogen
[CH3 acts as nucleophile] CHD – CH3
⊕
CH3 + CH3 – CH – I CH4 + CH2 = CH – CH3

CH3
[CH3 acts as base] D CH3
Isopropyl iodide can also accept electron C=C C=C
CH3 CH3 CH3 D
CH3 – CH – I – 2e CH3 – CH – I– E Z
more stable
CH3 CH3 predominant product
Hydrocarbon 3.165
CH2 H2SO4/Hg2+
(ii) CH3 – C ≡ CH CH3 – C = CH
C – CHD – CH3 OH
tutomerisation
CH3 – C – CH3
minor product
O
8. (a, b, c, d) BH3/THF
(iii) CH3 – C ≡ CH CH3 – CH = CH – OH
9. (c) anti Markonikov
tautomerisation
Ph – C – CHCl2 CH3CH2 – CHO
HOCl NaOH
Ph – C ≡ CH (excess)
O
H LINKED COMPREHENSION TYPE
Ph – C – CH
OH
Internalcannizaro
Ph – C – CO– COMPREHENSION-I
OO reaction OH O 1. (c) I2 is more polarisable
(±)
10. (a, b, d) Option (c) correctly represent this reaction CH3 CH3
OH 2. (d) H W W H
H W W H
CH = CH2 CH – CH2 – Br CH2CH3
HOBr/H⊕ CH2CH3
⊕
(1) [H2O – Br] Erythro dl pair
OH
3. (c) As CH3 – CH = CH – CH3 + HOCl →
Cl2/Fe CH – CH2 – Br ICl/ZnCl2
(2) (3) Cl+
Cl
I OH CH3 – CH – CH – CH3
I
CH = CH2 Reaction intermediate – 2
Zn/CH3COOH CH
CH2Br
Cl I (4)
Cl I Reaction is stereospecific
δ δ− ZnCl2
IC + ZnCl2 I + Cl (I⊕ + Zn CI3)
COMPREHENSION-II
11. (a, b, c)
LiNH2 ⊕ 4. (a)
Cu – C ≡ C – H Bu – C ≡ C Li Ph – CH = O
(A)
rigid cis rigid trans oid (minimum)
C ≡ CBu C ≡ CBu
⊕
oid actually not possible
H2O
Ph – CH – O Li Ph – CH – OH
(B) CH3 CH3
O
CH = O CH = O
C – C ≡ CBu MnO2
5.
δ− δ+
H ⊕ H 2 O⊕
12. (a, b) (i) CH 2 = C = CH 2 
→ CH = O
δ−
CH 2 = C = CH 2 = C − CH 3 − H ⊕ CH3
⊕
| |
⊕ δ+
H OH 2
tautomerisation CH3
CH 3 − C − CH 3 CH 2 = C − CH 3
|| | CH = O
OH O
3.166 Hydrocarbon
COMPREHENSION-VII
6. (b) CH2 19. (a) 20. (c) 21. (c)
Aromatic characteristic CHCHO COMPREHENSION-VIII

is less
22. (c) 23. (b) 24. ()
CH = O
COMPREHENSION-IX
25. (b) 26. (c) 27. (a)
ASSERTION AND REASON
COMPREHENSION-III 1. (d) Alkyne reactivity is less towards E⊕.

2. (a) 3. (a) 4. (a) 5. (c) 6. (a)
7. (d) 7. (a) 8. (a) 9. (a)
O
|| KMnO 4
8. (b) C3H 2 O 2 , HC ≡ C − C − OH MATRIX MATCH TYPE
O
||
CO 2 + HO − C − C − OH 1. A – P, Q, R, S B – P, Q, R, S
C – P, Q, R D–Q
O
CO2
2. A — Q B — P, R, S
9. (a) HC ≡ CMgBr HC ≡ C – C – OMgBr C — P, Q , S D — P, S
CH3
3. A — R B — P, R, S
CH3 – C – Br C — Q, R D — P, R
CH3 (d) Reactant molecule undergoes anti-elimination but
as the product can’t exhibit stereoisomerism, that’s
HC ≡ CH – CH2 = C – CH3 + MgBr2 why reaction is not stereospecific.
O 4. A — P, Q, R B — P, R
3° halide perfers elemination
rather than substitution C — P, S D — P, R
5. A — Q, S B — Q, R
COMPREHENSION-IV C — P, R D — R, S
10. (c) Br2, H2O is good oxidising agent. Aldehyde is 6. A = Q B = Q, R, S
oxidised to acid but ketone is not oxidised even
C = R, P D=P
alcohol is oxidised to carbonyl group.
11. (b) Mg, dry ether
CH = CH2 1. BH3, THF

12. (d) 2. H3O2, OH–
CH2 – X Zn, CH3OH CH2
CH2 – CH2 – OH Dehalogenation
CH2 – X CH2
COMPREHENSION-V
13. (c) 14. (b) 15. (d) Na, dry ether
COMPREHENSION-VI 7. A = R B=P
16. (d) 17. (b) 18. (c) C=S D=R
Hydrocarbon 3.167
&+±&+±&O CH3 CH3

2+
(O&% CH3
⊕ ⊕
H⊕
CH3 ring
(B) *14 *14 expansion
CH3
3K±&+±&+±&O 3K±&+±&+ *14
&DUEDQLRQ
CH3 CH3
CH3 CH3
&O =Qo=QH CH3shift H2O
3K±&+±&+ ⊕ HO
&O *14 *14
3K±&+±&+
&O CH3
3K±&+ &+ B2H6 /THF

3K±&+±&+ (antimarkonikov addition)
(C) 14* OH /H2O2
+
&DUEHQH CH3
) 0J7+)
14*
&O
EHQ]\QHGLHQRSKLOH
'LHOV$OGHUUHDFWLRQ
B2H6/THF
(D) PhC = CD PhC = CD
OH⊝/H2O2
&O ± &O D BD2
2&+&+ Tautomerisation
PhC = CD Ph – CD2 – CDO
2 1 2&+&+21 FDUEDQLRQ
D BD2
8. A. Q B. S C. P D. P, R
9. A. Q B. P,Q C. S D. R
INTEGER TYPE
10. A. R, S B. P
C. Q, R D. R, S
2+ H H
5HDFWLRQ$JLYHV &+
1. (A) CH3 C≡C CH3
2+
5HDFWLRQ%JLYHV OH OH
(R) (S)
&+
5HDFWLRQ&JLYHV 2&+
%U
2+
5HDFWLRQ'JLYHV &+
11. (A → s); (B → p); (C → q); (A → r)
(A)
tautomerisation
3.168 Hydrocarbon
Eriantiomers Opticallyactive. H
H
Total stereoisomers–3
Optically active–2; CH3 C≡C H
optically inactive–1 H CH3
H OH
H H (R) (S)
(B) H OH
CH3 C≡C CH3 Na / liqNH3
Syn CH3 C≡C CH3
anti
OH OH
(R) (S) OH OH
(R) (R)
H H
H
H
CH3 C≡C CH3 OH
CH3 C≡C
OH H H OH H CH3
(R) (S) OH H
(R) (R)
H OH H
OH
Lindlar
CH3 C≡C CH2 CH3 C≡C CH3
Syn
OH OH H OH
(R) (R) (S) (S)
H OH OH H H CH3
CH3 C≡C CH3 CH3 C≡C OH

H
H
HO H H H
(R) (R) (S)
oth R, R and S, S on reduction will give one
B
OH H stereoisomer optically active.
Total - 3: Optically active - 2;
CH3 C≡C CH3 Optically inacive - 1.
Syn
H OH H H
(D) CH (1) PhCOOH
OH H 3 C=C Cl3
H H (2) H3O⊕
OH OH
CH3 C≡C CH3
CH3 CH3
HO H H OH
H H H OH
Optically inactive –1 H OH HO H
HO H H OH
HO H H OH
(C) H H CH3 CH3
racemic mixture
CH3 C≡C CH3 Ans. (a) 3

(b) Optically active - 2; Optically inactive - 1
OH OH (c) 3 Optically active - 2; Optically inactive - 1
(R) (S) (d) 2 racemic.
Hydrocarbon 3.169
2. (4) SUBJECTIVE QUESTIONS

Cl2
CH3 – CH = CH2 CH3 – CH = CH2 1. (a) Electrophilic addition of HBr on carbon - carbon
double leads to the formation of 2°-carbocation
Cl Cl while that on carbon-carbon triple bond leads to the
Total → 2
(E⊕ Addn) formation of vinylic carbocation as the intermediate.
Vinylic carbocation being most unstable whereas
Cl2
CH3 – CH = CH2 2°-carbocation being relatively more stable, addition is
500°C radical subs favoured on ethylenic linkage more stable, addition is
favoured on ethylenic linkage rather than on acetylenic.
Cl2 * Addition on carbon-carbon double bond:
CH2 – CH = CH2 CH2 = CH – CH2 ⊕
CH2=CH—CH2—C≡CH + HBr CH3CHCH2C≡CH
Cl + 2°-carbocation
Cl Total - 2
CH2 = CH – CH2
Total No. of possible products CH 3CHCH 2C≡CH
CH3 Br
* Cl (Actual product)
3. * Total 3 chiral without symmetry so total Addition on carbon-carbon triple bond.
* Br
Et CH2=CH—CH2—C≡CH + HBr
produts m = 23 = 8. ⊕
CH2=CH—CH2—C=CH2
All optically active. (Vinylic carbocation)
4. Some initially formed singlet carbine consume
Br–
collides with inert gas molecule and changes to triplet.
CH3 CH3 CH3 H CH2=CH—CH2—C=CH2
C
H H H CH3 Br
Trans OH OH2
cis meso
optically active − H 2O
(b) H+
H H
H CH3
CH3
CH3
H3C CH3 CH3 CH3

2. I = CH C CH3 J = H3C C CH
Trans optically active I CH3 I CH3
Total 3 sterecisomers: 2 optically active; 1 optically O
inactive 3. H3C H + / Hg 2+ H3C LiAlH4
H2 O
N — OH CH CH3
(A) (B)
5. Two Geometrical centers; Total isomers
OH
N — OH Conc. H2 SO4
H3C H3C
H ∆
= 22 = 4 CH3 CH2
Ans. 4 (C) (D)
3.170 Hydrocarbon
(d) can also be obtained from (a) as follows: CH3 CH3

H
CH3 — C ≡ CH − 2 CH3 — CH = CH2 7. A = H3C
Pd CaCO3
(A)
CH3
CH3 Cl
CH3
CH3
4. (a) H C
3 B = H3C
CH3 CH3
CH3 Cl
H3C COOH
(b) C = H3C
CH3 CH3
CH3 CH3
CH3 Cl CH3
5. (a) (b) CH3
CH H3C
H3C D = H3C
Cl Cl
CH3 CH3
CH3
(c) CH3
H3C E = H3C
O CH3 CH2
CH3 CH3 CH3
F = H3C
6. A = H3C CH3
CH3
Br CH3 Cl
G = H3C CH3
B = H3C CH3
Br H3C CH3
CH3 8. The 6 different alkenes (A) to (F) are
CH3 CH3
C = H3C CH3
OH CH3 A= B=
H2C H3C
D = H3C CH3
CH3 CH2
OH
O C= D=
H3C H3C
E = H3C OH CH3 CH3
CH3
E= F=
F = H3C COOH
H3C H3C
Hydrocarbon 3.171
CH3 CH3
H3 C
12. A =
G = H3C H H3 C
H
H3C
CH3
9. (i) It should be an alkene as it adds one mole of H2 – +
B = H3C C Na
(ii) Alkene should be symmetrical of six carbon
atoms
CH3
CH3 CH 2 CH = CHCH 2CH3
H2
CH3
CH3 CH2 CH2 CH2 CH2 CH3
C = H3 C
[O] CH3 CH3
CH3CH 2COOH
KMnO4
CH3
O3+ H2O LiAlH 4 H3C
10. (i) O D=
CH3
H 2 SO4 H3C
OH –H 2O
H HO
C CH3
(ii) C H2 H H3C
CH3 13. H3C CH3
Lindlar
catalyst H3C
(iii) Cl Cl H3C
(X) (Z)
CH3 CH3 (CH3 )3COK
– HCl MgCl MgCl
11. H3C C C CH3 (E liminationoccurs)
Cl H
2-Chloro-2, 3-dimethylbutane H3C CH3
(X) (Y)
H3C CH3 H 3C CH3
14. A is obtained by syn addition
C C + C HC
H3C CH3
H3C CH3 H 2C CH3
A
2,3-dimethylbut-2-ene 2, 3-Dimethylbut-1-ene
=
(Y) (Z)
H H
cis
B is also obtained by syn addition

CH3
+ +
CH3
H3C %
+& &+
CH3 ' '

2,3-dimethylbutane PHVR
3.172 Hydrocarbon
C is obtained by anti addition CH3
+ &+ C = H3C
& CH3 CH3
+& + CH3 CH3
D is mix of d- and l- (reacemic mixture) D = H3C

+ ' CH3
' +& &+
16. (i) Peroxy formic acid hydroxylates double bond but
' + not triple bond. Therefore, compound (A) is
GDQGO UDFHPLF
CH3
E is obtained by syn addition
E = as A HO
Addition of Br2 is anti OH
+ %U
(ii) Oxidation of triple bond is very much slower than
) +& &+
that of double bond. Therefore, by using a suit-
%U + able oxidizing agent it is possible to selectively
UDFHPLF oxidize double bond in presence of triple bond.
+& %U CrO3 in presence of AcOH is one such oxidizing
* agent, which oxidizes double bond and not triple
bond. Thus, compound (b) is
%U &+
H = as F
15. CH3 HOOC COOH CH3

A = H3C H
(iii) Aqueous KMnO4 hydroxylates both the double
CH3 bond as well as triple bond. The compound (c) is
CH3 O O
B = H3C C Na C C CH3
HO
CH3 OH

PREVIOUS YEARS’ AIEEE QUESTIONS
1. In the following sequence of reactions, the alkene The compound B is

affords the compound ‘B’ (a) CH3CH2CHO
[2008] (b) CH3COCH3
O3 H2O (c) CH3CH2COCH3
CH3CH == CHCH3 A Zn B. (d) CH3CHO
Hydrocarbon 3.173
2. The hydrocarbon which can react with sodium in (a) n-butane (b) 1-butyne
liquid ammonia is [2008] (c) 1-butene (d) Isobutene
(a) CH3CH2CH2C ≡ CCH2CH2CH3
(b) CH3CH2C ≡ CH 6. On mixing a certain alkane with chlorine and
(c) CH3CH = CHCH3 irradiating it with ultraviolet light, it forms only one
(d) CH3CH2C≡CCH2CH3 monochloroalkane. This alkane could be
(a) propane (b) pentane
3. Of the five isomeric hexanes, the isomer which can (c) isopentane (d) neopentane
give two monochlorinated compounds, is
[2005] 7. Butene-1 may be converted to butane by reaction with
(a) 2-methylpentane [2003]
(b) 2, 2-dimethylbutane (a) Zn-HCl (b) Sn-HCl
(c) 2, 3-dimethylbutane (c) Zn-Hg (d) Pd/H2
(d) n-hexane
8. Acetylene does not react with [2002]
4. Which one of the following is reduced with zinc
(a) Na (b) ammoniacal AgNO3
and hydrochloric acid to give the corresponding
(c) HCl (d) NaOH
hydrocarbon? [2004]
(a) Ethyl acetate (b) Acetic acid 9. Acetylene reacts with hypochlorous acid to form
(c) Acetamide (d) Butan-2-one [2002]
5. Which one of the following has the minimum boiling (a) Cl2CHCHO (b) ClCH2COOH
point? [2004] (c) CH3COCl (d) ClCH2CHO
ANSWER KEYS
1. (d) 2. (b) 3. (c) 4. (d) 5. (d) 6. (d) 7. (d) 8. (d) 9. (a)
SOLUTIONS
O Actually it is truth that Na/liq NH3 induces internal

O3
triple bond and terminal double bond and do not
1. CH CH=CHCH CH3 — CH CH — CH3
3 3 reduce the terminal alkyne due to such alkylide
formation.
O O
Zn, H2O
3. (a) 2-methyl pentane →
Cl2
five types of monochlo-
Reductive rinated compounds
ozonolysis (b) 2, 2-dimethylbutane → Cl2
three types….
2CH3 — CH O (c) 2, 3-dimethylbutane → Cl2
two types….
‘B’ (d) n-hexane → Cl2
three types ….
4. Carbonyl compounds are reduced to corresponding
2. CH3CH 2C ≡ CH Na/Liq.NH3
∆ alkanes with (Zn + cone HCl). It is called Clemmensen
CH3CH2C ≡ CNa+ reduction.
O
Considering the options given it appears correct.
Na/liq NH3 is known for metal dissolved reduction. CH3CH.2C CH3 Z n(Hg) + HCL
3.174 Hydrocarbon
H3C CH ≡≡ CH == HCI → CH2 ═ CH — C1

5. Isobutene C CH 2 has minimum force of
H3C Usually occurs in the presence of Hg2+
CH ═ CH + NaOH → no reaction
attraction (due to steric hindrance). Thus minimum
boiling point. Because of hard acid hard base soft acid soft base
(HASB) theory
6. In neopentane, all H are equivalents.
CH ≡ CH+ NaNH2 → CH = C– Na+ feasible.
CH3 CH3
9. CH ≡ CH 
HOCl
→ Cl2 CHCHO
hv
H3C —C—CH3 Cl2
H3C —C—CH2Cl + +
CH = CH + Cl CH = CH – Cl
CH3 CH3 OH
7. CH CH — CH CH Pd/H2
2 2
butene-1
3
∆ pressure CH—CH2 — Cl CH=CH — Cl
CH3 — CH2 — CH2 — CH3 O OH
butane
Other reagents are successful with polar double bond.
CH=CH — Cl CH—CHCl2
8. CH ≡ CH + Na  1 − +
→ CH ≡ C Na + H 2 + O
2 OH Cl
tautomerising electrophile is Cl+ mainly.

ALKENES CH3
H H
STRAIGHT CONCEPTUAL TYPE
C3
2. In the given conformation, C2
H H
1. Consider the following reaction:
H3C—CH—CH—CH3 + Br → ‘X’ + HBr CH3
D CH3 C2 is rotated about C2–C3 bond clockwise by an of
angle 120°. The obtained conformation is
Identify the structure of the major product ‘X’(2002)
(2004)
(a) H3C—CH—CH—CH2
(a) anti conformation
(b) gauche conformation
D CH3
(c) partially eclipsed conformation
(b) H3C—CH—C—CH3 (d) fully eclipsed conformation
3. In the reaction
D CH3
(CH3)2CHCH2CH3 →
Cl2
N isomers of C5H11Cl
(c) H3C—C—CH—CH3 hv

Fractional
distillation
→ n distilled products. The values of N and
D CH3 n respectively are (2006)
(a) 6, 6
(d) H3C—CH—CH—CH3 (b) 6, 4
(c) 4, 6
CH3 (d) 4, 4
Hydrocarbon 3.175
MULTIPLE CORRECT CHOICE TYPE INTEGER ANSWER TYPE
1. In the Newman projection for 2,2 dimethylbutane 1. The maximum number of isomers (including
stereoisomers) that are possible on monochlorination
X of the following compound is
H 3C CH3
CH3
C
CH3CH2 CH2CH3
H H
Y H
X and Y can respectively be (2010) (2011)

(a) H and H (b) H and C2H5
(c) C2H5 and H (d) CH3 and CH3
ANSWER KEYS
1. (b) 2. (b) 3. (b)
Multiple Correct Choice Type

1. (b, d)
HINTS AND SOLUTIONS
STRAIGHT CONCEPTUAL TYPE Of the four products, two are optically active
each will produce two isomers. Hence, the
1. The choice (b) involves 3° radical. number of isomers is 6 and the number of product
is 4.
2. The resultant configuration is gauche.
H
H H
MULTIPLE CORRECT CHOICE TYPE
H CH3
CH3 CH3
3. Monochlorination of the given compound gives four 1. The given compound is X — CH2 — C — Y and
products.
Cl CH3
Cl2 CH3
(CH3)2CHCH2CH3 CH3– C – CH2CH3 +
hv
CH3 2, 2-dimethylbutane is CH3 — C — CH3 — CH3
Cl H2C – CH – CH2 – CH3 + CH3 – CH – CH – CH3 +
CH3
CH3 CH3 Cl
CH3 – CH – CH2 – CH2Cl Hence, either X should be H and Y should be
CH2CH3 or X should be CH3 and Y should also be
CH3 CH3.
3.176 Hydrocarbon
INTEGER ANSWER TYPE CH3
CH3CH2C—CH2CH3 1
CH3
* Cl
1. (8) CH3CH2C—CH2CH2Cl Enantiomeric pair = 2
CH3Cl
H
* 1
CH3 CH3CH2C—CH 2
CH3
*
CH3CH2C—CHCH3 Two Enantiomeric pairs = 4 H
*
H Total = 2 + 4 + 1 + 1 = 8

ALKANES (a) X = dilute aqueous NaOH, 20°C; Y = HBr/acetic

acid, 20°C
STRAIGHT CONCEPTUAL TYPE (b) X = concentrated alcoholic NaOH, 80°C; Y =
HBr/acetic acid, 20°C
1. Which one of the following alkenes will react fastest (c) X = dilute aqueous NaOH, 20°C; Y = HBr/CHCl3,
with H2 under catalytic hydrogenation condition? 0°C
(2002) (d) X = concentrated alcoholic NaOH, 80°C; Y = Br2/
R R R H CHCl3, 0°C
(a) (b)
5. The product of acid catalysed hydration of
H H R H 2-phenylpropene is
R R R R (2004)
(c) (d) (a) l-phenyl-2-propanol
R H R R (b) 2-phenyl-2-propanol
(c) 1-phenyl-l-propanol
2. The reaction of propene with HOCl proceeds via the (d) 2-phenyl-l-propanol
addition of (2001)
(a) H in the first step
+
6. In the reaction CH3 — CH = CH2 NOCl
→ A, the
(b) Cl+ in the first step compound A is (2006)
(c) OH– in the first step
(a) CH3CH(NO)CH2Cl
(d) Cl+ and OH– in a single step
(b) CH3CHClCH2NO
3. In the presence of peroxide, hydrogen chloride and (c) CH2(NO)CH2CH2Cl
hydrogen iodide do not give anti-Markovnikov (d) CH3CH(Cl)CH2CH(Cl)CH3
addition to alkenes because (2001)
(a) both are highly ionic 7. Amongst the given options, the compound (s) in
(b) one is oxidising and the other is reducing which all the atoms are in one plane in all the possible
(c) one of the steps is endothermic in both the cases conformations (if any), is (are) (2011)
(d) all the steps are exothermic in both the cases H H H
4. Identify the set of reagents/reaction conditions ‘X’ and (a) (b) H
C C C C C
‘Y’ in the following set of transformations: (2002)
CH3 – CH2 – CH2Br X Product Y H2C CH2 CH2
CH3 – CH – CH3 (c) H2C C O (d) H2C C CH2

Br (2011)
Hydrocarbon 3.177
REASONING TYPE Assertion (Column 1) Reason (Column 2)

3. Addition of bromine Bromine addition
In each subquestion below an assertion in the left hand to rnms-2-butene to an alkene is an
column and a statement in the right hand column are yields meso-2, electrophilic addition.
given. Select one of the correct codes from the following 3-dibromobutane (2001)
categories for each subsection.
4. Dimethylsulphide is It reduces the ozonide
Code commonly used for giving water soluble
(a) If both assertion and statement are true and statement is the reduction of an dimethyl sulphoxide
an explanation of assertion. ozonide of an alkene and excess of it
(b) If assertion is correct and statement is wrong and state- to get the carbonyl evaporates.
ment is not an explanation of assertion. compounds. (2001)
(c) If assertion is wrong and statement is correct, statement
is an explanation of assertion
(d) If both assertion and statement are wrong and state-
INTEGER ANSWER TYPE
ment is not explanation of assertion.
Assertion (Column 1) Reason (Column 2) 1. The total number of alkenes possible by
1. Addition of Br2 to The product contains dehydrobromination of 3-bromo-3-cyclopentlyhexane
1-butene gives one asymmetric carbon. using alcoholic KOH is
two optical isomers. (2011)
(1998)
2. 1-Butene on It involves the SHORT ANSWER TYPE
reaction with HBr formation of a primary
in the presence of a radical 1. CH2 = CH– is more basic than HC ≡ C–
peroxide produces (2002) (2002)
1-bromobutane.
ANSWER KEYS
1. (a) 2. (b) 3. (c) 4. (b) 5. (b) 6. (b) 7. (b, c)
Reasoning Type
1. (a) 2. (c) 3. (b) 4. (a)
Integer Answer Type
1. (5) Total no. of alkenes will be = 5
Br
H3C – CH2 – CH2 – C – CH2 – CH3 H3C – CH2 – CH2 – C = CH – CH3
(E & Z)
alc. KOH
H3C – CH2 – CH = C – CH2 – CH3

(E & Z)
or
H3C – CH2 – CH2 – C – CH2 – CH3

(only 1)
or
3.178 Hydrocarbon
Short Answer Type

1. The hydrogen atoms in acetylene are more acidic than those in ethylene. This is due to the fact that carbons in
acetylene are more electronegative (due to sp hybrid orbitals) than those in ethylene (which involves sp2 hybrid
orbitals). The conjugate base of acetylene and ethylene follow the reverse order. Thus
acidic character H — C ≡≡ C — H > H2C == CH2
–
basic character H — C ≡≡ C– < H2C == CH
HINTS AND SOLUTIONS
STRAIGHT CONCEPTUAL TYPE 6. Due to the electron-releasing methyl group, the

reaction proceeds as follows.
R H R R
1. C C is more stable than C C CH3 –CH == CH2 NO – Cl
CH3CH – CH2NO
R H H H |
Cl
2. –––––––––––––
7. Along C–C single bond conformations are possible
3. ––––––––––––– in butadiene in which all the atoms may not lie in the
4. CH – CH – CH Br conc. alcoholic NaOH same plane.
3 2 2 80°C
HBr/acetic acid REASONING TYPE
CH3 – CH = CH2 CH3 – CH – CH3
20°C
Br 1. -------------
OH 2. There is a formation of secondary radicals
H2O | 3. ---------------
5. The reaction is CH3 – C – CH2 CH3– C = CH3
| H+ | 4. ---------------
C6H5 C6H5 5. ---------------
2-phenyl-2-propanol 6. ---------------

ALKYNES (c) dilute H2SO4, HgSO4

(d) ammoniacal Cu2Cl2 solution
1. Propyne and propene can be distinguished by
3. Which of the following hydrocarbons has the lowest
(2001) dipole moment? (2002)
(a) cone. H2SO4 (b) Br2 in CCl4 H3C CH3
(c) dil. KMnO4 (d) AgNO3 in ammonia (a) C C
2. Identify a reagent from the following list which can easily H H
distinguish between 1-butyne and 2-butyne: (2002) (b) CH3C ≡ CCH3
(a) bromine CCl4 (c) CH3CH2C = CH
(b) H2, Lindlar catalyst (d) CH2 = CH— C ≡ CH
Hydrocarbon 3.179
4. In the reaction (i) conc. H2SO4

(2003) (catalytic amount)
P (i) dil. H2SO4/HgSO4 (–H2O)
Hg2+/H+ Q 2
Ph — C C CH3 A (C16H10) (ii) NaBH4/ethanol (ii) O3
(iii) dil. acid (iii) Zn / H2O
the product A is
O
(a) PhCOCH2CH3
(b) PhCH2COCH3
C
(c) PhC(OH)=CH—CH3
(d) PhC = C(OH)CH3 H3C CH3
5. Which of the following reagents is used for the
1. The structure of compound P is
conversion of 2-hexyne into cis-2-hexene?
(a) CH3CH2CH2CH2 – C ≡ C – H
(2004)
(b) H3CH2C – C ≡ C – CH2CH3
(a) H2/Pd-BaSO4 (b) H2, Pt H 3C
(c) Zn/HCl (d) Li-NH3/C2H3OH
(c) H — C — C — — C — CH3
—
6. The reagent(s) for the following conversion,
Br H3C
?
H – – H is/are
Br H3C
(2007) (d) H C — C — C —
—
— C— H
3
(a) alcoholic KOH
(b) alcoholic KOH followed by NaNH2 H3C
(c) aqueous KOH followed by NaNH2
2. The structure of compound Q is (2011)
(d) Zn/CH3OH
OH
H 3C
7. The synthesis of 3-octyne is achieved by adding a
bromoalkane into a mixture of sodium amide and an (a) H — C — C — CH2CH3
alkyne. The bromoalkane and alkyne respectively
H3C
are H
(2010) OH
H3C
(a) BrCH2CH2CH2CH2CH3 and CH3CH2C ≡ CH (b) H — C — C — H CCH
(b) BrCH2CH2CH3 and CH3CH2CH2C ≡ CH 3 3
(c) BrCH2CH2CH2CH2CH3 and CH3C ≡ CH H3C H

(d) BrCH2CH,CH2CH3 and CH3CH2C ≡ CH OH
H3C
PASSAGE (c) H — C — CH2CHCH3
An acyclic hydrocarbon P, having molecular formula
H3C
C6H10, gave acetone as the only organic product through
the following sequence of reaction, in which Q is an OH
intermediate organic compound.
(2011) (d) CH3CH2CH2CHCH2CH3
ANSWER KEYS
1. (d) 2. (d) 3. (b) 4. (a) 5. (a) 6. (b) 7. (d)
PASSAGE
1. (d) 2. (b)
3.180 Hydrocarbon
HINTS AND SOLUTIONS
STRAIGHT CONCEPTUAL TYPE H2O/Hg2+ H2O/Hg2+

Ph—C==C—CH3 Ph—C==CH—CH3
1. Propyne forms insoluble acetylides with ammoniacal OH
silver nitrate solution. OH
Propene does not form acetylides.
Ph—C—CH2—CH3 Ph—C—CH2—CH3
–H2O
2. 1-Butyne contains ac’etylinic hydrogen atom. It will O OH
form insoluble acetylides.
5. The use of Lindlar catalyst (Pb-BaSO4 produces cis
3. The dipole moment of CH3C ≡ CCH3 is zero. It is a
product.
linear molecule and has symetrical arrangements of
methyl substituents. 6. Alcoholic KOH can be used to remove one molecule
of HBr to generate a double bond. The removal of
+ – second HBr requires more stronger base, that is,
4. The carbocation Ph — C — C — CH3 is more stable NaNH2.
– +
than Ph — C = C — CH3. Hence, OH group is added 7. Only the constituents given by the choice (d) will
produce 3-octyne.
to the former molecule. NaNH 2
CH3CH2C ≡ CH + BrCH2CH2CH2CH3   →
CH3CH2C ≡ C CH2CH2CH2CH3
Electrophilic Aromatic
Substitution
4
Introduction
AROMATICITY
It has been discussed in detail in the chapter ‘General Organic Chemistry’.
ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS ON BENZENE
The most important reaction of benzene is electrophilic substitution on the benzene ring. Several types of reagents
yield substitution products. All follow similar reaction pathways. An electrophile (E+) attacks the benzene ring
to form an intermediate carbocation which has two paths available to it. If the carbocation intermediate formed
from the reaction of benzene with an electrophile were to react similarly with a nucleophile, the product would not
be aromatic. Because there is a great deal of stabilization associated with an aromatic ring, the carbocation, instead
of reacting with a nucleophile, loses a proton from the site of electrophilic attack. In this way, the aromaticity
of the benzene ring is restored. The end result is that a hydrogen attached to the benzene ring is replaced by an
electrophile.
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Figure 4.1 Reaction coordinate diagrams for electrophilic substitution of benzene

and for electrophilic addition to benzene.
4.2 Electrophilic Aromatic Substitution
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The reaction of benzene to form a substituted benzene has a DG° close to zero (Figure 4.1). The reaction of benzene
to form the much less stable nonaromatic addition product would have been a highly endergonic reaction. Consequently,
aromatic compounds such as benzene and substituted benzenes undergo electrophilic substitution reactions (an electrophile
substitutes for a hydrogen) rather than electrophilic addition reactions, which are characteristic of alkenes.
The p-electron cloud above and below the plane of the benzene ring is a source of electron density and confers
nucleophilic properties on the system. Thus, reagents that are deficient in electron density (electrophiles) are likely to
attack, but electron-rich nucleophiles should be repelled and, therefore, are unlikely to react. Furthermore, in electrophilic
substitution the leaving group is a proton (H+), but in nucleophilic substitution it is a hydride ion (H–); the former process
is energetically more favourable. In fact, nucleophilic aromatic substitution is not common, but it does occur in certain
circumstances.
It might be expected that the first phase of reaction would be interaction between the approaching electrophile and
delocalised p orbitals leading to p complexes (a weakly bonded charge-transfer complex which exists in solution only
and is formed by the association of an electrophilic species (E) and on electron-donating species), e.g., toluene form a 1:1
complex with HCl at –78°C, the reaction being readily reversible. DCl also forms p complex with toluene. This complex
on decomposition does not form deuterium substituted toluene. Formation of complex leads to a solution that is a non-
conductor of electricity.
When an electrophile reacts with an arene usually in presence of a catalyst, a salt is formed. This salt is composed of
an anioin and a complex, resonance stabilized carbenium ion (arenium ion) in which only two of the total p electrons of
arene are utilized to form a a bond between a particular C atom of the ring and the electrophile, known as s complex (also
called Wheland intermediate).
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Electrophilic Aromatic Substitution 4.3
Of course, one may assume that an aromatic substitution reaction consists of four stpes involving two p and are s
complexes as shown below.
1. Formation of a π-complex
(
(
2. Conversion of p a complex to a s complex

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(į

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3. Conversion of s complex into p complex
+
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76
4. Decomposition of p complex to products
+

( ( +
However the most widely accepted mechanism for aromatic electrophilic substitution reaction is the two step
mechanism:
i) a complex formation
ii) Loss of proton from the a complex
Step 1: +E+ —→ H
(
(
+
Step 2:
Of the following two steps, step 1, the formation of the arenium ion, is the rate-determining step in electrophilic
aromatic substitution.

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( +
Step 2: + )DVW
+ ( (
Step 2, the loss of a proton, occurs rapidly relative to step 1 and has no effect on the overall rate of reaction.
The energy changes that occur during the course of the reaction are related to the structural changes in the reaction
profile shown in the following figure. It should be noted that each step proceeds through a high-energy transition state in
which partial bonds attach the electrophile and the proton to the ring and the p-cloud is incomplete.
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Figure 4.2 Energy profile for the electrophilic attack on benzene
Most examples of electrophilic aromatic substitution proceed by this sequence of events:

1. Generation of an electrophile
2. Attack of the aromatic ring on the electrophile
3. The resulting carbocation is stabilized by resonance
4. A proton is eliminated from the carbocation, regenerating the p-cloud
5. A substituted aromatic compound is formed
The product is a substituted benzene derivative.
The evidence for the two step mechanism are

i) Detection and isolation of s complex
A large number of s complexes as intermediate has been detected, some of them have also been isolated.
ii) Displacement of an H (or D) atom of C6H6 (or C6D6) by a nitronium ion NO2+ (formed by the action of concentrated
H2SO4 on concentrated HNO3) is an aromatic electrophile substitution reaction. If the C – H bond breaking is the r/d,
step, then the reaction will exhibit a primary kinetic isotope effect. By contrast C6H6 and C6D6 are found to undergo
nitration at essentially the same rate, thus C – H bond breaking cannot be involved in the r/d step, that means a
complex formation is the r/d step.
Aromatic hydrocarbons are known generally as arenes. An aryl group is one derived from an arene by removal of a
hydrogen atom and its symbol is Ar –. Thus, arenes are designated ArH just as alkanes are designated RH.
The most characteristic reactions of benzenoid arenes are the substitution reactions that occur when they react with
electrophilic reagents. These reactions are of the general type shown below.
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The electrophiles are either a positive ion (E+) or some other electron-deficient species with a large partial positive
charge. For example, benzene can be brominated when it reacts with bromine in the presence of FeBr3. Bromine and FeBr3
reacts to produce positive bromine ions, Br+. These positive bromine ions act as electrophiles and attack the benzene ring
replacing one of the hydrogen atoms in a reaction that is called an electrophilic aromatic substitution (EAS).
Electrophilic aromatic substitutions allow the direct introduction of a wide variety of groups into an aromatic ring and
because of this they provide synthetic routes to many important compounds. The five electrophilic aromatic substitutions
that we shall study in this package are outlined in fig 4.2. All of these reactions involve the attack on the benzene ring by
an electron-deficient species–by an electrophile. Later we shall learn what the electrophile is in each instance.
Illustrations
1. (a) What types of reagents effect characteristic benzene substitution? (b) Why is it called electrophilic aromatic
substitution?
Ans. (a) Electrophilic reagents or Lewis acids, (b) An H is replaced by an electrophilic group, E, preserving the
aromatic system.
2. How does the substitution in Problem — 1 differ from (a) SN 1 and SN 2 reactions, and (b) free radical substitution?
Ans. (a) In SN1 and SN2 reactions the attacking group is a nucleophile or Lewis base and the group replaced is a weaker
base, (b) The attacking species, X-, removes an H- and leaves another radical, R-, which enters a chain reaction.
3. (a) What is the first step in the reaction of E+ with PhH? (b) Compare it with the first step in the addition to an
alkene.
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The s- complexed benzenonium ion (sometimes called benzenium ion) is one example of an arenonium ion,
formed by the electrophilic attack on an arene, PhR. It is not aromatic, since the cyclic delocalization is inter-
rupted by the sp3 hybridized C. [In (b) a cyclic onium ion such as bromonium ion (7) may substitute for the
carbocation.
4. (a) How do the second steps in Problem 3(a) and (b) differ? (b) Account for the difference.
Ans. (a) In (b) of Problem 3, the carbocation reacts with a Lewis base: (²&²&%± (²&²&±%
The arenonium (or arenium) ion in (a) of Problem — 3 loses an H+, regenerating the stable aromatic p system:
+ (
%±RU%
(
±+
+ +
(b) Were the arenonium ion to add B:~ a much less stable cyclohexadiene derivative would form.
5. (a) Write (i) the contributing resonance structures and (ii) the delocalized hybrid structure to account for the
relative stability of the benzenonium ion. (b) Describe the orbital hybridization of the C’s in the benzenonium
intermediate.
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(b) The benzenonium ion is a stable allylic carbocation. The C attacked by E+ becomes sp3 hybridized. The other five
C’s are sp2 hybridized and their remaining p AO’s overlap laterally to form a delocalized p electron cloud.
6. Draw an enthalpy diagram for the reaction of PhH with E+, indicating the intermediate, In, the TS and TS2 for the
two steps, the relative energies of activation for the two steps, and the heat of reaction DH.
Ans. See figure
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7. Which is the rate-determining step in electrophilic aromatic substitution?
Ans. Formation of the intermediate arenium cation is usually slow and rate-determining. Elimination of H+ is fast since
it restores aromaticity—it has no effect on the overall reaction rate.
8. How is the absence of a primary isotope effect used to (a) eliminate a one-step substitution of H by E and
(b) establish that the first step is rate-determining?
Ans. Recall that the isotope effect, or rate ratio kH/kD, is based on the more rapid breaking of a
C — H than a C — D bond in the rate-determining step. The absence of an isotope effect in most aromatic
electrophilic substitutions shows that breaking the C-H bond is not part of the rate-controlling step. Therefore,
(a) a simultaneous bond-forming and C — H bond-breaking mechanism is eliminated and (b) the first step
in which E+ bonds to the aromatic ring without cleavage of a C—H bond is rate-determining. The C — H or
C—D bond is broken in the fast second step that restores the stable aromatic system. Hence the overall rate is
independent of the particular isotopic species used.
9. Why are most aromatic substitution reactions irreversible? (Hint: Refer to Figure)
Ans. The energy barrier DH for the reaction of the sigma complex to form products is less than DH for the reverse
rejection of E+. (If it were not, the first step would be fast and reversible and not rate-determining.) To summarize:
N + (
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The different Electrophilic Aromatic Substitution reactions on benzene are described below.
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NITRATION OF BENZENE
Benzene reacts slowly with hot concentrated nitric acid to yield nitrobenzene. The reaction is much faster if it is carried
out by heating benzene with a mixture of concentrated nitric acid and concentrated sulfuric acid.
12
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The ‘classical’ explanation for the presence of the sulphuric acid is that it absorbs the water formed in the nitration
C6H6+ HNO3 → C6H5NO2 + H2O
and so prevents the reverse reaction from proceeding.
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If the purpose of the sulphuric acid is merely to function as a highly acid medium in which ⊕NO2 can be released from
HO—NO2, it would be expected that other strong acids, e.g., HC1O4, would also promote nitration. This does indeed turn
out to be the case, and HF plus BF3 are also found to be effective.
The relatively poor performance of nitric acid alone—without added sulphuric acid—in effecting nitration of benzene
can, in the light of this information, now be explained. While nitric acid itself is found to contain some nitronium ion,
12, produced in the following way,
+12 1212Ւ+2
this concentration is very much lower than that in the presence of an equal quantity of concentrated sulphuric acid, in
which the conversion of nitric acid to 12 is essentially complete.

The various nitrating agents which are commonly employed are:

1. N2O5 in CCl4 in the presence of P2O5 is used when anhydrous conditions are required.
2. Ethyl nitrate (C2H5ONO2) is used to carry out nitration in alkaline medium.
3. In the case of polycyclic hydrocarbons N2O4 and nitronium salts such as NO +2 BF4- NO 2+ PF6- , NO 2+ SO3- can be used. The
electrophile involved in nitration reaction is nitronium ion 12 .
That ⊕NO2, once formed, is a highly effective nitrating agent is borne out by the rapid nitration that may be effected, of
even relatively unreactive aromatic species, by the salt ⊕NO2BF4Q at room temperature or below.
Highly reactive aromatic compounds, such as phenol, are found to undergo ready nitration even in dilute nitric acid,
and at a far more rapid rate than can be explained on the basis of the concentration of ⊕NO2 that is present in the mixture.
This has been shown to be due to the presence of nitrous acid in the system which nitrosates the reactive nucleus via the
nitrosonium ion, ⊕NO (or other species capable of effecting nitrosation).
+12+12 +212
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12

2+ 2+ 2+ 2+
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12 12 +12

+12
+ 12 12 12

The nitrosophenol (10), which may be isolated, is oxidised very rapidly by nitric acid to yield the p-nitrophenol (11)
and nitrous acid; further nitrous acid is produced thereby and the overall reaction is thus maintained.
FRIEDEL-CRAFTS REACTION
Introduction
Introduction of an alkyl or an acyl group into an aromatic nucleus in the presence of an acid catalyst (usually Lewis acids)
is known as Friedel-Crafts reaction.
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Commonly used solvents in this reaction are nitrobenzene, carbon disulphide, petroleum ether, etc. The scope and
application of Friedel-Crafts reactions have proliferated tremendously. Although there is apparently wide variety of types,
Friedel-Crafts reactions are broadly classified into two general categories:
(a) Friedel-Crafts alkylation and (b) Friedel-Crafts acylation.
(a) Friedel-Crafts Alkylation
Reagents and catalysts
The generally used alkylating agents are alkyl halides, alkenes and alcohols; but many others such as alkynes, ethers,
thiols, sulphate and sulphonates, cycloalkanes (under conditions where they can be converted into carbocations) may also
be employed. However, the order of reactivity for all types of reagents is:
allylic ~ benzylic > tertiary > secondary > primary.
In case of alkyl halides, the reactivity order has been observed as: F > Cl > Br > I. Thus, benzene on treatment with
FCH2CH2Cl in the presence of BCl3 yields PhCH2CH2Cl.
The most commonly used Lewis acid catalysts are anhydrous AlCl3 and BF3, but a variety of Lewis acids and also
proton acids such as HF, H2SO4, H3PO4 are in use.
It has been observed that for active halides, a trace amount of a less active catalyst (e.g. ZnCl2) is enough—while for
less active halides (such as chloromethane), a more active catalyst (e.g., AlCl3) is required and also in larger amounts.
The order of effectiveness of Lewis acid catalysts has been shown to be: AlBr3 > AlCl3 > GaCl3 > FeCl3 > SbCl5 > ZnCl4,
SnCl4 > BC13, BF3, SbCl3. However, the reactivity order in each case depends on substrates, reagents, and conditions.
Mechanism
The Friedel-Crafts reaction follows the mechanistic pathway of aromatic electrophilic substitution involving the formation
of Wheland intermediate. It is evident that in most cases the electrophile in Friedel-Crafts alkylation is a carbocation
(in free-state or as a part of an ion-pair). Alcohols and alkenes also furnish carbocation electrophiles on reaction with
Lewis or proton acids. In case of tertiary alkyl halides, where formation of stable carbocation is feasible, the alkylating
species is the actual carbocation:

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In case of primary alkyl halides, alkylation takes place via a polarized complex. Secondary alkyl halides are on the
boarder line and alkylation may occur through either mechanism:
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(b) Friedel-Crafts Acylation
Reagents and catalysts

This is a good method for the preparation of aryl ketones. The acylating reagents are usually acyl halides, carboxylic
acids, acid anhydrides and ketenes. Among the acyl halides, chlorides are most commonly employed. One of the
most common catalysts for intramolecular Friedel-Crafts acylation (ring closure) is poly phosphoric acid. The
catalysts for usual Friedel-Crafts acylation are those of the Friedel-Crafts alkylation, but in acylation, a little more
than one mole of catalyst is required per mole of acyl halide—because one mole of the catalyst remains complexed
with the carbonyl oxygen of the ketone formed. When acid anhydride is the reagent, slightly more than two moles
of the catalyst is required—one mole is used up in liberating acyl halide and the other one for complexing with the
product.
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Mechanism
Depending upon conditions probably two mechanisms may operate for Friedel-Crafts acylation. In most cases the attack-
ing species is the acyl cation, either free or as an ion-pair:

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In other mechanism instead of acyl cation, a 1:1 complex attacks the aromatic ring directly:

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Critical Views
(a) Friedel-Crafts alkylation suffers from few limitations, A frequent limitation of the reaction is di-and poly-alkylations
of the substrate—this happens since the entering group (alkyl) is the activating one. Another important synthetic
limitation is that during the reaction, rearrangement usually takes place in the reactant. For example, benzene treated
with n-propyl bromide gives mostly isopropyl benzene (cumene) and much less n-propyl benzene. It is also interesting
to note that the electron-releasing groups like –OH, –OR, –NH2 do not facilitate the reaction, since the catalyst
forms complexes with these groups. Moreover, in most cases, meta-directing groups deactivate the ring making it too
inactive to undergo alkylation—thus nitrobenzene does not respond towards Friedel-Crafts reaction.
(b) An extension of Friedel-Crafts reaction is the arylation of an aromatic substrate—the reaction is called Scholl reaction.
The coupling of two aromatic molecules takes place in the presence of both a Lewis and a proton acid.
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(c) A variety of substrates including heterocyclic compounds (except pyridines and quinolines) undergo Friedel-Crafts
acylation reaction. Compounds having ortho/para-directing groups such as alkyl, hydroxy, alkoxy, and halogen
are easily acylated and furnish exclusively the para-products because of the relatively large size of the incoming
acyl group. Since the entering acyl group is deactivating unlike the alkyl, a mono-substituted product is usually
obtained.
Applications
The contributions of Friedel-Crafts reaction to synthetic organic chemistry are remarkable. A variety of compounds can
be synthesized with the help of this reaction. A few examples are cited below:
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6. 2
2 &22+ &22+
FRQF+62
L1D+J+&O
LL6H
2
&2&+
&2&+
&+&2&O &+&2&O
7.
&+&ORU &+ &O 3K12&
ĮLVRPHU ORZWHPSHUDWXUH EQDSKWK\OPHWK\ONHWRQH
&2&+0H
0H&+&2&O 0H&+&2&O
8.
%)&+&O $O&O&+&O

VXEVWLWXWHGSURGXFW 0H&+²& 2
VXEVWLWXWHGSURGXFW

0H 0H
0H&+&2) >5HI@
%)&+&O
0H&+&2
2+ 2+ 2
2 20H 20H
$O&O
9. 2 >5HI@
20H 20H
2 2
DQWKUDTXLQRQHGHULYDWLYH
&25 &25
L1D+ 5&2&O 1D2++2
10.
1 LL3K62&O 1 RU 5&2 2 1 1 >5HI@
+ 623K 623K +
DF\ODWHGS\UUROH
11. Aliphatic and alicyclic compounds also undergo Friedel-Crafts reactions. In cases of acylation of olefins, silyl group
is usually incorporated into the substrate molecule to avoid strenuous reaction conditions. For example, acylation
of trialkyl-silylolefins under mild Friedel-Crafts conditions produce a,b-unsaturated ketones by replacement of the
trialkylsilyl group by the acyl moiety.
2+
6L0H &2&+
L&+&2&O$O&O
LL11D2+
0H 0H
Cyclohexene on reaction with crotonyl chloride yields the cyclopentenone derivative as one of the products, which
is an important precursor of terpenoids.
2 2
$O&O
&O &+&O
0H
Cyclododecene (cis and tram) reacts slowly with crotonyl bromide at –78°C to furnish a ketone that is an important
intermediate in the synthesis of (+/–)-muscone, a effective perfumery product.
2 2 2
$O&O
%U
0H 0H
± PXVFRQH
Friedel-Crafts alkylations are not restricted to the use of alkyl halides and aluminum chloride. Many other pairs of
reagents that form carbocations (or carbocation like species) may be used as well. These possibilities include the use of a
mixture of an alkene and an acid.
&+ &+
&
&+&+ &+
&
&

&
A mixture of an alcohol and an acid may also be used.
&
2+ %)
The Friedel-Crafts acylation reaction is an effective means of introducing an acyl group into an aromatic ring. The
reaction is often carried out by treating the aromatic compound with an acyl halide. Unless the aromatic compound is one
that is highly reactive, the reaction requires the addition of at least one equivalent of a Lewis acid (such as AlCl3) as well.
The product of the reaction is an aryl ketone.
2
2 &
$O&O &+
+& & H[FHVVEHQ]HQH
&
&O
DFHW\OFKORULGH $FHWRSKHQRQ
PHWK\OSKHQ\ONHWRQH
Acyl chlorides, also called acid chlorides, are easily prepared by treating carboxylic acids with thionyl chloride
(SOCl2) or phosphorus pentachloride (PCl5).
2 2
&
+ & & 62&O +& 62+&O
7KLRQ\OFKORULGH
2+ &O
DFHWLFDFLG DFHW\OFKORULGH
2 2
3&O 32&O+&O
2+ 3KRVSKRUXV &O
EHQ]RLFDFLG SHQWDFKORULGH EHQ]R\OFKORULGH
Friedel-Crafts acylations can also be carried out using carboxylic acid anhydrides. For example,
2 2
+ & & & 2
$O&O &+
2 H[FHVVEHQ]HQH +&
+ & & 2+
$FHWRSKHQRQH
2
DFHWLFDQK\GULGH
Limitations of Friedel-Crafts Reactions

Several restrictions limit the usefulness of Friedel-Crafts reactions.
1. When the carbocation formed from an alkyl halide, alkene, or alcohol can rearrange to a more stable carbocation, it
usually does so and the major product obtained from the reaction is usually the one from the more stable carbocation.
When benzene is alkylated with butyl bromide, for example, some of the developing butyl cations rearrange by a
hydride shift––some developing 1o carbocations (see following reactions) become more stable 2o carbocations. Then
benzene reacts with both kinds of carbocations to form both butylbenzene and sec-butyl-benzene:
$O&O &+ &+
+& %U +& +&

&+
+& +&
EXW\OEHQ]HQH VHFEXW\OEHQ]HQH
2. Friedel-Crafts reactions do not occur when powerful electron-withdrawing groups are present on the aromatic ring or
when the ring bears an –NH2, –NHR, or –NR2 group. The applies to alkylations and acylations.

2 2+ 2 5
12 1 &+
& & &) 62+ 1+
7KHVHGRQRWXQGHUJR)ULHGHO&UDIWVUHDFWLRQV
We shall learn that groups present on an aromatic ring can have large effect on the reactivity of the ring towards
electrophilic aromatic substitution. Electron-withdrawing groups make the ring less reactive by making it electron
deficient. Any substituent more electron withdrawing (or deactivating) than a halogen, that is, any meta-directing group,
makes an aromatic ring too electron deficient to undergo a Friedel-Crafts reaction. The amino groups, –NH2, –NHR,
and –NR2, are changed into powerful electron-withdrawing groups by the Lewis acids used to catalyze Friedel-Crafts
reactions. For example,
+
+ +
1 + 1 $O&O
$O&O
'RHVQRWXQGHUJRD)ULHGHO&UDIWVUHDFWLRQ
3. Aryl and vinylic halides cannot be used as the halide component because they do not form carbocations readily.
&O
$O&O 1R)ULHGHO&UDIWVUHDFWLRQ
1R)ULHGHO&UDIWVUHDFWLRQ
&+
&O
+ &
&+
4. Polyalkylations often occur. Alkyl groups are electron-releasing groups, and once one is introduced into the benzene
ring, it activates the ring toward further substitution.
&+ &+
+&
%)
&+2+ &
+&
,VRSURS\OEHQ]HQH
&+
SGLLVRSURS\OEHQ]HQH
Polyacylations are not a problem in Friedel-Crafts acylations, however the acyl group (RCO–) by itself is an electron-
withdrawing group, and when it forms a complex with AlCl3 in the last step of the reaction, it is made even more
electron withdrawing. This strongly inhibits further substitution and makes monoacylation easy.
5. Lewis acid catalysts can also effect dealkylation, i.e., the reaction is reversible. Thus ethylbenzene (22) with BF3 and
HF, is found to disproportionate:
(W (W (W
+)

%)

(W
This reaction must be intermolecular, but rearrangements involving change in the relative positions of substituents in
the benzene ring are also known, and these are found to be intramolecular. Thus heating p-dimethylbenzene (p-xylene,
23) with A1C13 and HC1 results in the conversion of the majority of it into the more stable (cf. p. 163) m-dimethyl-
benzene (m-xylene, 24). The presence of HC1 is essential, and the change is believed to involve migration of an Me
group in the initially protonated species (25):
0H + 0H
0H 0H

+ ±+
+
0H 0H 0H 0H

Apart from the possibility of rearrangement, the main drawback in the preparative use of this Friedel-Crafts reaction
is polyalkylation.
Synthetic Applications of Friedel-Crafts Acylations

Rearrangements of carbon chain do not occur in Friedel-Crafts acylations. The acylium ion, because it is stabilized by
resonance, is more stable than most other carbocations. Thus, there is no driving force for a rearrangement. Because
rearrangements do not occur, Friedel-Crafts acylations often give us much better routes to unbranched alkylbenzenes than
do Friedel-Crafts alkylations.
As an example, let us consider the problem of synthesizing propylbenzene. If we attempt this synthesis through a
Friedel-Crafts alkylation, a rearrangement occurs and the major product is isopropylbenzene.
&+ &+
%U $O&O
+ & +%U
LVRSURS\OEHQ]HQH
By contrast, the Friedel-Crafts acylation of benzene with propanoyl chloride produces a ketone with an unrearranged
carbon chain in excellent yield.
2
&O
+& $O&O +&O

2 &+
SURSDQR\OFKORULGH (WK\OSKHQ\ONHWRQH
]LQF
[Caution : As we shall discuss later, zinc and hydrochloric acid will also reduce nitro groups to amino groups.]
2
&+
=Q +J
&+ +&OUHIOX[
(WK\OSKHQ\ONHWRQH SURS\OEHQ]HQH
RU
2
=Q +J
$U
+&OUHIOX[
$U5 5 5
When cyclic anhydrides are used as one component, the Friedel-Crafts acylation provides a means of adding a new
ring to an aromatic compound.
&25 &+5
5&2&O 5HGXFWLRQ
$QK\G$O&O =Q +J +&O
2 2
$QG$O&O
&O±&±&O & +&O
3KRVJHQH EHQ]RSKHQRQH
Illustration
10. Why is PhNO2 a suitable solvent for the Friedel-Crafts alkylation of PhBr while benzene is not?
Ans. Benzene is more reactive than bromobenzene in the Friedel-Crafts reaction and would alkylate more rapidly.
Nitrobenzene may be used because it does not undergo the Friedel-Crafts reaction owing to the deactivating
effect of the NO2 group (CS2 can also be used).
1. Explain Friedel Crafts acylation requires on excess of the catalyst but Friedel-Crafts alkylation
requires only a catalytic amount.
2. During reaction of benzene with neopentyl chloride with benzene in the presence of AlCl3 the
major product is 2-methyl-2-phenylbutane and not neopentylbenzene. Explain
&+±&+ &+
3. $ Identify A and also the electrophile involved in the reaction.
+)RU%)
4. How will you synthesize
&+&+&+
from benzene?
5. Convert benzene to a-tetralone.
6. Which of the following is the major organic product of the following reaction?
+ &
$O&O
"
+ & &O
&+
+ & &+
&+ &+
(a) (b) &+ (c) (d)
&+ &+
SOLUTIONS
1. The product of acylation co-ordinates with the catalyst and removes the latter from the reactant side
and thereby stops further acylation. For this reason, Friedel-Crafts acylation requires an excess of
the catalyst. The product of alkylation does not co-ordinate with the catalyst. So, the catalyst can
form complex with the alkylating agent and the catalyst propagates the reaction.
2. The initially formed primary carbocation rearranges by methyl migration to form a more stable
tertiary carbocation which acts as a electrophile and attack the benzene to give the major product.
&+ &+
±
&+±&±&+±&O$O&O &+±&±&+$O&O
&+ &+
&+ FDUERFDWLRQ
&+±&±&+±&+
&+
&+±&±&+±&+

FDUERFDWLRQ PRUHVWDEOH
3.
+
&+±&+ &+ &+±&+±&+
&+±&+±&+
_

&+±&+±&+
$
(A) is iso propyl benzene or cumene and electrophile involved is CH3 – CH⊕ – CH3
(Isopropyl Carbocation). Rearrangements are also possible in Friedel Crafts, reactions when
benzene is treated with n-butyl chloride and Lewis acid the product obtained is isobutyl
benzene.
4.
2
2
$O&O &±&+&+
&+±&+±&±&O
=Q +J +&O
&OHPPHQVHQUHGXFWLRQ
&+±&+&+
If we would have tried to synthesize it using CH3CH2CH2Br then we would have got iso-
propylbenzene. Try to explain it.
5.
2
2
$O&O
2
2 2+
H[FHVV 6XFFLQLFDQK\GULGH 2
EHQ]R\OSURSDQRLFDFLG
2+ &O
62&O
2 & 2
SKHQ\OEXWDQRLFDFLG SKHQ\OEXWDQR\OFKORULGH
$O&O&6
2
Į7HWUDORQH
6. The product obtained by the more stable carbocation

∴ (b)
The presence of an electron-withdrawing substituent is generally sufficient to inhibit Friedel-Crafts alkylation; thus
nitrobenzene is often used as a solvent for the reaction because A1C13 dissolves readily in it, thus avoiding a heterogeneous
reaction.
HALOGENATION
In contrast to nitration, halogenation can involve a variety of different electrophiles in attack on the aromatic system.
The free halogens, e.g., C12 and Br2, will readily attack an activated nucleus such as phenol, but are unable to substitute
benzene itself (photochemical activation can lead to addition, however, through the agency of free halogen atoms) a Lewis
acid catalyst such as A1C13 is required to assist in polarising the attacking halogen molecule, thereby providing it with an
‘electrophilic end’; the energy required to form Cl⊕ is prohibitive. The rate equation found is often of the form:
Rate = k[Ar—H][Hal2][Lewis acid]
It seems likely that benzene forms a p complex (12) with, for example, Br2 (cf. p. 131), and that the Lewis acid then
interacts with this. The catalyst probably polarizes Br—Br, assists in the formation of a s bond between the bromine
molecule’s now electrophilic end and a ring carbon atom, and finally helps to remove the incipient bromide ion so as to
form a s complex (13):
%U²%U)H%U + %U %U
%U

)H%UՒ +%U)H%U

The anion FeBr4Θ assists in the removal of a proton from the s complex (13). At the same time this step regenerates
the catalyst FeBr3.
The Lewis acids most commonly used to effect chlorination and bromination reactions are FeCl3, FeBr3, and AlCl3 all
in the anhydrous form. Ferric chloride and ferric bromide are usually generated in the reaction mixture by adding iron to
it. The iron then reacts with halogen to produce the ferric halide:
2Fe + 3X2 ––→ 2FeX3
Order of Reactivity
F2 > Cl2 > Br2 > l2
The mechanism of the chlorination of benzene in the presence of ferric chloride is analogous to the one for bromination.
Ferric chloride serves the same purpose in aromatic chlorinations as ferric bromide does in aromatic brominations. It
assists in the generation and transfer of a positive halogen ion. The rate reaction found is often of the form:
Rate = K [Ar – H] [Hal2] [Lewis acid]
Hypo-halous acids (HO – Hal) in presence of strong acid also become a very powerful halogenating agent.

+2²+DO+ +2²+DO +2+DO
Fluorine reacts so rapidly with benzene that aromatic fluorination requires special conditions and special types of
apparatus. Even then, it is difficult to limit the reaction to monofluorination. Fluorobenzene can be made, however, by an
indirect method.
Iodine, on the other hand, is so unreactive that a special technique has to be used to effect direct iodination; the reaction
has to be carried out in the presence of an oxidizing agent such as nitric acid.
,
+12
,
Kinetic isotope effects have not been observed for chlorination, and only rarely for bromination, i.e., the reactions
normally follow pathway [2a] like nitration. In iodination, which only takes place with iodine itself on activated species,
kinetic isotope effects are the rule. This presumably arises because the reaction is readily reversible (unlike other halogena-
~
tions), loss of I occurring more often from the s complex (14) than loss of H, i.e., k–1 > k2:
2+ 2+ 2+
N N
, ,Ւ +,
N±
+ , ,

Thus kH/kD the iodination of phenol and 2,4,6-trideuteriophenoI is found to be ≈ 4, i.e., pathway [2b]. Iodination is often
assisted by the presence of bases or of oxidising agents, which remove HI and thus displace the above equilibrium to the
right. Oxidising agents also tend to produce I⊕, or a complex containing positively polarised iodine, from I2, thus provid-
δ+ δ− δ− δ−
ing a more effective electrophile. Halogenation may also be carried out by use of interhalogen compounds Br − Cl, I − Cl,
etc., attack occurring through the less electronegative halogen as this will constitute the ‘electrophilic’ end of the molecule.
The two species above are thus found to effect bromination and iodination, respectively.
7. Benzene on reaction with ICl in presence of anhydrous AlCl3 gives?
,
&O
(a) &O (b) , (c) (d) , &O
SOLUTION

7. When ICl is heated with AICI3 I+ A ICI4 complex formation is more farourable than
Cl+ AlCl3I complex. So iodiobenzene is formed.
∴ (b)
SULPHONATION
The mechanistic details of sulphonation have been less closely explored than those of nitration or halogenation. Benzene
itself is sulphonated fairly slowly by hot concentrated sulphuric acid, but rapidly by oleum (the rate then being related to
its SO3 content) or by SO3 in inert solvents. The nature of the actual electrophile depends on the conditions, but is probably
always SO3: either free or linked to a ‘carrier’, e.g., H2SO4.SO3 (H2S2O7) in sulphuric acid.
Fuming sulphuric acid is sulphuric acid that contains added sulphur trioxide (SO3). Sulphonation also takes place in
concentrated sulfuric acid alone, that more slowly.
2
2 2
6 +
2 6 &
FRQF+62 2
2
6XIIHUWULR[LGH %HQ]HQHVXOIRQLFDFLG
Step 1: A small concentration of SO3 is developed in H2SO4 itself through the equilibrium:

+62 62+2+62Ւ
When sulphur trioxide reacts with benzene the following steps occur.
2 + + +
VORZ 62± 62± 62±
Step 2: 6 2

2
$UHQLXP,RQ
+
62
62±
Step 3: +62 ± +62 )DVW

62 62+
Step 4: +2 )DVW
+ 2
All of the steps are equilibria, including step 1 in which sulphur trioxide is formed from sulfuric acid. This means that
the overall reaction is an equilibrium as well. In concentrated sulphuric acid, the overall equilibrium is the sum of steps 1–4.
62+
+62 +2
In fuming sulphuric acid, step 1 is unimportant because the dissolved sulphur trioxide reacts directly.
Because all of the steps are equilibria, the position of equilibrium can be influenced by the conditions we employ. If we
want to sulphonate benzene we use concentrated sulphuric acid or better yet fuming sulphuric acid. Under these conditions
the position of equilibrium lies appreciably to the right and we obtain benzenesulphonic acid in good yield.
On the other hand, we may want to remove a sulphonic acid group from a benzene ring. To do this, we employ dilute
sulphuric acid and usually pass steam through the mixture. Under these conditions with a high concentration of water the
equilibrium lies appreciably to the left and desulphonation occurs. The equilibrium is shifted even further to the left with
volatile aromatic compounds because the aromatic compound distills with the steam.
Sulphonation, like iodination, is reversible and is believed to take place in concentrated sulphuric acid via the pathway:
+ 62Ւ 62Ւ 62+
N N
62 +
N± IDVW

PROTONATION
Although benzene is a very weak base, it is protonated in concentrated sulphuric acid to a very slight extent. This reaction
can be detected if the protonating mixture contains deuterium or tritium, the isotopes of hydrogen, since isotope exchange
takes place. Some deuteriated benzene is produced when benzene is treated with D2SO4, and this can be detected by mass
spectrometry and NMR spectroscopy. The more deuterium there is in the protonation mixture, the more exchange occurs.
Notice that the regeneration of the aromatic system occurs by elimination of a proton.
+ '
'
'
+
Gattermann’s Koch. Reaction
&+2
DQK\G
&2+&O +&O
=Q&O
The mechanism of this reaction is uncertain, but probably the formyl cation (HC⊕ = O) is the active electrophilic species.
+±& 2
& 2+ +±& 2 +

IRUP\OFDUERQLXPLRQ
Gattermann’s Aldehyde Synthesis

&+ 1+
DQK\G
+&1+&O =Q&O +&O
+2+
&+2
1+
This reaction is electrophilic aromatic substitution reaction and proceeds as follows:

&O +
$O&O
+±&Ł1+&O +±& 1+ +1 &&O$O&O
LPLGRIRUP\O&KORULGH į į±
*
+& 1+&O±
*
&+2 &+ 1+
* +2+ +&O
+±1±+
+
CHLOROMETHYLATION
Certain other reactions of aromatic nucleus are related to the Friedel-Crafts reaction. The introduction of a chloromethyl
group is effected by HCl and ZnCl2.
&+&O
+&+2+&O
=Q&O
%HQ]HQH &KORURPHWK\O
%HQ]HQH
Like iodination, sulphonation exhibits a kinetic isotope effect, indicating that C—H bond-breaking is involved in the
~
rate-limiting step of the reaction, i.e., that k –1 > k2.
Practical is made of the reversibility of the reaction in order to replace SO3H by H on treating sulphonic acids with
steam.��
Sulphonation and desulphonation reactions are often used in synthetic work. We may, for example, introduce a sul-
phonic acid group into a benzene ring to influence the course of some further reaction. Later, we may remove the sulphonic
acid group by desulphonation.
Illustrations
11. (a) Show the formation of the electrophile in the following reactions:
(i) Cl2 + AlCl3, (ii) HNO3 + H2SO4, (iii) Br2 + Fe, (iv) H2SO4, and (v) H2S2O7 (HOSO2OSO2OH, pyrosulphuric
acid, often called ‛fuming’ sulphuric acid or ‛oleum’), (b) Identify each base.
Ans. (a) (i) Cl2AlCl3 → [Clδ+---Cl---δ-AlCl3]
(ii) HONO2 + H:OSO3H [H2ONO2]+ H2O + NO2+ (nitronium ion)
(iii) 3Br2 + 2Fe → 2FeBr3; Br2 + FeBr3 → [Brδ+ Br---Bδ– ---FeBr3]
(iv) 2H2SO4 → H3O+ + HSO4– + SO3
(v) HOSO2OSO2OH → H+ + HSO4– + SO3
(b) (i) AlCl4– (ii) HOSO2O– (From Protonation of H2O by a second H2SO4), (iii) FEBr4–, (iv) and (v) HOSO2O–.
12. Discuss the essential role of the catalysts used for aromatic electrophilic substitutions.
Ans. The catalyst makes the reagent more electrophilic, thereby raising the HGS, lessening the DH of TS1; and enabling
the substitution to proceed at a faster rate. The catalyst plays this role by either actually forming the electrophile
as in (ii) and (iv) of Problem 10 or by polarizing the reagent as in (i) and (iii) of Problem 10.
13. Write an equation for each of following reactions and identify the electophile (E) and base (B) for each: (a) HOCl
+ H+, (b) HNO3, (c) ICl + ZnCl2, (d) HOMO + H+.
Ans. (a) HOCl + H+ → H2 OCl+ → Cl+ (E) + H2O (B)
(b) 2HONO2 → NO3– + H2ONO+2 → NO+2 (E) + H2O (B)
(c) 2I – Cl + ZnCl2 → 2I+ (E) + ZnCl2–
4
(B) (I+ is more stable than Cl+.)
(d) HONO + H+ → H2ONO → NO+ (E) + H2O (B)
14. (a) Some of the evidence for the existence of NO2+ [(ii) of Problem —10] is the four-fold depression of freezing
point of H2SO4 G' = 4, where is the number of particles formed according to the balanced equation). Give
equations to illustrate this fact, (b) Can nitronium ion be isolated?
Ans. (a) 1. HONO2 + H2SO4 ⇌ [H2 ONO2]+ + HSO4–
2. [H2ONO2]+ ⇌ H2O + NO+2
3. H2O + H2SO4 ⇌ H3O+ + HSO+4
Summation: HNO3 + 2H2SO4 → NO2+ + H3O+ + 2HSO4– (four particles, i = 4).
(b) Salts such as nitronium perchlorate, NO2+ClO4– and tetrafluoroborate, NO2+BF4 have been isolated and can be
used for aromatic nitrations.
15. (a) Provide an enthalpy diagram for the reversible aromatic sulphonation: (b) Would you expect this reaction to
show a moderate kH/kD isotope effect? (c) Which experimental conditions encourage desulphonation (reverse of
sulphonation)?
Ans. (a) See Figure. In halogenation, nitration, and other irreversible electrophilic substitutions, DH for formation of
the s complex is considerably greater than for its expulsion of H+, k2 >> k–1. sulphonation, DH for loss of SO3 is
only slightly greater than for loss of H+ and k2 is slightly greater than k-1.
+
N N
$U+62 $U $U62+
N±
62
Therefore the s complex can react about equally well in either direction and sulphonation is reversible.
76
76
VXOIRQDWLRQ GHVXOIRQDWLRQ
(QWKDOS\
+
$U ±
62
$U+62 ±
$U62 +
3URJUHVVRI5HDFWLRQ
(b) Yes because k2 affects the overall rate. The loss of D+ from the deuterated a-complex has a great-
er DH than the comparable loss of H, is slower, and sulphonation exhibits a moderate primary isotope
effect.
(c) The equilibrium may be shifted toward desulphonation by employing hot dilute aq. H2SO4.
16. (a) Account for the following differences in the primary kinetic isotope effect: kH/kD ≅ kH/kT ≅ 10–20, where T is
tritium, H. (b) With the aid of an enthalpy diagram compare the rates of the following reactions and explain the
difference.
(1) C6D6 + H2SO4 C6D5SO3H + DOH
(2) C6T6 + H2SO4 C6T5SO3H + TOH (Use a dashed line for this reaction.)
Ans. (a) Isotope effects are attributed solely to mass differences, which are manifested in the vibrational frequencies
of the C—H, C—D, and C—T bonds. The greater the mass of the isotope whose bond is broken in the rate-
controlling step, the greater is the primary isotope effect. Since the mass of T is greater than the mass of D, kH/kr
> kH/k0.
(b) See Figure. The pathway leading to the two intermediates are practically identical for both reac-
tions because there are no bonds broken. The second step involves breaking a C — D or C—T bond,
and has a lower H* than the reversal of step 1 that involves breaking a C—S bond. Furthermore, H*
for breaking the C—T bond is more than for breaking the C — D bond. Reaction (2) is slower than
reaction (1).
76 76
(QWKDOS\
,QWHUPHGLDWHV
*V¶V 3URGXFWV
3URJUHVVRI5HDFWLRQ
Note that the presence of D or T has very little effect on the enthalpies of the ground states, transition states for
the first step, intermediates, and products.
17. Typically I2 gives purple solutions with nonpolar s-bonded solvents such as cyclohexane. Yet its benzene solution
is brown and only unreacted benzene is isolated from it with no iodobenzene. (a) Discuss the chemical difference
in the two kinds of solutions, (b) Give a MO explanation for the structure formed in benzene, (c) What is the role
of these types of structures in aromatic halogenations? Illustrate with Br2.
Ans. (a) The purple color in cyclohexane is typical for I2 molecules. (Recall I2 vapor is also purple.) In benzene, I2
molecules form brown - colored p complexes (charge-transfer complexes) . These are similar
to those formed from halogens and alkenes.
,
,
ʌFRPSOH[ FKDUJHWUDQVIHUFRPSOH[
Since no s bonds are formed, the recovered benzene is unchanged.

The name ‘charge-transfer’ indicates electron transfer from the electron-rich it system of the arene (the do-
nor) to the electrophilic I2 (the acceptor). For this to happen the donor HOMO must have a low ionization
potential (be ‘high-lying’) and the acceptor must have a ‘low-lying’ LUMO. Because of the e– transfer from
HOMO to LUMO, the tt complex is a radical anion. The orbital picture has a pAO of an I of I2 overlapping
with the p cloud of PhH without being attached to any one ring C.
(c) The p complex of PhH and Br2 precedes the a complex. It is likely that FeBr3 then removes the Br– from
the p complex which in turn collapses in the rate-determining step to the complex.
į±%U±±±)H%U
į%U +
%U
±
)H%U
ʌFRPSOH[ZLWK%U Â )H%U ıFRPSOH[
18. (a) Identify the electrophile formed from the reaction of CH3CH2Cl + AlCl3. (b) Show how a comparable
electrophile can be formed from each of the following: (i) CH2=CH2 and (ii) CH3CH2OH. (c) Show the reaction
of benzene with the electrophile in (a), (d) What is the product of the reaction of benzene with the electrophiles
in (b)? (e) Why is HF and not HBr used with CH2=CH2?
Ans. (a) The incipient CH3CH+2 from CH3CH2δ+----Cl---δ–AlCl3.

(b) (i) add conc. H2SO4 or HF; CH3CH2δ+---δ–OSO3H or +&²²&+ )± (ii) add BF3, conc.
+
H2SO4, or H3PO4; &+&+ 2 %) .
į į±

+
In this Friedel-Crafts alkylation benzene displaces [ClAlCl3]– from the electrophilic Cd+ to give the a-complex.
Subsequent ejection of H+ results in formation of HAlCl4 and ethylbenzene,
&+&+ + &+&+
(W&O ±
3K+ $O&O
$O&O +$O&O +&O$O&O
ıFRPSOH[
(e) The proton donor must afford a weak nucleophile (F–); a stronger nucleophile like Br– would add to the
protonated alkene, forming CH3CH2Br and preventing reaction of the alkene with benzene.
19. (a) Compare the products of the reaction of benzene with i-PrCl and n-PrCl in AlCl3. (b) Account for the products
mechanistically.
Ans. (a) The expected Ph —CHMe2 is isolated from the reaction with i-PrCl. With n-PrCl, both Ph—CH2CH2CH3 and
Ph—CHMe2 form, (b) 1° RX’s are less reactive than 2° and 3° halides. At the higher temperatures required for
1° RX, some rearrangement always occurs. A possible pathway is for benzene to displace on the 2 °C while a : H
shifts to the 1° carbon:
±
3K+&+±&+±&+į

±±±&O±±±į±$O&O 3K±&+0H$O&O+
+
Formation of a ‛free’ 1° carbocation is unlikely. Rearrangement limits the scope of this reaction.
20. (a) Give the product of the reaction of benzene and AlCl3 with (i) CH3CH2CH2COCl, an acyl chloride, and
(ii) (CH3CH2CH2CO)2O, an acid anhydride, (b) What is the electrophile? Show contributing resonance structures,
(c) Why is the product in (a) not rearranged? (d) How can we use the acylation to synthesize unrearranged alkyl
side chains on an aromatic ring? Illustrate by preparing Ph(CH2)3CH3.
Ans. (a) (i) and (ii) PhCOCH2CH2CH3

(b) 5&2&O$O&O 5±&Ł2 5±& 2 $O&O
±
DQDF\OLXPLRQ
$ %
A is the main contributing resonance structure for the acylium ion (the electrophile) because both C and O have
an octet. The anhydride gives the same acylium ion and [AlCl3OAc]-.
(c) The acylium ion is much more stable than any alkyl carbocation and so it cannot rearrange to a more stable
cation.
(d) The ketone prepared in (a) is reduced to the hydrocarbon:
PhCOCH 2 CH 2 CH 3 
Zn/Hg, HCI ( Clemmensen )
or H NNH , OH - (Wolff -Kishner )
→ PhCH 2 CH 2 CH 2 CH 3 .
2 2
21. Compare the Friedel-Crafts alkylation with RX and acylation with RCOX as to the (a) mechanism, and (b) kind
and amount of catalyst.
Ans. (a) Alkylation, see Problem 17(c). Acylation:
į±
5&2 +&O²$O&O
2
3K±+5±&Ł2 3K&5+$O&O
(b) Both require a Lewis acid of the type MXn, most commonly AlCI3, but also BF3, FeO3, ZnCl2. In acylation, a
1:1 complex of RCOCl and catalyst forms, which then dissociates into the acylium ion:
2
į±
±
5²&±±±&O±±±$O&O 5²&ŁŁ2$O&O
į
Acylations require more than one equivalent of catalyst because the ketonic product also complexes with
AlCl,:
į į±
2 ±±± $O&O
&
3K 5
22. How is the ketonic product of the Friedel-Crafts acylation isolated from the reaction mixture?
Ans. Dilute aq. HCl is added to decompose the complex and dissolve the Al salts. The ketone is soluble in the organic
layer, from which it is isolated by distillation or crystallization.
23. Supply structures for the products of the reaction of benzene with (a) CH,CH=CH2 (HF, 0°C) (b) cyclohexanol
(BF3, 60°C), (c) [Me2CHCO]2O (AlCl3), and (d) CH2=CHCH2Cl (ZnCl2).
Ans.
(a) PhCH(CH3)2 (b) 3K
+
2
(c) 3K²&²&+0H (d) PhCH2CH = CH2

24. Give the product of reaction of benzene with ethylene oxide/AlCl3.

į į±
2 2±±±$O&O
3K+
Ans. $O&O&+±&+ &+±&+ 3K&+&+2+$O&O
25. Benzene reacts with covalent mercuric acetate [Hg(OCOCH3)2] and HClO4 to form PhHgOCOCH3. (a) Give a
mechanism for this electrophilic substitution, (b) Explain that kH/kD = 6.
Ans. (a) Step1. Formation of electrophile:
2 2 2
2+ 2
+
&+&2²+J²2&&+ &+&2²+J²2&&+ &+&2+J ( &+&22+
Step 2. Electrophilic substitution:

+
VORZ
3K++J2&2&+ 3K 3K+J2&2&++
+J2&2&+
Thallium (Problem 11.27) may also be introduced into the aromatic ring by this method,
(b) A C — H bond is broken in the rate-determining step 2.
26. (a) Why cannot benzene be iodinated with I2 directly? (b) Show how benzene can be iodinated with I2.
Ans. (a) Iodination with I2 is slow (F2 > Cl2 > Br2 > I2) and somewhat reversible (DH = 12 kcal/mol). (b) HNO3 affects
the reaction by oxidizing I2 to a more powerful electrophile, hydrated I+.
1 +
1. →  δ + I − − − δ + OH 2  + NO 2
I 2 + 2H + + NO3− 
2 electrophile
+ ,
±+2 +2
2. 3K+>,±±±2+@ 3K 3K,+2
The electrophilic HOd —Id+ is formed when H2O2 is the oxidant. In direct iodination I– would be a product , and
its presence could reverse the reaction. An oxidizing agent converts I– to I2.
27. Explain why iodination of an arene occurs with ICl.
Ans. ICl is more electrophilic than I2 because it is polarized; i.e., d+I — Cld-. The aromatic ring more easily displaces
Cl– from d+l then it displaces I– from the nonpolar I — I.
28. Why cannot fluoroarenes be prepared by direct reaction of F2? (b) How may fluorobenzene be prepared by
thallation? (Hint: see Problem 24.) Indicate the electrophile.
Ans. (a) Fluorine is too reactive. Both addition and polysubstitution occur.
(b) Tl(OCOCF3)3 is reacted with benzene, followed by addition of KF and BF3.
7O 2&2&)
7O 2&2&) ( &)&22±
±+ .)%)
3K+7O 2&2&)
3K7O 2&2&)
3K)
8. How are the following conversions achieved?
& + &+
(a) C6H5C2H5 —→ C6H6 (b) (c)
& + &+
2+ /L
(d) (e)
SOLUTION
&+ 2 2+
.0Q2 6RGDOLPH
8. (a) '
&+
%)
(b) &+2+
&+
&+ &+ &+ &+ &+

%U
&+, %U 6HSDUDWH &+%U
(c)
$O&O )H 1D &+ 2
%U %U &+
2
&O &1
&+ 2+
&+, &O .&1 +2+

(d) $O&O 6XQOLJKW
%U /L
(e) /L%U
)H
%U /L
REACTIVITY AND ORIENTATION IN ELECTROPHILIC AROMATIC SUBSTITUTION

In benzene, the six hydrogen atoms are chemically equivalent and an electrophilic attack would give rise to a single prod-
uct only. But if a group is already present on the ring, the hydrogens become non-equivalent and the incoming electrophile
can attack either the ortho, meta or para positions to yield a mixture of products. It is believed that electrophiles have a
tendency to attack a position of high electron density. The substituent can thus cause compound to react faster or slower
than benzene itself.
Two experimental observations illustrate that the behaviour is quite varied. The rate of nitration of toluene is appre-
ciably faster than that of benzene and produces a mixture of 2- and 4-nitrotoluenes. On the other hand, the nitration of
nitrobenzene is more difficult than that of benzene and gives just one product 1,3-dinitrobenzene.
12 12
12
+12 +12

+62 +62
12
12
A substituent in a benzene ring, therefore, influences the course of electrophilic substitution in two ways:
• It affects the reactivity of the molecule.
• It controls the orientation of attack, that is, it controls which isomer is formed.
The orientation and reactivity effects of each group are explained on the basis of resonance and field effects on the
stability of the intermediate arenium ion. It is important to understand why this should happen. In the examples given
earlier, the two substituents, the methyl group and the nitro group, exhibit different electronic behaviour. The methyl group
is an electron donor and so increases the electron density of the ring. The nitro group is an electron acceptor and withdraws
electron density from the ring.
These properties influence the course of the reactions of aromatic compounds with electrophiles. An electron-releasing
group increases the electron density of the benzene ring, promoting electrophilic attack. Such substituents are known as
activating groups. An electron-withdrawing group is deactivating and reduces the electron density of the ring, making at-
tack by the electron-deficient reagent more difficult.
Both types of substituents affect the electron density at all positions of the ring, but exert their greatest effects at the
ortho and para positions, making these sites the most electron rich in the case of donor groups and most electron-deficient
when electron-withdrawing groups are present. Donor groups therefore direct attack of the electrophile to the ortho
and para positions and are known as ortho/para directors (for example, CH3, OH, OR, NH2, NR^ NHCOCH3, X, etc).
Conversely, aromatic compounds containing electron acceptor groups are attacked at the meta position, as this is the least
electron-deficient site. Such groups are called meta directors for example, +NR3, NO2, CHO, RCO, CO2H, CO2R, SO3H,
CN, CF3, etc). Not all substituents fit exactly into this picture: halogens are deactivating but direct attack to the ortho and
para positions.
• Electron-donating substituents activate the benzene ring to electrophilic attack, which results in the formation of the
ortho- and para-disubstituted benzene derivatives.
• Electron-withdrawing substituents deactivate the ring at ortho and meta positions to attack by electrophiles, which
occurs at the meta-position.
Substituents exert their influence on a molecule through either the s-bonds or the p-bonding system, in other words,
by inductive and mesomeric (resonance) effects, respectively. The interaction influences both the electron density at the
various ring positions and stability of the intermediate carbocation. The outcome can be understood by superimposing the
electronic effects of the substituents on the slow, rate-determining step of the aromatic substitution discussed above.
In a s-bond between two atoms of differing electronegativities, there is an unequal sharing of the electron-pair,
with the electrons being attracted towards the more electronegative atom. This causes a permanent polarization of
the molecule. This influence of an atom or group on the distribution of the electron-pair is called the inductive effect.
Inductive effects rapidly die away along a saturated carbon chain. Substituents in an aromatic ring that withdraw electrons
in this way exert a –I effect. They include not only halogens, the hydroxyl and nitro groups, where an electronegative
atom is attached to the ring, but also groups such as carbonyl and nitrile, in which an electron-deficient carbon atom is
bonded to the ring. Alkyl groups behave in the opposite manner, exerting a +I effect and releasing electron-density to
the ring.
The mesomeric effect is the analogous redistribution of electrons in p-bonds. However, this resonance effect is
transmitted throughout the whole of a conjugated system and creates alternate polarity at the carbon atoms along the
system. Substituents that withdraw electron density in this way (–M groups) include carbonyl and nitro groups, whilst
electron-releasing (+M) functions include amino and hydroxy groups.
Note that some groups can withdraw electrons by one of the two effects but release electrons by the other, although
one of the effects usually predominates. Fluorine has a weaker +M and –I effect than oxygen. Both the +M and –I effects
of the halogens fall in the order, F > Cl > Br > I, and the resultant effect leads to the order, F ~ H > Cl ~ Br ~ I. The ortho
positions of all four halobenzenes are less reactive than the para positions and the meta positions are strongly deactivated.
Inductive and Resonance Effect: Theory of Orientation

We can account for the electron-withdrawing and electron-releasing properties of a group on the basis of two factors:
inductive effect and resonance effects. We shall also see that these two factors determine orientation in aromatic substitution
reactions.
The inductive effect of a substituent S arises from the electrostatic interaction of the polarized S to ring bond with
the developing positive charge in the ring as it is attacked by an electrophile. If, for example, S is a more electronegative
atom (or group) than carbon, then the ring will be at the end of the dipole:
į
į±
6 HJ6 )&ORU%U
Attack by an electrophile will be retarded because this will lead to an additional full positive charge on the ring. The
halogens are all more electronegative than carbon and exert an electron-withdrawing inductive effect. Other groups have
an electron-withdrawing inductive effect because the atom directly attached to the ring bears a full or partial positive
charge. Examples are the following:
;į
2±
2
15 5DON\ORU+ &į ;į 1 6²2+
2±
2
;į
2 2
&²* &²* * +52+RU25

(OHFURQZLWKGUDZLQJJURXSVZLWKDIXOORUSDUWLDO
FKDUJHRQWKHDWRPDWWDFKHGWRWKHULQJ
Then resonance effect of a substituent S refers to the possibility that the presence of S may increase or decrease
the resonance stabilization of the intermediate arenium ion. The S substituent may, for example, cause one of the three
contributors to the resonance hybrid for the arenium ion to the better or worse than the case when S is hydrogen. Moreover,
when S is an atom bearing one or more nonbonding electron pairs, it may lend extra stability to the arenium ion by
providing a fourth resonance contributor in which the positive charge resides on S.
( (
6 6
+ +
This electron-donating resonance effect applies with decreasing strength in the following order:
0RVWHOHFWURQV ²1+²15!²2+²25!²; /HDVWHOHFWURQV
This is also the order of the activating ability of these groups. Amino groups are highly, activating, hydroxyl and
alkoxyl groups are somewhat less activating, and halogen substituents are weakly deactivating. When X = F, this order
can be related to the electronegativity of the atoms with the nonbonding pair. The more electronegative the atom is the less
able it is to accept the positive charge (fluorine is the most electronegative, nitrogen the least). When X = Cl, Br, or I, the
relatively poor electron-donating ability of the halogens by resonance is understandable on a different basis. These atoms
(Cl, Br, and I) are all larger than carbon and, therefore, the orbitals that contain the nonbonding pairs are further from the
nucleus and do not overlap well with the 2p orbital of carbon. (This is a general phenomenon: resonance effects are not
transmitted well between atoms of different rows in the periodic table.)
Activating Groups: Ortho-Para Directors

The methyl group in an activating group is an ortho-para director. Toluene reacts considerably faster than benzene in all
electrophilic substitutions.
&+
$QDFWLYDWLQJJURXS
0RUHUHDFWLYHWKDQEHQ]HQH
WRZDUGHOHFWURSKLOLFVXEVWLWXWLRQ
We observe the greater reactivity of toluene in several ways. We find, for example, that with toluene, milder conditions
––lower temperatures and lower concentrations of the electrophile—can be used in electrophilic substitutions than with
benzene. We also find that under the same conditions, toluene reacts faster than benzene. In nitration, for example, toluene
reacts 25 times as fast as benzene.
We find, moreover, that when toluene undergoes electrophilic substitution, most of the substitution takes place at its
ortho and para positions. When we nitrate toluene with nitric and sulfuric acids, we get mononitrotoluenes in the following
relative proportions.
RUWKR SDUD PHWD
&+ &+ &+ &+
12
+12

+62
12
RQLWUREHQ]HQH
12 PQLWURWROXHQH
SQLWUREHQ]HQH
Of the mononitrotoluenes obtained from the reaction, 96% (59% + 37%) has the nitro group in an ortho or para posi-
tion. Only 4% has the nitro group in a meta position.
Predominant substitution at the ortho and para positions of toluene is not restricted to nitration reactions. The same
behavior is observed in halogenation, sulphonation, and so forth.
All alkyl groups are activating groups, and they are all also ortho-para directors. The methoxy group, CH3O–, and the
acetamido group, CH3CONH–, are strong activating groups and both are ortho-para directors.
The hydroxyl group and the amino group are very powerful activating groups and are also powerful ortho-para
directors. Phenol and aniline react with bromine in water (no catalyst is required) to produce products in which both of the
ortho positions and the para position are substituted. These tribromo products are obtained in nearly quantitative yield.
2+ 2+
%U %U
%U
+ 2
%U
WULEURPRSKHQRO
1+ 1+
%U %U
%U
+ 2
%U
WULEURPRDQLOLQH
Group donating electrons by mesomeric effect

Groups in which the atom attached to the benzene ring possesses a lone pair of electrons can interact with the aromatic
ring, promoting ortho and para attack. The ring becomes more electron rich and, so, the reaction with electrophiles is
facilitated.
In order to assess the influence that substituents have on the reactivity of aromatic molecules, it is important to consider
their effects not only on the benzene ring itself, but also on the carbocation intermediates resulting from electrophilic
attack. These species are relatively unstable and any feature that affects their stability will influence their ease of formation,
and, therefore, the outcome of a reaction. We can illustrate the latter point by examining the attack by an electrophile E+
on methoxybenzene (anisole) at the three possible sites of attack.

20H 20H 20H 20H
+ + + +

( ( ( (

, ,,
RUWKR
DWWDFN
20H 20H 20H 20H
(
PHWD
DWWDFN + + +
( ( (

SDUD
DWWDFN
20H 20H 20H 20H

+ ( + ( + ( + (
,,, ,9
Consider first the attack at the ortho position. Structure I has a positive charge located on the carbon atom to which
the methoxy group is bonded. Notice that this is a tertiary carbocation, a species that is recognized as being particularly
stable (remember nucleophilic aliphatic substitution reactions). An additional canonical structure can be drawn, involving
donation of the lone pair of electrons on the oxygen atom to the electron-deficient C+. This fourth canonical form confers
extra stability on the intermediate and lowers the energy of the transition state leading to it. An oxonium species such as II
is more stable than a carbocation, for example, I, and, hence, can be considered to contribute more to the resonance hybrid.
A similar situation arises with species III associated with attack at the 4-position, and this carbocation intermediate,
therefore, is also additionally stabilized by IV. However, no such structure can be drawn following meta attack and so the
cation derived from this mode of attack is not additionally stabilized.
A similar situation arises with species III associated with attack at the 4-position, and this carbocation intermediate,
therefore, is also additionally stabilized by IV. However, no such structure can be drawn following meta attack and so the
cation derived from this mode of attack is not additionally stabilized.
The consequences of the involvement of the methoxy group are to stabilize especially the carbocations arising from
ortho and para attack and to lower the energy of activation for their formation. Notice that even attack at the meta position
has lower activation energy than does benzene.
It should, therefore, be no surprise that the nitration of methoxybenzene is easier and faster than that of benzene and
yields essentially only the 1,2- and 1,4-isomers (in almost equal amounts). Less than 1 per cent of 3-nitroanisole is formed.
Other electrophilic reactions follow this pattern. Hydroxy and amino groups behave like a methoxy group. Phenoxides, in
which the oxygen carries a full negative charge, are especially activated towards electrophilic attack.
The negative end of the dipole of chlorobenzene is on the chlorine atom, whereas in methoxybenzene, the oxygen atom
is the positive end of the dipole, supporting the view that overall a halogen is an electron-withdrawing substituent.
Halogen atoms also fall into this category. Possessing a lone pair of electrons, they are able to stabilize the intermedi-
ate cation arising from ortho/para attack. However, the halogenobenzenes behave differently from methoxybenzene and
aniline in that the reaction with electrophiles is slower than for benzene. The nitration of chlorobenzene is about 30 times
slower than that of benzene. Halogens are weakly deactivating substituents and yet are ortho/para directors. The halogens
withdraw electrons inductively more strongly than they donate electrons by the mesomeric effect, with the result that
the three intermediates from ortho, meta and para attack are all less stable than that arising from electrophilic attack of
benzene. Nonetheless, ortho/para attack is still favoured because of the additional stabilization of the cations from the
resonance forms.
SDUDDWWDFN RUWKRDWWDFN
&O &O &O &O
( (

+ +
+ ( + (
Benzene reacts with bromine in the presence of catalysts only, while phenol reacts rapidly without a catalyst with
bromine to give a white precipitate of 2,4,6-(tribromophenol. The difference in reactivity is due to the enol nature of
phenol.
2+ 2+
%U %U
%U
(W2++2
%U
The phenoxide ion is even more reactive towards electrophilic attack than phenol. It reacts with weak electrophiles as
carbon dioxide. This reaction, known as the Kolbe-Schmidt process, is used industrially to prepare salicylic acid, precursor
in making aspirin.
2Ւ 1D 1D 2+ 1D

2+ 2 2Ւ 2+ 2&2&+
2 &2Ւ &2+ &2+
2
1D2+ + +
&
2 VDOLF\OLFDFLG DVSLULQ
Groups donating electrons by inductive effect

It is well known that, in comparison to hydrogen, alkyl groups donate electrons. It is therefore to be expected that toluene
and other alkyl benzenes will react with electrophiles rather more easily than benzene. This is certainly the case, with
toluene reacting with mixed acid at room temperature.
The canonical forms that contribute to the structure of the intermediate carbocation are shown here. Once again, one
contributing form derived from attack at the 2- and the 4-positions has the positive charge located on the carbon atom to
which the substituent is attached. It is noted that these structures. IX and X, are tertiary carbocations and that they are further
stabilized by delocalization of the charge onto the methyl group, which, therefore, shares some of the electron deficiency.
No such benefit results from attack at the 3-position, which is therefore not a favoured site for reaction. Nitration of toluene
occurs about 25 times faster than that of benzene under similar conditions. It leads to a 2:1 mixture of 2- and 4-nitrotoluenes;
only about 5 per cent of the product is the 3-isomer (remember there are two ortho positions but only one para position).
&+ &+ &+
+ + +

( ( (

RUWKR
DWWDFN ,;
&+ &+ &+
(
PHWD
DWWDFN + + +
SDUD ( ( (

DWWDFN
&+ &+ &+

+ ( + ( + (
;
The more efficient the alkyl group is at releasing electrons, the greater is the stabilization of the intermediate carboca-
tion and the rate of electrophilic attack. Thus, tert-butylbenzene is nitrated faster than toluene.
&+ &+ &+ &+

12
+12+62

&
12
12

This picture is somewhat generalized, since there are some exceptions. For instance, the chlorination of toluene
proceeds faster than that of tert-butylbenzene. Hyperconjugation is at a maximum for a methyl group and has been offered
as an explanation for these anomalies. (Hyperconjugation is stabilizing interaction between a C–H bond and an adjacent
s-bond). For example, propene may be regarded as a resonance hybrid of two canonical forms. The stability of carbocations
increases along the series. The increasing number of electron-releasing methyl groups attached to the carbocation centre
helps to spread the positive charge more effectively.
Deactivating Groups: Meta Directors

The nitro group is a very strong deactivating group. Nitrobenzene undergoes nitration at a rate only 10–4 times that of
benzene. The nitro group is a meta director. When nitrobenzene is nitrated with nitric acid sulfuric acids, 93 per cent of the
substitution occurs at the meta position.
12 12 12 12

12
+12

+62
12

12

The carboxyl group (–CO2H), the sulfo group (–SO3H), and the trifluoromethyl group (–CF3) are also deactivating
groups; they are also meta directors.
Groups withdrawing electrons by mesomeric effect
Substituents that fall into this category include NO2, CO2R, COR, CN and SO3R. All are characterized by the atom attached
to the ring being linked to a more electronegative atom by a multiple bond, and may be represented by X=Y, where Y is
more electronegative than X. Electrons are therefore attracted towards Y, making X more electron-deficient and, therefore,
more strongly electron-withdrawing. Formally, a positive charge is placed on the ortho and para positions.
< <± <± <± <± <

; ; ; ; ; ;

The following substituents decrease the stability of the intermediate arenium ion and thus are deactivating substituents.
6 2
2 2 2 2
2+ ±&Ł1 ±&) ±1 ±15
1+ 25 5 + 2±
6
LQFUHDVLQJGHDFWLYDWLRQ
Electrophilic attack on compounds, which contain a substituent that withdraws electrons from the ring, always leads to
the 3-substituted compound, with very little yield of the 2- and 4-isomers being formed. The reaction is more difficult than
for benzene, in keeping with the reduced electron density at the ring carbon atoms.
2 2±
12 12 1
+ + +

( ( (

2 2± 9
1 RUWKR
DWWDFN 12 12 12
(
PHWD
DWWDFN + + +
( ( (
SDUD
DWWDFN 2 2±
12 1 12

+ ( + ( + (
9,
Again, it is important to examine the intermediates formed by attack of an electrophile, E+, at the ortho, meta and para
positions. This time, nitrobenzene will be used as the substrate. It should be noticed that in the structures V and VI, associ-
ated with ortho and para attack, a positive charge is placed on the carbon to which the substituent is attached. The resulting
situation is destabilizing because positive charges are located on adjacent atoms.
While attack at the 3-position is still much slower than for benzene, no canonical form places positive charges on adja-
cent atoms, and so the intermediate is less destabilized than those arising from ortho and para attack. Hence, meta attack is
the preferred reaction. For example, nitration of nitrobenzene gives 88 per cent of 1,3-dinitrobenzene and only 8 per cent
and 1 per cent of the 1,2- and 1,4-isomers, respectively. The reaction occurs at a relative rate of 6 × 108 to that of benzene.
12 12 &+ &+
12
+12+62

&
12
12

Groups withdrawing electrons by inductive effect

Withdrawal of electrons through a s bond is called inductive electron withdrawal. Groups such as trifluoromethyl (CF3),
trialkylammonium (R3N+), PMe3+ and AsMe3+ are unable to interact with the p-system, but withdraw electrons as a result
of the electronegativity of the fluorine atoms and the positively charged nitrogen, phosphorus and arsenic, respectively. A
study of the canonical forms for electrophilic attack at the three sites indicates a situation similar to that discussed above
for mesomerically withdrawing groups. The intermediates are overall destabilized by electron withdrawal, but structures
VII and VIII are particularly unfavourable because the positive charge is adjacent to the electron-deficient atom of the
substituent. Thus, attack occurs preferentially at the 3-position (meta), but is more difficult than electrophilic attack on benzene.
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Halo Substituents: Deactivating Ortho-Para Directors

The chloro and bromo groups are weak deactivating groups. Chlorobenzene and bromobenzene undergo nitration at rates
that are, respectively, 33 and 30 times slower than for benzene. The chloro and bromo groups are ortho-para directors,
however. The relative percentages of monosubstituted products that are obtained when chlorobenzene is chlorinated,
brominated, nitrated, and sulphonated are shown in Table 4.1.
Table 4.1 Electrophilic Substitution of Chlorobenzene
Reaction Ortho Product (%) Para Product (%) Total Ortho and Para (%) Meta Product (%)
Chlorination 39 55 94
Bromination 11 87 98 6
Nitration 30 70 100 2
Sulphonation 100 100
Similar results are obtained from electrophilic substitutions of bromobenzene.
Illustrations
29. Why Halobenzene is ortho para directing and deactivating in electrophilic substitution reaction?
Ans. Halogens withdraw electrons through inductive effect and release electrons through resonance. Through inductive
effect, halogens destabilize the intermediate carbocation formed during the electrophilic substitution.
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Through resonance, halogens tend to stabilize the carbocation and the effect is more pronounced at ortho-
and para-positions. The inductive effect is stronger than resonance and causes net electron withdraw and thus
causes net deactivation. The resonance effect tends to oppose the inductive effect for the attack at ortho and
para-positions and hence makes the. deactivation less for ortho- and para-attack. Reactivity is thus controlled by
the stronger inductive effect and orientation is controlled by resonance effect.
Ortho/Para Ratios
It is expected that in monosubstituted benzene if the substituent is ortho, para-directing, the ortho to para ratio should
be 2:1. But usually in ortho, para-directing systems, the ortho substitution occurs to lesser extent than expected. This
difference may be due to many factors, that is, polar effects of the substituent, solvent, temperature, size of the substituent,
and the entering group (steric factors). The last two factors play a dominant role in determining the ortho to para ratios.
The relative proportion of ortho-product decreases, that is, the ortho/para ratio falls off sharply as the size of both the
substituent Y and the attacking electrophile E+ increases, as a result of steric hindrance to ortho-substitution.
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The size is not the sole consideration in determining o-/p-ratio. This fact is demonstrated by the nitration of the four
halogenobenzenes.
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This reversal, compared with the effect of the four alkyl groups shown here, stems from the fact that the alkyl groups
differ very little in polarity from CH3 to Me3C, whereas the difference in polarity from F to I is marked indeed, F being very
much more powerfully electron-withdrawing than I. Such electron withdrawal from the benzene ring will serve to inhibit
attack by NO2+, and this effect will be exerted to a greater extent on the ortho-positions, adjacent to Y, than on the much
more distant para-position. This polar effect dominates over the steric effect that will be operating in the opposite direction.
The para-position in tert-butylbenzene is more reactive than that in toluene in nitration but less reactive in chlorination. It
is believed that although the tert-butyl group stabilizes the positively charged transition state more effectively than methyl,
it hinders the stabilizing solvation of the positively polarized ring carbon atom adjacent to it more strongly than does the
smaller methyl group.
The electrophilic sulphonation of t-butyl benzene produces almost exclusively para product because the bulky alkyl
group effectively blocks ortho attack. Thus, electronic factors favour ortho and para attack, and steric hindrance further
favours para substitution.
62
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A classic example of the steric factor dominating in electrophilic substitutions is p-cymene. From electronic consider-
ations, the substitutions should be expected to occur at the position ortho to isopropyl group, but invariably, it takes place
ortho to the methyl group.
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But sometimes, because of the chemical interaction between the substituent and the electrophile, the ortho to para ratio
becomes abnormally high. For example, nitration of anisole with the conventional nitrating mixture, where the nitrating
agent is NO2+, gives ortho- and para-nitroanisoles in the ratio 31: 67. But when the same reaction is carried out with N2O5
(HNO3-Ac2O) this ratio becomes 71:28. This has been ascribed to the following mechanism:
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THEORY OF SUBSTITUENT EFFECTS ON ELECTROPHILIC AROMATIC SUBSTITUTION

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We see that four reasonable resonance structures can be written for the arenium ions resulting from ortho and
para attack, whereas only three can be written for the arenium ion that results from meta attack. This, in itself,
suggests that the ortho-and para-substituted arenium ions should be more stable. Of greater importance, however,
are the relatively stable structures that contribute to the hybrid for the ortho-and para-substituted arenium ions.
In these structures, nonbonding pairs of electron from nitrogen form an extra bond to the carbon of the ring. This
extra bond—and the fact that every atom in each of these structures has a complete outer octet of electrons –
makes these structures the most stable of all of the contributors. Because these structures are unusually stable,
they make a large—and stabilizing—contribution to the hybrid. This means, of course, that the ortho- and
para-substituted arenium ions themselves are considerably more stable than the arenium ion, that results from the
meta attack.
Phenol reacts with acetic anhydride, in the presence of sodium acetate, to produce the ester, phenyl acetate.
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Phenyl acetate, like phenol is an ortho-para director. (a) What structural feature of phenyl acetate explains this?
(b) Phenyl acetate, although an ortho-para director, is less reactive toward electrophilic aromatic substitution than phenol.
Use resonance theory to explain why this is so. (c) Aniline is often so highly reactive toward electrophilic substitution that
undesirable reactions take place. One way to avoid these undesirable reactions is to convert aniline to acetanilide (above),
by treating aniline with acetyl chloride or acetic anhydride.
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What kind of directive effect would you expect the acetamido group (CH3CONH–) to have? (d) Explain why it is much
less activating than the amino group, –NH2.
The directive and reactivity effects of halo substituents may, at first, seem to be contradictory. The halo groups are the
only ortho-para directors (in Table 2) that are deactivating groups. All other deactivating groups are meta directors. We
can readily account for the behavior of halo substituents, however, if we assume that their electron-withdrawing inductive
effect influences reactivity and their electron-donating resonance effect governs orientation.
Let us apply these assumptions specifically to chlorobenzene. The chloro atom is highly electronegative. Thus, we
would expect a chloro atom to withdraw electrons from the benzene ring and thereby deactivate it.
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On the other hand, when electrophilic attack does take place, the chloro group stabilizes the arenium ions resulting
from ortho and para attack relative to that from meta attack. The chloro group does this in the same way as amino groups
and hydroxyl group do—by donating an unshared pair of electron. These electrons give rise to relatively stable resonance
structures contributing to the hybrids for the ortho-para-substituted arenium ions.
What we have said about chlorobenzene is, of course, true of bromobenzene. We can summarize the inductive
and resonance effects of halo substituents in the following way. Through their electron-withdrawing inductive
effect halo groups make the ring more positive than that of benzene. This causes the free energy of activation for
any electrophilic aromatic substitution reaction to be greater than that for benzene, and, therefore, halo groups are
deactivating. Through their electron donating resonance effect, however, halo substituents cause the free energies
of activation leading to ortho and para substitution to be lower than the free energy of activation leading to meta
substitution. This makes halo substituents ortho-para directors.
CLASSIFICATION OF SUBSTITUENTS
Studies like the ones that we have presented in this section have been done for a number of other substituted benzenes. The
effects of these substituents on reactivity and orientation are included in table 4.2.
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Introduction of a Third Group into the Benzene Ring

The position takes up by a third gruop entering the ring depends on the nature of the two groups already present.
i) If the two substituents belong to the activating group, the stronger o/p director will control the orientation; nevertheless
several tri-substituted isomers will form. The order of decreasing directing powers of the activating groups is
O–‑ > NH2 > NR2 > OH > OMe, > NHAc > Ar > Me > X
ii) When both groups belong to the deactivating groups then its difficult to introduce a third group. However the order
of decreasing directing powers of deactivating groups are
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iii) If one substituent belongs, to activating group and other belongs to deactivating group the first group determining the
orientation. Further, if the orientations reinforce each other, the third group enters almost entirely one position. The
above scheme is purely qualitative.
iv) If there are two benzene rings in the same molecule ,the more electron rich benzene ring is preferentially attacked.
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REACTIONS OF ALKYL BENZENES

Halogenation of the Side Chain
The side halogenation of alkyl benzenes takes place in the presence of light or high temperatures. Side chain halogenation
is many times carried out by using the reagent N-bromosuccinimide (NBS) in the presence of light.
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An alkyl benzene with side chain other than methyl may lead to the formation of more than one products.
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Product (I) is the only product obtained, and the formation of such product can be attributed to the mechanism governing
this reaction. Side chain halogenation has a similar mechanism as that of alkanes. It involves the formation of free radical
intermediates. Now if we observe the free radicals formed by attack of Bromine free radical on Ethyl benzene, we will find
that product (I) involves formation of Benzyl free radical and (II) involves formation of Primary free radical.
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The benzyl free radical is more stable than primary free radical because its bond dissociation energy is 19 kcal/mole
less than that of primary free radical.
Order of stability of free-radicals. Benzyl > Allyl > 3° > 2° > 1° (from bond dissociation energy data).
Illustrations
30. (a) Compare the reactions of PhCH2CH2CH3 with Br2 (i) and Fe, (ii) with light or heat, and (iii) in the dark.
(b) Give steps for the reaction in (ii).
Ans. (a) (i) Ring substitution by Br occurs at the o and p positions, (ii) Bromination of the side chain occurs at the
benzylic position, the one a to Ph, giving PhCHBrCH2CH3. (iii) No reaction.
(b) This is a radical chain reaction:
Initiation step: (1) Br2 light
 → 2Br ⋅
Propagation steps: (2) PhCH 2 CH 2 CH 3 + Br ⋅ 
→ HBr +
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(3) PhCHCH2CH3 + Br2 → PhCHBrCH2CH3 + Br–
Reaction at the b or g carbon of PhCH2CH2CH3 would give PhCH2CHCH3 or PhCH2CH2CH2- respectively, with
no possible stabilization by delocalization.
31. How does the benzyl radical compare in stability with alkyl radicals mentioned previously?
Ans. Benzyl, allyl > 3° > 2° > 1° > Me > vinyl.
32. Compare the products of the reactions of PhCH2CH3 with Br2 and Cl2 in light, and explain any differences.
Ans. Bromination gives a-bromoethylbenzene exclusively, [as you may remember]. The 2° benzylic position
is only slightly favored over the 1° alkyl position in chlorination, the products being PhCHClCH3 (56%) and
PhCH2CH2Cl (44%). The less reactive Br– is more selective than the Cl–, which abstracts an H– in a more random
fashion (Reactivity-Selectivity principle).
33. (a) Using the relative reactivities towards free radical chlorination of 3°: 2°: 1° H’s as 5.0:3.8:1.0, calculate the
predicted percentages of a- and b-chlorophenylethane (A and B) from PhCH2CH3. (b) Compare these calculated
percentages yields with those reported in Problem 30 and give an explanation.
Ans. (a) PhCHClCH3 (A): 2(3.8) = 7.6; 7.6/(3.0 + 7.6) × 100% = 72%
PhCH2CH2Cl (B): 3(1.0) = 3.0; 3.0/(3.0 + 7.6) × 100% = 28%
(b) If abstraction of the benzylic H from CH2 had the same energy requirement as abstraction of a 2°H of
.
an alkane, the percentages would be 72% and 28%, respectively. The observed values of 56% vs. 44%
indicate that in radical chlorinations the phenyl group diminishes the expected reactivity of the 2° H while
leaving it more reactive than the 1°H. Because abstraction of the benzylic 2°H. by the highly reactive
Cl. is slightly exothermic, the TS more resembles the ground state reactants (Hammond postulate). In
the ground state of PhCH2CH3, electron-withdrawal by Ph makes the abstraction of the benzylic H of
CH2 more difficult and less so the b-H of CH3. Thus in PhCH2CH3 the difference in relative reactivities
of 2° vs. 1° has narrowed. Note there is very little radical character in the TS, and factors that contribute
to its stability by p delocalization are thus minimal. In this respect chlorination differs from bromination
34. (a) Give the product of the reaction of p-xylene with NBS or with 2Br2, 125°C, light, dibromination at one Me
occur? (c) Which reacts faster, p-xylene or toluene? Explain.
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(b) Electron-withdrawal by one Br makes removal of an additional H. more difficult.

(c) p-Xylene; the electron-releasing Me provides additional stability to the radical.
35. Irradiation of an equimolar mixture of cyclohexane and PhCH3 gives mostly cyclohexyl chloride with Cl2, and
PhCH2Br with Br2. Explain.
Ans. In these competitive reactions the reactivities of cyclohexane and toluene are compared, Cl., being more reactive
and less selective than Br, reacts with the kind of H present in greatest number, which in this case is one of the
twelve equivalent H’s of cyclohexane. The less reactive and more selective Br. reacts with the most reactive H,
in this case one of the three alkyl H’s of PhCH3.
9. What happens when benzene is treated with methyl chloride in presence of anhydrous AlCl3 and
the product is treated with excess of chlorine in presence of UV light?
10. Predict the major product if the following compounds are undergoing electrophilic substitution
reaction.
0H 1+ 2+ 0H
12 2+
12 2+
SOLUTIONS
9. C6 H 6 + CH 3 Cl AlCl
anhy.
 Cl2
→ C6 H 5 CH 3 UV
light
→ C6 H 5 CH 2 Cl Cl
2 → C6 H 5 CHCl2 Cl
2 → C6 H 5 CCl3
3
Benzene Benzotrichloride
0H 1+ 2+ 0H
( ( 12 2+
10.
(
1+ 2+ (
Oxidation of Side Chain

Although benzene itself is not susceptible to oxidation, side chain attached to the benzene ring undergoes oxidation and con-
verts itself into a –COOH group. Oxidation of side chain takes place after substance is heated for a long time with KMnO4.
5 &22+
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The above reaction can be used for identifying substitution pattern in aromatic compound. If any compound gives
phthalic acid on heating with KMnO4, then we can infer that it is ortho disubstituted benzene.
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There is no reaction because of the absence of a benzylic hydrogen.
Illustrations
36. Ph (CH 2 )Me KMnO

4 → ?
Ans. Ph(CH2)3Me KMnO
4 → PhCO2H
NO matter how long the side-chain is, oxidation with strong oxidising reagents results in benzoic acid.
37. Find the product

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38. Convert: Benzene → Benzoic acid

Ans. i) CH3Cl/AlCl3
ii) KMnO4 (oxidation)
BIRCH REDUCTION
The reaction where aromatic rings are partially reduced to nonconjugated 1,4-cyclohexadienes by treatment with metallic
sodium, potassium or lithium in a mixture of liquid ammonia and an alcohol is known as Birch reduction. Such reduc-
tions are known as dissolving metal reductions. The alcohol (oftenly used alcohols are ethanol, methanol, isopropanol or
t-butylalcohol) acts as a proton source. Presence of iron salts in commercial ammonia lowers the yields, and thus use of
distilled ammonia is suggested. The reaction is usually carried out at the boiling temperature of ammonia (–33°C). Birch
reduction provides a convenient method for preparing a wide variety of interesting and useful cyclic dienes. The simplest
example of this kind of reaction is the reduction of benzene to 1,4-cyclohexadiene.
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Mechanism
The generally accepted mechanism for Birch reduction is depicted below, taking the example of unsubstitued benzene as
substrate. The mechanism involves solvated electrons, which are transferred from the metal to the solvent, and hence to
the ring.
The mechanism of reduction involves formation of radical anion (1) followed by protonation by an alcohol to give
free radical (2), which is reduced by receiving further an electron transferred from the metal to form a resonance-stabilized
carbanion (3). Finally, cyclohexadienyl carbanion (3) accepts proton from another molecule of alcohol to yield cyclohexadiene
(4). Protonation to the radical anion is supposed to be the rate-limiting step. Such protonation eliminates the possibilities of
formation of undesirable side products arising out of dimerization and/or polymerization of the radical anions.
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Critical Views
a) The relative rate and regioselectivity of Birch reaction is largely dependent upon the nature of substituents in the aromatic
nucleus3. The substituents have profound impact on the stability of the radical anion. As such, electron-donating
and electron-withdrawing substituents behave differently towards Birch reduction.
(i) Effect of electron-donating substituents

The electron-donating groups (such as alkyl or alkoxyl) retard the rate of the reaction, and usually remain at the nonreduced
positions of the product.
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In fused aromatic ring systems (like naphthalene), an electron-donating substituent directs the reduction in the unsub-
stituted ring.
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(ii) Effect of electron-withdrawing substituents

The electron-withdrawing groups (such as –COOH, –COOR, –CONH2, –Ph, –SiMe3 etc.) enhance the rate of the reaction,
and generally remain at the reduced positions of the product.
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An electron-withdrawing substituent in a fused aromatic system, like naphthalene, promotes reduction of that ring to
which it is attached.
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b) Though an isolated olefinic bond is not usually reduced under Birch conditions (exceptions as found in an end
methylene or in strained systems), but olefinic bonds conjugated with aromatic systems or with carbonyl groups are
readily reduced by Na/NH3(l). Under Birch conditions halogen, nitro, aldehyde, and keto groups may also be reduced.
Besides, alkynes are also reduced with Na/NH3(l) or Li/NH3(l) affording trans-alkenes.
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c) As already mentioned that strongly electron-releasing groups (for example, –OCH3) deactivate the aromatic ring towards
Birch reduction, and in case of such deactivated systems lithium is often used together with a co-solvent (very often THF)
and a weaker proton source (t-butylalcohol). The stronger reducing agent, combined with a weaker proton source, promotes
the reduction. It is noticed that the rate of the Birch reduction increases with metals in the order of K > Na > Li. It is also
reported that Na+ ions retard the fast Li-Birch reduction, and while Li+ ions accelerate the slow Na-Birch reduction.
Applications
Applications of Birch reduction in organic syntheses are multifold, and this beautiful reaction offers a simple technique for
carrying out a variety of useful conversions; this reaction find immense utility as a key step in the syntheses of a number
of organic compounds of interest. A few examples of reaction undergoing Birch reduction are cited:
1) Birch reduction offers a convenient method for preparing 1,4-dihydroderivatives of aromatic compounds:
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2) Selective reduction of a benzene ring in the presence of another reducible group can be achieved by applying
protective-technique:
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3) Substituted cyclohexenones can be prepared by using Birch reductive technique:

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11. Arrange the following substances in order of activating a benzene ring.
(a) Benzamide, Acetanilide, Aniline (b) Phenylacetate, Acetophenone, Phenol
SOLUTION
11. (a)
2 2
1+ 1+±&±&+ &±1+
! !
In aniline, benzene ring is directly attached –NH2 which releases electrons by resonance effect,
where as the activation of –NH2 group can be decreased by converting it to anilide, and in amide,
ring is attached to electron withdrawing group which deactivates the ring.
2 2
2+ 2±&±&+ &±&+
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Illustrations
39. Draw an enthalpy diagram for the reaction of E+ with PhBr compared to the reaction with benzene.
Ans. See Figure.
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40. Compare the activating effects of the following o, p-directors and explain your order.
(a) ±2+±2 DQG ±2&±&+ (b) ±1+ DQG ±1+±&±&+

2 2
Ans. (a) The order of activation is —O >—OH >—OCOCH3. The —O , with a full negative charge, is best able to
– –
donate electrons, thereby giving the very stable uncharged intermediate

(
2
+
2
In ±2&&+ the C of the δ+C = Oδ– has a positive charge and makes demands on the —O— for electron density.
This cross-conjugation diminishes the ability of the —O— to donate e–’s to the arenonium ion.
(b) The order is —NH2 > —NHCOCH3 because of cross-conjugation in the amide, $U±1 &±&+
2 2
41. Predict and account for the reactivity and orientation in (a) Ph — N=O= and (b) Ph — SMe2.
Ans. (a) The nitroso group behaves like halogen in that it deactivates the ring inductively by attracting e‑’s, but orients
ortho and para as a consequence of delocalization of the unshared pair of e–’s on N. The delocalized structure A
for the s-complex is quite stable with all atoms having an octet.
+

1 2
(
$
(b) R2S — behaves like R3N — for the same reason — the positively-charged atom strongly attracts electron
density from the ring.
42. Compare the rate of nitration under similar conditions of PhOMe and PhSMe. Explain.
Ans. PhOMe > PhSMe. The p bond from O (which uses a 2p orbital) to the ring C is shorter and stronger than the
comparable bond from S (which uses a 3p orbital) to the ring C.
43. PhNH2 reacts with Br2 in H2O to give more than 90% yield of 2,4,6-tribromoaniline, while PhNMe2 is mononitrated
at the meta position with the more powerfully electrophilic reagent HNO3/H2SO4. Explain.
Ans. The tribromoderivative forms because NH2 is a strongly activating o,p-orienting substituent (as is NMe2). Recall
that amines are also proton acceptors, so in strong acid they are completely protonated. Consequently, the only
species present in HNO3/H2SO4, is the conjugate acid PhNMe2H+, and it is the species undergoing nitration. The
NR2H+ group, with a full + charge, is a deactivator that orients meta.
44. (a) Categorize the following G substituents as activating o,p; deactivating o,p or deactivating m, and give reasons:
(i) PhSR, (ii) PhSR (sulphoxide), and (iii) PhSR (sulphone). (b) Compare the reactivity of PhSOR with PhNO.
Ans. (a) (i) Activating, o,p. There is a delocalizable unshared pair of e–’s on S. (ii) Deactivating, o,p. Like PhNO
(Problem 42) it is p-donating and s-withdrawing (Problem 38). (iii) Deactivating m. Lacking an unshared
pair on S, the strong inductive effect of Sd+ makes this G behave like — SO3H (J in Problem 37).
(b) PhNO > PhSOR. The smaller N delocalizes electron density better than the larger S (Problem 43).
45. Place each of the following in decreasing order of relative DH++ for forming an arenonium ion intermediate:
benzene, toluene in meta and para positions, nitrobenzene in meta and para positions.
Ans. Relative DH++’s are: p-Me < m-Me < H (in PhH) <m-NO2 <p-NO2. Benzene has an intermediate DH++ because it
lacks the activating Me or deactivating NO2 group.
46. Given the percentage yields of meta-substituted toluene from the following reactions: 0.5% bromotoluene
from bromination in acetic acid; 3.5% nitrotoluene from nitration in acetic acid; and 21% ethyltoluene
from reaction with CH3CH2Br in GaBr3. Determine and account for the relative reactivities of the three
reagents.
Ans. The Reactivity-Selectivity principle states that more reactive attacking species are less selective, and the yields
from their reactions are more nearly like those calculated from probabilities. Since Me is an o,p-director, reagents
that form larger amounts of meta isomer are less selective; the relative reactivities are: CH3CH2+> +NO2 >
Br2(Brd+—Br—d‑FeBr3).
12. Complete the following:
+& &O
%) $O&O
(a) &+ " (b) + & "
+&
+&
2+
&+2+ %U
(c) " (d) "
1D
13. Compounds (A), (B) and (C) are three methyl isomeric derivatives of benzene. Identify which is
o-, m- or p-from the products of nitration?
A →
conc. HNO3
H 2SO 4
two mononitro product
B 
conc. HNO3
H 2SO 4
→ three mononitro products
C →
conc. HNO3
H 2SO 4
one mononitro product
SOLUTIONS
+&
&+
+ &
%)
12. (a) &+ &+
+ &
+&
&O
$O&O
&+
(b) +& +
+ &
2+ 2
&+2+
(c)
1D
+ %U
%U
(d)
+ %U
13.
&+ &+ &+
&+ &+ &+
+12
+62
R[\OHQH
12
$ 12
&+ &+ &+ &+

12
+12

+62
&+ &+ &+ 21 &+
P[\OHQH
% 12
&+ &+
+12 12
+62
&+ &+
S[\OHQH
&
Illustrations
47. Explain the different percentages of o- and p-toluenesulfonic acids formed when PhMe– is sulfonated – at the
following temperatures:
0°C 100°C
o-toluenesulfonic acid (A) 43% 13%
p-toluenesulfonic acid (B) 53% 79%
Ans. The principle of thermodynamic vs. kinetic control is applicable because sulfonation is one of the few reversible
aromatic electrophilic substitutions (Problem 14). At 0°C, kinetic control prevails for formation of the rate-
determining TS1. The somewhat higher yield of B indicates that, for TS1 DHB+ is less than DHA+ but not enough
to preclude a significant yield of A. As the temperature increases, thermodynamic control becomes predominant.
Some initially formed A reverses (desulphonates) and eventually in the equilibrium mixture of products the more
stable, relatively sterically unhindered para isomer dominates.
48. Explain the following percentages of meta electrophilic substitutions:

(a) ArCH 3 , ArCH 2 CI, ArCHCI 2 , ArCCI3 (b) ArN + Me3 , ArCH 2 N + Me3 , ArCH 2 CH 2 N + Me3
4.4% 15.5% 33.8% 64.6% 100% 88% 19%
Ans. (a) Successive replacement of H’s in electron-releasing CH3 by electronegative Cl’s makes G increasingly
electron-attracting and m-orienting. (b) The + charge on N in +NMe3 makes the substituent electron-attracting
and m-directing by an inductive effect. Its influence wanes with increasing CH2’s between +N and Ar. With two
CH2’s, the electron-releasing effect of the alkyl group is more significant and o,p-orientation dominates.
49. Describe and account for the reaction, if any, of D2SO4 in D2O with: (a) C6H5SO3H, (b) C6H5OH, and (c) C6H6.
Ans. (a) There is no ring deuteration because —SO3H is deactivating. However, the acidic H is exchanged for D
to give C6H5SO3D. At elevated temperatures desulfonation can occur (Problem — 14) giving initially C6 H5 D.
(b) o,p-Orientation yields 2,4,6-triD-C6H2OD. The acidic H is exchanged, (c) Slow reaction produces
hexadeuterobenzene because there is no activating or orienting substituent.
50. Give the principal monosubstitution products from the following reactions and indicate whether each reaction is
faster (F) or slower (S) than with benzene:
(a) Nitration of PhNHCOMe (d) Nitration of Ph – Ph (g) Nitration of PhC ≡ N
(b) Bromination of PhCBr3 (e) Nitration of PhCOOMe (h) Bromination of PhI.
(c) Chlorination of PhCMe3 (f) Sulfonation of PhCHMe2
Ans. (a) p-O2NC6H4NHCOCH3 (F); (b) m-BrC6H4CBr3 (S); (c) p-ClC6H4CCMe3 (F); (d) p-O2NC6H4Ph (F) (Ph is
an activating o,p group); (e) m-O2NC6H4COOMe (S); (f) p-HSO3C6H4CHMe2 (F); (g) m-O2NC6H4CN (S);
(h) p-BrC6H4I (S).
51. Classify the following substituent groups by their orientation and reactivity:
(a) –CH = CHNO2, (b) ±2&5 (c) ±&1+
2 2
(d) –OAr (e) –CH2OH (f) ±&&+
2
Ans. (b), (d), (e) Activating o,p; (c), (f) deactivating m; (a) deactivating (by NO2) o,p (by C=C).
52. Give the structures, indicating by an arrow the position(s) most likely to undergo electrophilic substitution in
each of the following compounds, and explain your choices, (a) Phenyl benzoate, PhOCOPh; (b) p-nitrobiphenyl,
p-O2N — C6H4—Ph; (c) phenyl-m-cyanophenylmethane; and (d) 1,4-diphenylbenzene (p-terphenyl).
Ans. (a) See A below. The ring bonded to & 2 is deactivated; the ring bonded to —O— is activated, (b) See B.
Although the ring with NO2 is deactivated, it nevertheless activates the unsubstituted ring. Para substitution is
less hindered than ortho. (c) See C. The ring with CN is deactivated, and the —CH2—Ar group activates the
unsubstituted ring. Para is less hindered than ortho. (d) See D. Reaction occurs on the middle ring since it is
bonded to two activating Ph’s.
&²2 12
$ %
&1
&+
& '
53. Indicate by an arrow the position(s) most likely to react in each of the following three isomeric nitrotoluenes.
Explain your choices.
&+ &+ &+

12
12
12
( RUWKR ) PHWD * SDUD
Ans. In E, Me directs E+ ortho and para to C* and C6, positions that are also meta to NO2—the substituents reinforce
each other. In F, the orientation is in opposition. The o,p-director controls the orientation, but somehow E+ enters
mostly ortho, not para, to the meta-directing NO2. Both G’s are reinforcing in G, and E+ is directed ortho, on to C2.
54. Show by an arrow the preferred product of reaction with E+ of each of the three isomeric methoxytoluenes and
explain your choices.
Ans.
2&+ 2&+ 2&+
&+
&+
&+
+ RUWKR , PHWD - SDUD
Both groups are activating and o,p-directing. In I, their influence is reinforcing, and a mixture of two isomers is in-
evitable. Very little substitution occurs in the sterically-hindered position between the meta G’s. In H and J, the two
G’s are in opposition. The more strongly activating OMe controls the orientation, and E+ bonds mainly o and p to it.
55. Place the following compounds in the order of their relative reactivity with E+. (a) p-nitrochlorobenzene,
chlorobenzene, 2,4-dinitrochlorobenzene; (b) acetanilide (PhNHCOCH3), aniline (PhNH2), acetophenone
(PhCOCH3); (c) 1,3-dimethylbenzene, 1,4-dimethylbenzene, toluene, benzene, 1,3,5-trimethylbenzene; and
(d) p-CH3C6H4COOH, p-HOOCC6H4COOH, p-CH3C6H4CH3, C6H5CH3.
Ans. (a) Chlorobenzene >p-nitrochlorobenzene > 2,4-dinitrochlorobenzene
(b) Aniline > acetanilide > benzene > acetophenone
(c) 1,3,5-trimethylbenzene > 1,3-dimethylbenzene (Me’s reenforcing) > 1,4-dimethylbenzene (Me’s not
reenforcing) > toluene > benzene
(d) p-CH3C6H4CH3 (two A groups) > C6H5CH3 (one A group) >p-CH3C6H4COOH (one A and one D group)
>p-HOOCC6H4COOH (two D groups), where A and D mean activating and deactivating, respectively.
56. Show with arrows the principal position(s) sulfonated by reaction of (a) p-CH3C6H4NH3 Cl–, (b) o-HOC6H4COOH,
and (c) m-C6H4(NO2)2.
Ans.
1+ &O 2+
&22+
(a) (b) (c) No reaction; two strongly deactivating G’s
&+
57. Account for the greater reactivity and the o,p-orientation in electrophilic substitution of biphenyl despite the
electron-attracting inductive effect of the phenyl group.
Ans. In attack at the o,p positions the unreacted ring can stabilize the + charge on the attached C of the a complex
by electron-releasing delocalization that results in delocalizing the + charge to both rings. Such delocalization is
impossible with the intermediate from meta substitution which does not have the + charge on the C bonded to the
Ph substituent. The + charge cannot be incorporated into the second ring, and delocalization is confined to one ring.
58. (a) Explain the rapid formation of 2,4,6-Br3C6H2NH2 (C) when either p-H2NC6H4SO3H (A) or p-H2NC5H4COOH
(D) is treated with bromine in H2O. (b) What is the name of this type of reaction?
Ans. (a) A exists as the dipolar ion, p-H3NC6H4SO3–(A'). Br+ probably first attacks the ring carbon displacing SO3
(a good leaving group). The initially formed p-bromoanilinium ion, p-BrC6H4NH3+ (B), is a strong enough acid
to revert to the amino group (in B'), which strongly activates the ring to further substitution by additional Br+ in
the two ortho positions. A similar reaction occurs with D, which loses CO2, also a good leaving group.
± ±
62 62 %U %U %U %U
%U ±62 ±+ %U

%U %U

1+
1+
1+
1+ 1+
$ƍ % %ƍ &
&22+ +22& %U %U
%U ±+ %U

±&2
&
1+ 1+ 1+
(b) The displacement of one ring substituent by another is called an ipso substitution. The ipso carbon is the one
on which such substitution occurs.
59. (a) Give an orbital overlap explanation for the o,p-orientation of an activating R group such as CH3. (b) Give
the name for this overlap, (c) Why does nitration of 2-ethyltoluene yield more 4-nitro-2-ethyltoluene (A) than
5-nitro-2-ethyltoluene (B)?
Ans. (a) The empty p AO of C+ can overlap weakly with the C—Ha bond of CH3, thereby delocalizing the + charge
from C to H as shown in Figure.
GHORFDOL]DWLRQ
+
+ +
+ VSRUELWDO RU &+
&
( + (
+
(b) The orbital overlap is called hyperconjugation.

(c) Hyperconjugation is more effective with —CH3, which has three H’s, than with —CH2CH3, which has two
H’s. Consequently, —CH3 is a somewhat better activator than —CH2CH3 and there is a higher yield of A,
formed by para substitution to CH3, than B where nitration is para to —CH2CH3.
60. Why can a t-butyl substituent be used as a blocking group in aromatic electrophilic substitutions?
Ans. The Friedel-Crafts alkylation can be reversed, especially when a 3° alkyl group such as Me3C is present.
Dealkylation is effected with AlCl3 by transfer of Me3C+ to another arene, used as the solvent, or at high
temperatures by protonation with H+ and loss of Me3C as Me2C=CH2. Me3C—, introduced into a ring, is used to
block an active position and/or to direct another G into the ring, and then removed.
61. Illustrate the use of t-Bu as a blocking group to synthesize (a) o-benzoyltoluene from toluene, and
(b) 1,3,-dimethyl-2-ethylbenzene from m-xylene.
0H 0H 0H
&23K &23K
0H&&O 3K&2&O 3K+$O&O
Ans. (a) 3K±&+
$O&O $O&O ±0H& &+
&0H &0H
(b) m-Xylene is first t-butylated, giving the less sterically-hindered thermodynamic product, A.
0H 0H 0H 0H
(W (W
0H&&O &+ &++) P[\OHQH+)
$O&O & & $
0H
0H& 0H 0H& 0H 0H
$
In the dealkylation, benzene or m-xylene may be used as an acceptor. If the latter is used, A is the product, and
it can be recycled.
62. Explain the isomerization of 1,2,4-trialkylbenzenes (B) to the 1,3,5-isomers (C) during AlCl3 catalyzed Friedel-
Crafts alkylation reactions.
Ans. A 1,2,4-tri-alkylbenzene (B) is first formed, rapidly but reversibly, along with HAlCl4 (AlCl3 + HCl), a very
strong Bronsted acid. In its presence, B rearranges slowly but irreversibly to the less sterically-hindered,
thermodynamically more stable C. This preference for 1,3,5-trialkyl isomers is a consequence of having the
more stable a- complex, whose 8+ resides only on 3°C’s bonded to R, in contrast to any other tri-R-substituted
s complex. R
5
5 5 5 5
+$O&O 5&O +
±5&O $O&O
IDVW VORZ
5 5 5
% &
+ + + + + +
5 5 5 5 5 5
±
$O&O

5 5 5
VWDEOHVDOW
63. (a) Give a mechanism for the following bromodealkylation:
ArC(CH 3 )3 + Br2 

AlBr3
→ ArBr + (CH 3 ) 2 C == CH 2 (+ AlBr3 + HBr)
(b) Why does this reaction not occur with ArCH2CH2CH2CH3?
Ans. (a) In this ipso substitution, Br+ displaces Me3C+ which loses H+ giving isobutylene.
%U
$U& &+
%U & &+
$U%U &+ & &++
$U
(b) Ejection of the unstable 1° n-Bu+ requires too high an energy.
64. Account for the products of the following reactions and explain their formation, (a) Both p-and o-xylene, with
large amounts of a Friedel-Crafts catalyst, are converted partly into m-xylene. (b) Ethylbenzene, in the presence
of HF—BF3 reacts to form benzene and 1,3-diethylbenzene.
Ans. (a) Since the Friedel-Crafts alkylation is reversible, the thermodynamically more stable m-isomer forms under
equilibrium conditions, (b) In this disproportionation the catalyst protonates Cl and the s complex ethylates a
second molecule of PhEt to give the diethyl s complex and benzene. Under these equilibrium conditions, the
former loses H+ to give the thermodynamically more stable 1,3-diethylbenzene. Ethylation occurs without the
formation of the very high energy Et+ as an intermediate.
65. (a) Which position in naphthalene preferentially reacts with E+? (b) Account for this preference
mechanistically.
Ans. (a) The A position, (b) Attack at the s position has a lower DH because the intermediate s complex A and its TSt
are more stable than the a complex B and its TS1 from is attack. They both have an intact benzene ring, but A is
an allylic R+ and B is not. Thus, the + charge in A is better delocalized.
+ ( + ( + (
+

RU (
DQDOO\OLF5 QRWDQDOO\OLF5
ĮVXEVWLWXWLRQ EVXEVWLWXWLRQ
$ %
(In both A and B the intact aromatic ring has the same effect on stabilizing the + charge.)
66. (a) Which is more reactive in electrophilic substitution, naphthalene or benzene? Why? (b) How may naphthalene
be brominated?
Ans. (a) Napthalene, at both the 1 and 2 positions. The loss of aromaticity in one ring of naphthalene ‘costs’
255–151 = 104 kJ/mol, much less than that for the loss of the single ring in benzene (151 kj/mol). (b) Because
of the significant activation of one ring by the other, naphthalene is easily brominated in CCl4 without a Lewis
catalyst like FeBr3, which is required to brominate benzene.
14. Indicate which positions in each of the following compounds will be preferentially deuterated
when 1 mole of DCl is employed for the reaction.
(i) Anisole; (ii) Benzotrifluoride
15. Complete the equations and comment:
(i) PhBr + Ac 2 O AlCl

 3
→ ? (ii) PhCH2CN HNO
 3
→?
0H 0H
+12+62 $O&O
(iii) " (iv) $F&O "
&+0H &+0H
16. Complete the following:
+& &O
%) $O&O
(a) &+ " (b) +& "
+&
+&
2+
&+2+ %U
(c) " (d) "
1D
SOLUTIONS
14. (i) –o/p; (ii) –m
%U %U
$O&O
15. (i) $F2
&20H
Two molecules of aluminimum chloride must be used, since the acylating species is acetic anhy-
dride. The formation of the p-product is probably due to steric effects.
&+&1 &+&1
+12
(ii)
12
The cyano-group directly attached to the benzene ring has a very strong –R effect and so is
m-orienting. When ‘isolated’ from the benzene ring, it exerts only a –I effect on the ring. This
effect must be weak, otherwise m-substitution would have occurred. At the same time, the CH2
group exerts a hyperconjugative, which favours o/p substitution. Presumably the steric effect
largely decides p-substitution rather than o–.
0H 0H
+12+62 12
(iii)
&+0H &+0H
Both alkyl groups have a +I effect, Me2CH > Me. Both also have a hyperconugative effect,
Me > Me2CH. Since these effects are in opposition, it is not easy to predict the orientation.
However, steric effects due to Me2CH are far larger than those due to Me, and this decides
(presumably) in favour of substitution ortho to Me.
0H 0H
$O&O
(iv) $F&O &20H
&+0H &+0H
The explanation is similar to that given for (iii).

+ &
+& &+
%)
16. (a) &+ &+
+&
+&
&O &+
$O&O
(b) + & +
+ &
2+ 2 + %U
&+2+ %U
(c) (d)
1D
+ %U
Illustrations
67. Account for the formation of mostly 1-naphthalenesulfonic acid at 40–80°C and when naphthalene is sulphonated.
Ans. The 1-isomer (kinetically-controlled product) is formed faster at lower temperatures. Since the reaction
is reversible the thermodynamically-con trolled, more stable, but more slowly formed 2-isomer is produced
at 160°C.
68. (a) Why is b-naphthalenesulphonic acid more stable (Question 67) than the alpha-isomer? (b) Devise an
experiment to confirm the relative stabilities.
Ans. (a) The –SO3H group is about as large as a t-butyl group. In the 1 position it is sterically hindered, being within
the van der Waals radius of the C8H. This is called a peri interaction, (b) Subject pure a-naphathalene-sulphonic
acid to the same reaction conditions (H2SO4, 160°C). The same equilibrium mixture (= 85% b and 15% a)
is obtained.
69. State the rules for deciding which ring reacts with E+ in naphthyl-G under kinetically-controlled conditions.
Ans. Rule 1. a-Substitution always dominates.
Rule 2. When one ring has a deactivating G on it, further substitution occurs in the unsubstituted ring at an a
position if available.
Rule 3. When one ring has an activating a-G, further substitution occurs in the same ring at position 4, and to a
smaller extent at position 2. An activating b-G orients E+ to position 1.
70. Write the structures for the product(s) of (a) nitration of 1-methoxynaphthalene and (b) bromination of
2-methylnaphthalene.
2&+ 2&+
12
Ans. (a) VRPH
12
%U
&+
(b)
In (b) the activated ring has no available p position so substitution occurs at the more reactive ortho (a) position.
71. (a) Why is Friedel-Crafts acylation but not alkylation of naphthalene practical? (b) Give the product of acylation of
naphthalene with CH3COCl and AlCl3 in the solvent (i) CS2, and (ii) PhNO2. (c) Explain the different products in (b).
Ans. (a) Acylation introduces a deactivating group (–COR) that prevents further acylation from occurring. Introduction
of an activating-R group induces polyalkylations. (b) (i) 1-Acetylnaphthalene and (ii) 2-acetyl-naphthalene.
(c) PhNO2 may form a bulky complex with RCOCl—AlCl3 that can only attack the more spacious 2 position.
72. Provide the product(s) of the reaction of naphthalene with succinic anhydride and AlCl3 in PhNO2.
Ans. A separable mixture of a- and b-products is obtained:
2
&±&+&+&22+
2
& $O&O E 1DSKWKR\O SURSLRQLFDFLG
+& 3K12
2
2
+ & &±&+&+&22+
&
2
E 1DSKWKR\O SURSLRQLFDFLG
73. Contrast the CrO3/HOAc oxidation of toluene and b-methylnaphthalene.

Ans. The Me of toluene is more susceptible to oxidation than the aromatic ring and the product is PhCOOH. In
b-methylnaphthalene, the reactive a positions are more easily oxidized than Me and, under these conditions of
oxidation, the main product is the quinone A.
2
&+ &+
&U2+2$F
17.
&
2
$0HWK\OQDSKWKRTXLQRQH
18. Which of the following is correct for the mononitration of phenyl benzoate?
&22
2 2
2 2
(a) (b) 12
12
&22
(c) 12 (d) &22
19. What are A and B in the following reaction sequence?

%U
$O&O%U +12
" $%
+62
%U %U %U %U
12 12
(a) (b)
12
12
%U %U %U %U
(c) (d)
12 12
&+ 12 12
20. Arrange the following compounds in order of increasing dipole moment Toluene
(I)
m-dichlorobenzene o-dicholrobenzene p-dichlorobenzene
(II) (III)
(IV)
(a) I < IV < II < III (b) IV < I < II < III
(c) IV < I < III < II (d) IV < II < I < III
+ &
21. The reaction of 2+ with HBr gives:
&+ &+
%U
(a) 2+ (b) 2+
%U
&+ &+
%U
(c) %U (d) %U
%U
22. When cinnamic acid is nitrated, the incoming electrophile ( NO +2 ) goes at

(a) ortho position only (b) para position only
(c) meta position only (d) both ortho and para positions
23. Predict the structures of the intermediates in the following reaction sequence.
&+
2 2 &+ 2
2
L $O&O =Q+J +32
2 LL +2 $ +&O %
24. Describe how mescaline could be synthesized from toluene.

1+
+& 2 2
2 &+
+&
PHVFDOLQH
%)
25. &+&2 2 33LV
2
2
2
2 2
&+ &+
&+
(a) (b) (c) (d)
2 2 &+ 2 2 2
2
SOLUTIONS
17. The product obtained by the more stable carbocation.
∴ (b)
18. ∴ (a)
19. Since Br is on o- and p-directing group.

∴ (a)
20. ∴ (b)
21. The benzylic carbocation is more stable.

∴ (b)
22.
+ (
+ (±
2 (±
DWSDUDSRVLWLRQ 2 DWRUWKR 2
( SRVLWLRQ
+ + +
+ (
+
2
2
(
+
+
+
2
(
+
The delocalization of positive charge in arenium ion is extensive (occurs even in the side chain)
when the electrophile attacks at ortho and para position in comparison to when it attacks at meta
position (where the delocalization all occur only in the ring).
∴ (d)
23.
&+
2 2 &+
2 &+ 2
L $O&O =Q+J 2
2 LL +2 +&O
2
2 2
+2
2 %
+2
$ &+ 2
2
+32
RU+)
24.
&+ &+ &+ &+

62+ 2+ 2+
IXPLQJ+62 L 1D2+' FRQF+62+12
' LL +
21
62+ 2+ 2+
FRQF+62'
&+ &+ &+

2 2+ 2+
&+ &+ 621D2+' 1D2+'
+
2 1 2 2+ 62+
21 21
2 &+ 2+ 2+
+&
6Q+&O
1D12+&O
+32
&+
2 2 +& 2
&+ DON.0Q2ǻ &+ &+&O$O&O ([FHVV &+
+HDW
2 2 2
2 &+ 2 &+ 2 &+
+& +& +&
+ 1 &OKY
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2
&+ 2 2
/L$O+ &+ .&1 &+
2
2 2
2 &+
+& 2 &+ 2 &+
+& +&
25. ∴ (b)
ARYL HALIDES
Aryl halides are the compounds that contain halogen atom directly attached to the benzene ring. They have general
formula ArX.
&O &O &O &O
12
FKORUREHQ]HQH FKORURQLWUREHQ]HQH
12 1+
FKORURQLWUREHQ]HQH FKORURDQLOLQH
Any halogen compound that contains a benzene ring is not classified as aryl halide. e.g., Benzyl chloride is not an aryl
halide, but is a substituted alkyl halide.
Preparation Methods of Aryl Halides

Halogenation
Lewis acid
Ar − H + X 2 (
X = Cl , Br )
→ Ar − X + HX
For introducing only the halogen at para position, the Lewis acid thallium acetate is used.
&+ &+
&2 &2
1+ 1+
%U
7O 2$F
$FHWDQLOLGH
&+
From diazonium salts
&O
1
+12 UHGXFWLRQ 1D12

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1&O± ,
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Special Note on Sandmeyer Reaction
Introduction
The reaction leading to the formation of aromatic halogeno or cyano compounds from the corresponding diazonium salts
under the catalytic action of cuprous halide or cyanide is called as the Sandmeyer reaction.
+ -
Ar N 2 X + CuX 
→ Ar - X
The reaction is not useful for the direct preparation of fluorides or iodides, but for bromides and chlorides, it is of wide
scope. The yields become usually high. During preparation of benzonitrile derivatives (ArCN), the reaction is generally
conducted in neutral solution to avoid evolution of HCN.
+
CuCN + KCN
Ar N 2 X 
50° C
→ Ar - CN
The Sandmeyer reaction can thus generally be represented as:
+ +1 +1
Ar N 2 X + C uNu 
( Nu = CI , Br , CN)
→ Ar - Nu + N 2 + C u X
The Cu(I)-species is regenerated and is thus a true catalyst.

1+ %U
&+ &+
L 1D12+%U
LL &X%U
1+ &1
L 1D12+&O
LL &X&1
12 12
Mechanism
The mechanism of the Sandmeyer reaction is not rigorously known, however is believed to proceed in the following
manner. In the first two steps, the arenediazonium ion species is reduced by Cu(II) salt to give an aryl radical species.
But two alternative mechanisms are possible for the third step — either the resulting Cu(II) salt binds to the aryl radical
forming the intermediate Ar-Cu(III)NuX followed by its dissociation into Cu(I)X and the substitution product Ar-Nu, or
the aryl radical reacts with the Cu(II) salt giving the substitution product Ar-Nu through ligand transfer and Cu(I) through
concomitant reduction.

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$U 1 1 $U 1

$U &X1X; $U &X1X; $U 1X&X;
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RQHVWHS

$U 1X&X;
Critical Views
(a) In case of in situ preparation of required diazonium salt from an aryl amine by means of diazotization reaction, an acid
HX is used, that corresponds the halo substituent (X) to be introduced onto the aromatic ring; otherwise—e.g., when
using HCl/CuBr—a mixture of aryl chloride and bromide will be obtained.
(b) Aryl iodides and fluorides can also be prepared from the corresponding diazonium salts. The cuprous catalyst is not
necessary for the preparation of aryl iodide because iodide ion is sufficient enough to decompose the diazonium salt.
.O
$U 1 1 ; $U ,1.;
,±
$U 1 1 , $U 1 1 ,

$U 1 1
$U 1 $U 1 1
,
$U±,, , ,
Aryl fluoride can be prepared by careful heating of diazonium fluoroborate (Schiemann salt); careful handling is
required (using proper equipment) because the Schiemann diazonium salt is potentially explosive.
+%) KHDW
$U 1 1 &O $U 1 1%) $U±)1%)
6FKLHPDQQVDOW
However, the advantageous method of preparing aryl fluoride that does not require forming and isolating potentially
explosive Schiemann diazonium fluoroborate is as follows:
+1(W +)
$U 1 1 &O $U 1 1 1(W $U 1 1)
±+1(W&O S\KHDW
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$U 1 1, $U ,
Applications
The Sandmeyer reaction is a very useful synthetic tool in organic synthesis. A few examples are:
1+ &O
L 1D12+&O
i)
LL &X&O
1+
L 1D12+&O
ii)
LL .O
2 2
%U %U
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.O
iii) ±1
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1+ &1
12 12
L 1D12+&O
iv)
LL &X&1

1+ &1
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L 1D12+&O
v) >5HI@
LL &X&1
1+
%U %U
L 1D12+&O
vi) >5HI@
LL .O
NUCLEOPHILIC AROMATIC SUBSTITUENTS

Nucleophilic substitution is not a typical reaction of aromatic compounds. However, appropriately substituted aromatic
compounds do undergo nucleophilic substitution. There are two distinct and major mechanisms by which a nucleophile
can be introduced into the aromatic ring. In one, the nucleophilic attacks at a ring carbon atom and this type is
covered in detail below. The second method depends on an electron-rich species behaving as a base and attacking at
hydrogen.
By Addition-Elimination Mechanism (SNAr)
Whereas electrophilic attack of benzene is both well known and important, the corresponding reaction with nucleophiles
is very difficult and is not typical of aromatic compounds. However, if the aromatic ring is p-electron-deficient, because
an electron-withdrawing group (EWG) is present, then nucleophilic attack may occur. The mechanism for the addition-
elimination sequence for nucleophilic substitution is shown below.
(:* (:* (:* (:* (:*

; ; ; ; 1X
±;
1X 1X 1X
1X
The initial attack disrupts the p-cloud and the resulting intermediate species, a carbanion, is stabilized by resonance.
There is a close similarity between this mechanism and that proposed earlier in this chapter for electrophilic attack on
benzene, although in that reaction the intermediate was a carbocation.
The intermediate species are called Meisenheimer complexes, many of which are strongly coloured (The first such
intermediate was isolated by Meisenheimer in 1902 from the reaction of 2-ethoxy-l,3,5-trinitrobenzene with sodium
methoxide).
In the second step, aromaticity is restored through elimination of an ionic species and it is here that the two reaction
types diverge:
(i) In electrophilic attack, a proton, H+, is lost through abstraction by a base.
(ii) In nucleophilic substitution the leaving group is X–.
The nature of X is of fundamental importance to the success of the reaction. Displacement of hydrogen is very
difficult, because the hydride ion, H–, is a very poor leaving group. Benzene itself does not react with nucleophiles.
The important nucleophilic substitution reactions involve the displacement of a group other than hydride ion.
The more effective leaving groups are the halogens, the diazonium group and the sulphonic acid group. The
diazonium group is the most effective because a very stable nitrogen molecule results from the elimination step.
In these reactions, nucleophilic attack occurs at the carbon atom to which the substituent is attached. In the product,
the nucleophile occupies the position of the original substituent. This process is called aromatic nucleophilic ipso
attack.
&O &O 2+ 2+
±
2+ ±&O
12 1 12
±
2 2±
&O 2&+
12 12
2&+
&O
12 12
In both cases, this first step is usually the slower and, therefore, rate-determining.
The carbon–leaving group bond strength has no effect on the rate as it is not broken in the rate determining
step.
The greater the stability of Meisenheimer complexes, the more is the reactivity.
Since activating group towards nucleophilic substitution can stabilise the Meisenheimer complexes most effectively
from the ortho and para positions with respect to the leaving group, they must be at ortho and para position with respect
to the leaving group to promote the reactions.
Since halogens as leaving group can stabilise the Meisenheimer complexes through the –I effect only,the following
reactivities of the aryl halides have been observed: RF > RCl > RBr > Rl (as per the intensity of –I effect of halogens)
Electron releasing group which destablize carbanion and increase electron density of the ring deactivates halogen towards
nucleophilic attack. E.g.
&O 2+

L 1D2+.DWP
LL +
1D2&+
9LD &O
&+2+
1 &O 1 2&+ 1 2&+
Ւ
&KORURS\ULGLQH 0HWKR[\S\ULGLQH $QLRQLFLQWHUPHGLDWH
intermediate anion has negative charge on nitrogen. Because nitrogen is more electronegative than carbon, the intermedi-
ate is more stable and is formed faster than the one from chlorobenzene.
) 2&+
) ) ) )
1D2&+
&+2+&
) ) ) )
) )
&O 2+
L 1D2+.
LL +
12 12
&O 2+
12 12
L 1D2+.
LL +
12 12
&O 2+
2 1 12 21 12
+2+
&O
&
12 12
3LFU\OFKORULGH 3LFULFDFLG
In picric acid substitution takes place at room temperature by using water. Due to strong electron withdrawing effect of
three nitro-group it is highly reactive and its intermediate carbanion is highly resonance stabilized by three nitro groups.
Relative Rate
12 12
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±

+2&+&
12 12
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12 12
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Illustrations
74. (a) Compare nucleophilic and electrophilic aromatic substitutions, (b) What kind of aromatic compounds undergo
nucleophilic substitution?
Ans. a) Nucleophilic aromatic displacement of =H–, a very strong base and extremely poor leaving group, is rare
and occurs only when an oxidant that converts =H– to H2O is present. The steps are similar except that the
intermediate is a arenanion in which the negative charge is dispersed to the ortho and para positions.
2RU
+ .)H &1
$U1X+2
1X $U+
±
$U
1X
$U1X +±
(b) Aromatic halides and tosylates. Such good leaving groups are more easily displaced, especially when elec-
tron-attracting substituents, such as NO2 and C = N, are ortho and/or para to the reacting C. The greater the
number of these ortho and para substituents, the more rapid the reaction and the less vigorous the conditions
required.
75. Show the structure of the intermediate arenanion formed from the reaction of Nu– with p-XC6H4G, where G is
(a) NO2, (b) C = N, (c) N — O, (d) CH = O, and (e) SO3H.
Ans.
; 1X ; 1X ; 1X ; 1X
(a) (b)
1 1 &Ł1 &
2 2 2 2 1
; 1X ; 1X ; 1X ; 1X
(c) (d)
1 1 & &
2 2 + 2 + 2
; 1X ; 1X
(e)
2 6 2 2 6 2
2+ 2+
76. Give the products of the reactions of 2,4-dinitrochlorobenzene with (a) aq. Na2CO3, 100 °C, (b) NH3, pressure,
(c) EtONa, (d) PhCH2SNa, and (e) MeNH2.
Ans.
2+ 1+
12 12
(a) (b)
12 12
'LQLWURDQLOLQH
'LQLWURSKHQRO
2(W 6&+3K
12 12
(c) (d)
12 12
'LQLWURSKHQHWROH 'LQLWURSKHQ\O
EHQ]\OWKLRHWKHU
1+0H
12
(e)
12
'LQLWUR1
PHWK\ODQLOLQH
77. For the reaction of p-halonitrobenzenes with MeO–, the experimental rate equation is rate = k2[p-XC6H4NO2]
[OH–] and the order of reactivity for the halides is ArF >> ArCl, ArBr > Arl. (a) Give a mechanism, (b) Explain
the order of reactivity of the halides. Why is this order evidence for the first step being rate-determining?
(c) Provide an enthalpy diagram for the reaction.
VORZ IDVWHOLPLQDWLRQ
(a) $U²;0H2± ;20H $U²20H;±
$U
LQWHUPHGLDWH
(b) Since F is the most electronegative of the halogens, it best stabilizes the-charge on the neighboring C’s in the
TS and in the intermediate. If the second step were rate-determining, ArF would react the slowest, because
F– is the poorest leaving group of the halide ions.
;
LQWHUPHGLDWH $U
20H
(QWKDOS\
$U20H;±
$U;0H2±
3URJUHVVRI5HDFWLRQ
78. Give the structure for the product of the reaction of 2,4,6-trinitroethoxybenzene with NaOMe.
Ans. The resulting ionic salt is called a Meisenheimer complex or salt, and its existence is taken as evidence for the
formation of the tetrahedral anionic intermediate that is at the dip in the curve in above figure.
(W2 20H (W2 20H
2 1 12 21 12
7KHFDWLRQLV1D

1 1
2 2± ±
2 2±
0HLVHQKHLPHUFRPSOH[ VDOW
79. (a) Compare nucleophilic addition-elimination (A-E) and electrophilic (E) substitution reactions with ArX
in terms of (i) number of steps, (ii) rate-determining steps, and (iii) character of intermediates, (b) Compare
nucleophilic A-E with SN2 reactions.
Ans. (a) (i) Both types of reactions have two steps, (ii) In E reactions, the first step is rate-determining which is also
usually true for A-E reactions. However, with certain nucleophiles and in some solvents, the second step
may be slow, (iii) In E reactions the intermediate is a cation, variously called a s complex, benzenium,
benzenonium, arenium or arenonium ion. The intermediate in A-E reactions is an anion, sometimes isolable
as a Meisenheimer salt with the countercation.
(b) For both, rate = k[substrate] [Nu–]. The same nucleophiles are effective (MeO–, RNH2, OH–),
and the rate increases with increasing nucleophilicity of attacking reagent. SN2 reactions go
through a one-step sequence involving a TS in which the three s-bonded nonreacting groups to the
C have a trigonal planar geometry, while the nucleophile and the group being displaced are 180°
from each other. In A-E there are two TS's; in the first step leading to the benzenanion, the aromatic
system is destroyed, and the hybridization of the reactive C changes from sp2 to tetrahedral sp3. In
the second step, the aromatic system is regenerated by loss of ‘Nu– or X:–, while C regains its sp2
hybridized state.
80. (a) Compare the rates of the reactions of piperidine, an unhindered cyclic 2° amine (R2NH) in base, with
4-nitrobromobenzene (A) and 3,5-dimethyl-4-nitrobromobenzene (B), and explain the difference, (b) Do you
expect a difference in the rates of the reaction of 4-cyanobromobenzene (C) and 3,5-dimethyl-4-cyanobromoben-
zene (D)? Explain.
Ans. (a) In the TS and the intermediate, stabilization occurs primarily through delocalization of the — charge to the
4-nitro group. See Figure(a) showing the intermediates for the reaction of R 2NH with A and B. The two Me’s
ortho to the nitro in B prevent it from achieving coplanarity with the ring, and delocalization is diminished. This
steric inhibition of resonance raises the enthalpy of the TS and slows the rate compared with that of A. (b) There
is little difference in the rates of C and D. The coplanarity of the CN group is hardly disturbed because of its linear
shape. See Figure (b) showing the intermediates for the reaction of R2NH with C and D. (The base in (a) and (b)
removes H from the N to form the intermediate.)

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²2 2²
1± 1±
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D E
Aryl halides only undergo substitution with extreme difficulty unless activated by electron-withdrawing
groups, its role being to stabilize the intermediate species and so lower the energy of activation of the first
step. In this respect, they serve the same purpose as donor groups in electrophilic substitution reactions.
Nitro, nitrile arid carbonyl are typical activating groups. Activation is best achieved when the group
is ortho or para to the halogen, since both inductive and mesomeric withdrawal of electrons operate.
The latter is of prime importance, providing additional resonance stabilization of the negative charge
of the intermediate. This is illustrated for l-chloro-2-nitrobenzene. A 3-substituent is much less efficient
at promoting nucleophilic attack since only the –I effect assists the process. Note that an electron-
withdrawing substituent also reduces the electron density of the ring, thereby helping the initial attack by the
nucleophile.
REACTIONS WITHBENZYNE AS THE INTERMEDIATE BY

ELIMINATION-ADDITION MECHANISM
When simple aryl halides react with strong bases such as the amide ion, NH2–, the base abstracts a hydrogen atom adjacent
to the C-halogen unit. The resulting carbanion acts as a nucleophile and displaces the halide ion in an intramolecular process
(an intramolecular reaction is one that occurs between two functional groups in the same molecule. In an intermolecular
reaction, different molecules are involved). The initial product is a highly reactive species called an aryne. It is rapidly
attacked by NH2–, or its protonated derivative NH3, now acting as a nucleophile. The final product, which results from
protonation of a second carbanion, is the new substituted benzene derivative.
2 2± 2 2± 2 2± 2 2± ±
2 2±
1 1 1 1 1 12
&O &O &O &O &O 1X
1X 1X 1X 1X ±&O
1X
+DO +DO 1+ 1+
±+DO±
+ 1+ DU\QH +
One disadvantage upon the use of benzyne in synthesis is that the nucleophile may attack at either end of the triple bond
of the benzyne, giving a mixture of two products if the benzyne is monosubstituted. For example, p-chlorotoluene with
hydroxide ion at 340°C gives an approximately equimolar mixture of m- and p-cresol.
0H 0H 0H 0H
±
2+ + 2

±+&O
2+
&O 2+
In the absence of nucleophiles, benzyne dimerizes to give biphenylene and, in the presence of dienes, it reacts as a
dienophile to give Diels-Alder adducts.
2
2

The common feature possessed by a base, B: or B:–, and a nucleophile, Nu: or Nu:–, is a lone pair of electrons. They
differ in that the base donates the lone pair to an H atom, whereas donation to a carbon atom is an example of nucleophilic
attack. Many species with a lone pair of electrons can act as both a base and a nucleophile.
Nucleophilic aromatic Substitution occur by an elimination-addition mechanism. This path way is followed, when the
Nucleophile is an exceptionally strong base such as amide ion (NH⊝2 ) in the form of KNH2 or NaNH2. Benzyne and related
arynes are intermediates in such reaction.
; % %
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+ Ւ +
%HQ]\QH
Electron withdrawing group will favour these reaction. These reactions can lead to substitution on the same carbon
that bore the leaving group or on an adjacent carbon. Order of reactivity in such reactions for various halide is RF < RCl
< RBr < Rl.
Benzyne is aromatic intermediate with one triple bond. Triple bond of benzyne is formed by pp–pp overlapping and
sp2 – sp2 overlapping which lies in the plane of the ring and does not interact with the aromatic p-system. This n bond is
relatively weaker p bond and will be readily attacked by nucleophile. Base act as a nucleophile and add to the strained
bond of benzyne to form a carbanion.
+
+ 'HJUHHRIRYHUODS
LVVPDOOHUWKDQLQ
WKHWULSOHERQGRI
+ DQDON\QH
+
Diel’s alder reactions of Benzyne

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Compounds containing two groups on both ortho position do not show this reaction as no benzyne will be formed. As
there is no ortho hydrogen to be lost, benzyne cannot be formed.
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+&2 &+
1+
QRUHDFWLRQ
1+
Isotope Effect
A difference in the rate due to a difference in the isotope present in the reaction system is called an isotope effect. Accord-
ing to this effect if a particular atom is less tightly bound the transition state of a reaction than in the reactant, the reaction
involving the heavier isotope of that atom will go more slowly.
For example when a 50 : 50 mixture of bromobenzene and o-deuteriobromo benzene is allowed to react with a limited
amount of amide ion recovered unreacted material contains more of the deuteriobromo benzene, the dueterated compound
is less reactive and is consumed more slowly.
%U 1+ %U
1+ 1+Ւ
1+ 1+
+ '
$QLOLQH
2UWKRK\GURJHQLVLQYROYHG R'HXWHULREURPREHQ]HQH
LQUDWHGHWHUPLQLQJVWHS 5HDFWVPRUHVORZO\
0RUHOHIWXQFRQVXPHG
On the other hand o-Deuteriofluorobenzene is converted into aniline only very slowly, but loses its deuterium rapidly
to yield ordinary fluorobenzene.
) )
Ւ
1+
1+
' +
Abstraction of hydrogen (Step I) takes place, but before the very strong carbon-fluorine bond can break, the carbanion
reacts with the acid, which is almost all NH3 with only a traces of NH2 D- to regenerate fluorobenzene but without its
deuterium. Where as in the case of o-deuteriobromobenzene, breaking of weaker carbon-bromine bond (Step II) is much
faster than he protonation by ammonia (reverse of step I) as fast as a carbanion is formed, it loses bromide ion.
m-bromo anisol and o-bromo anisol under same condition gives major products m-amino anisol. Ortho amino anisol is
minor product. It depends on stability of carbanion formed.
2&+ 2&+ 2&+
%U +
1+
+ %U
1+
2&+ 2&+ 2&+

1+
1+ Ւ
1+ 1+ Ւ
0RUHVWDEOH /HVVVWDEOH
Only inductive effect will be considered no resonance effects will be used to compare stability of carbanion as reso-
nance will not stabilize carbanion (can not disperse negative charge).
Aryl halides react with acetonitrile in the presence of ammonia and sodium amide to form benzylcyanide.
C6 H 5Cl + CH 3CN 

NH3 , NaNH 2
→ C H CH Cl
6 5 2
Chlorobenzene Benzy ln itrile (Benzyl cynide)
Mechanism
Halo arene undergoes the usual electrophilic reaction of benzene ring such as halogenation nitration, sulphonation and
Friedel Craft’s reactions.
The reaction proceeds through the initial formation of a benzyne. The anion of acetonitrile attacks this attacks this
intermediate in the manner shown below.
&O
1D1+
&+&1
Ւ
&+&1
1+
1+
Illustrations
81. (a) Give the product when PhCl is treated with (i) K+NH–2 in liquid NH3 at –33°C and (ii) aq. NaOH at 340°C.
(b) What products are formed when p-chlorotoluene is reacted with aq. NaOH at 340°C? (c) Explain why the
reactions in (a) and (b) are not considered to be addition-elimination reactions.
Ans. (a) (OPhNH2 + KCl and (ii) PhOH + NaCl. (b) m- and p-hydroxytoluene + NaCl. (c) (1) The halogen is not
activated by electron-Withdrawing G’s. (2) The base is much stronger ONH2) or the temperature is elevated
(340°C). (3) The entering group does not always occupy the vacated position (called cine
substitution).
82. (a) PhCl labeled at C1 with 14C reacts with KNH2 to give PhNH2 labeled at both C1 and C2. Classify the reaction
in Problem 81 (a) and give a mechanism consistent with this observation, (b) How does the mechanism for this
type of aromatic displacement account for the formation of the products in Problem 81 (b)? (c) Which property
of G, here CH3, affects the relative yield of these products? Explain.
Ans. (a) This reaction is an elimination-addition reaction. The strong base removes H+ to give a high energy
carbanion which ejects X– to give a triple-bonded intermediate called a benzyne (elimination). The
nucleophilic solvent adds to the very reactive benzyne (addition) giving the final product after redistribution
of H’s.
&O &O
1+ ±&O 1+
±+
+
DQLRQLQWHUPHGLDWH ³DEHQ]\QH´
1+
1+ 1+
UHGLVWULEXWLRQRI+¶V
RU

1+ 1+
The nucleophile bonds with the labeled benzyne at either C1 or C2 resulting in half of the radioactiv-
ity at each position. This is the same as saying that both positions are labeled, because chemically the
two radioisotopic isomers are indistinguishable. The radiocarbon is said to be scrambled between both
positions.
(b) This reaction is also an elimination-addition reaction. The benzyne from p-chlorotoluene can be attacked by
H2O at C3 giving m-hydroxytoluene or at C4 giving p-hydroxytoluene.
0H 0H 0H
+2IROORZHGE\

UHGLVWULEXWLRQRI+¶V
2+
2+
DEHQ]\QH IURPDWWDFNDW& IURPDWWDFNDW&
(c) The arene carbanion can only be affected by inductive effects, not by extended p orbital overlap [see Problem
82 (a)]. A-charge is better stabilized when generated as close as possible to an electron-withdrawing G and
as far away as possible from an electron-donating G such as CH3. Attack at C3 generates a-charge at C4 and
the major product is m-hydroxytoluene.
83. Show how a benzyne intermediate accounts for the formation of m-MeOC6H4NH2 (C) from either
o-MeOC6H4Br (A) or m-MeOC6H4Br (B).
Ans. Both isomers react through the same intermediate benzyne (D). It is the only benzyne that can arise from A, but
one of two possibilities from B.
20H 20H 20H

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1+ ±%U±
±+
$ '
20H
±%U±
'
20H
%U
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1+
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%U
%
%U
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The–charge in the carbanion is better stabilized when on C2, nearer to the electron-withdrawing MeO, as in E,
and not on C4. Consequently, little or no benzyne forms with the triple bond between C3 and C4. C results when
NH3 bonds to C3 of D, the–charge again ending up on C2.
20H 20H
1+ +WUDQVIHUVZLWK
'
1+VROYHQW

1+ 1+
PRUHVWDEOHDGGXFW
&
26. Predict the products in the following reactions:
&O &O
&O
.1+ .1+
(a) $ (b) %
1+ 1+
&O &O
.1+
(c) 1+
&
&O
SOLUTION
26.
&O &O &O

&O 1+
(a)
1+
Ւ
&O &O &O
(b) Ւ
1+
&O 1+
&O &O &O

1+
(c) Ւ
1+
&O
IPSO SUBSTITUTION
Nucleophilic attack can also occur at a position already occupied by a substituent, the ipso position. Such ipso substitutions
are not common, but they are industrially useful. An example is ipso nitration by displacement of a sulphonic acid group.
A proton can also displace the sulphonic acid group, with benzenesulphonic acid being converted into benzene.
Nucleophilic ipso substitution reactions also occur.
LSVRVXEVWLWXWLRQ
< < ( (
( ±<

62+ + 2+ 2+
+26 21
+ +12
+62
+ 2 DT+62
The more deactivating (electron-withdrawing) the substituent, the more it increases the acidity of a COOH, OH, or
NH3+ group attached to a benzene ring. For example, the pKa of substituted phenols are given below:
2+ 2+ 2+ 2+ 2+ 2+
2&+ &+ &O &+2 12

S.D
&22+ &22+ &22+ &22+ &22+ &22+
2&+ &+ &O &2&+ 12

S.D
SOLVED CONCEPTUAL EXAMPLES '

'±&O &+'&O
1. Predict the major product in each of the following ʌFRPSOH[&
reactions.
4. Give structure of the principal organic products
2
%U HTXLYDOHQW
expected from mononitration of
&+ 1D%+ (a) o-nitrotoluene (b) m-dinitrobenzene
" (c) m-cresol (d) m-nitrotoluene
%DVH
Sol.
Sol. &+ 12
2 12
(a) (b)
21 12
12
2. What would be the major product in following
reaction? 2+ &+
2 2 1
HT%U)H (c) (d)
1 " &+ 12
12
Sol.
2 5. Account for the following
%U
1 %U 3K 3K
&+ HT%U KY &+
+ & +&
3. When benzene is treated with DCl at low temperatures
a compound C6H6DCl(C), is formed. On warming the with little or no PhCH2C(Br)(CH3)2 formed.
reactants, C6H6 and DCl are re-formed. However, in 3K %UKY
the presence of AlCl3 an isomer of C6H6DCl(D) is Sol. &+
produced, which on warming, gives mainly C6H5D + &
and HCl. Explain
3K 3K
Sol. Since D is not incorporated into the benzene ring &+ DQG &+
in the absence of AlCl3, isomer C has no C – D s bond. + & +&
Instead, the D end of DCl is attracted to the p cloud of EHQ]\OLF DON\O
benzene to form a loosely bound p complex, indicated
by an arrow in the structural formula. p complexes %U %U
are also called charge – transfer complexes, because %U &+
the electron – rich benzene ring, the donor molecule, 3K 3K
transfers some electron density to the electron-poor &+
D of DCl, acceptor molecule. With the catalyst AlCl3, + & +& %U
exchange of D+ for H+ occurs on warming. This ex- PDMRU OLWWOH\LHOG
change requires the formation of a C – D bond to give This reaction proceeds via free radical mechanism form-
the s complex. with D+. The benzene ring is reformed ing 2 free radicals, of which 2° benzylic free radical is
by losing an H rather than the D because the C – H stabilized more by resonance of phenyl ring and with
bond is weaker than the C – D bond. Notice the delo- hyperconjugation of –CH3 group, thus resulting in the
calization of the positive charge in the s bond. formation of PhCH(Br)CH(CH3)2 as the major product.
+& DOF.2+ +%U 11. Give the products of the following reactions:
6. &+ KHDW
$ %
%U
1
Sol.
%U
+& (a) %U
$ &+ % +&
&+
&+
7. Oxidation of toluene by acidic KMnO4 gives poor
1%6'
yield of benzoic acid while oxidation of p-nitrotoluene 0J(W2
gives good yield of p-nitrobenzoic acid. Why? (b)
HWK\OHQHR[LGH
Sol. Oxidant is an electrophile, it can attack and de- +
stroy the ring in case of toluene. But in p-nitrotoluene, )
the –NO2 group deactivates the electrophilic attack
) )
on benzene nucleus and thus increases the yield of
p-nitrobenzoic acid. DQK\)H&O
(c) &O
8. What happens when p-xylene is treated with
concentrated sulphuric acid and the resultant product Sol.
is fused with KOH?
Sol.
&+ &+ &+ 1 1 1
62+ 2+ %U %U
FRQF IXVLRQ
+62 ZLWK.2+ (a) %U
PLQRU
&+ &+ &+ %U
S;\OHQH 'LPHWK\OSKHQRO PDMRU
9. Predict the major product in the following reactions: &+ 2+

C6 H 6 + (CH 3 ) 2 CHCH 2 OH → ? H 2SO4 1%6'
0J(W2
& &+ (b) HWK\OHQHR[LGH

+
Sol.
) )
&+ ) ) ) )
)H&O
10.
FRQF+12FRQF+62 (c) &O
&O
20H 12. Give the product(s) obtained from the reaction each of
In the above reaction which is the major product and the following compounds with Br2/FeCl3.
why?
&+ ZHDN &+ &+ (a) 2
12
12 12
Sol.
12
(b)
20H 20H 20H
VWURQJ PDMRU YHU\OLWWOH +& 2
Sol. 15. Complete the following:

(a) 2
2 %U
$O&O
(a) 2 "
&+12
12
(b) %U 2
2
+& 2 1D2&O
&+ "
(b) &
13. How will you synthesize
&+ +& 2
$O&O
(c) "
+& &O
from benzene?
+)
2 (d) "
+&
Sol. $O&O 2
2
&+ $O&O
&O Sol. (a) 2 &+12
&+
=Q +J +&O
&OHPPHQVHQUHGXFWLRQ 2
2
14. Complete the following reactions: 2
(a) 4-bromo-2-methylphenol treated with 2-methyl-
2+
propene and sulphuric acid.
(b) p-cresol treated with propanoyl chloride and alu- 2 2
minium chloride. 1D
(c) 2,5-dichlorophenol reacts with chlorine in acetic &+ 1D2&O 2
(b)
acid. &
Sol. 2
2+ &+ 2+ + & 2 &+
&+ &+ +& &+ (c) $O&O
+62

(a) + & +& &+
+ & &O
&+
%U %U
2+ 2+ 2 +)
(d)
(b) + & $O&O
16. Phenyl ring is known to exert negative inductive
2 &+ effect. But each phenyl ring in biphenyl (C6H5 – C6H5)
&+ &O &+ is more reactive than benzene towards electrophilic
substitution. Explain.
&O &O
Sol. Phenyl group also can exert +R effect; in biphe-
2+ 2+
&O nyl one of the phenyl groups acts as electron donor
(c) and other electron acceptor. This makes biphenyl
&+&22+
&O &O more reactive than benzene towards electrophilic sub-
&O &O stitution.
17. Fill in the blanks with appropriate structure of reaction &2+ &2+ &2+
products in the following transformations:
&RQF .+)
o — HOOC — C6 H 4 — CH 2 — C6 H 5 Sol. +62 )XVLRQ

SOCl2
→ A 
Anhydrous Zn − Hg
→ B  →C [IIT-1995] 62+ )
AlCl3 HCl

2 20. Predict the product
2
&O
Sol. (a)
&+ &O)H&O 1D±+J+&O
$ %
2 &O +12+62
&
(b) [IIT-2002]
2
(c)
Sol. (a) &O

18. Predict the structures of the intermediates/products in &O
the following reaction sequence. [IIT-1996]
20H 2 (b)
$O&O =Q+J+&O +32 &O
2 $ % &O
+2
2
2 12
20H
(c)
&O
20H 2&+
&O
Sol. (a) (b) 21. 7-bromo-1, 3, 5-cycloheptatriene exists as a ionic
&2+ &2+
substance whereas 5-bromo-1, 3-cyclopentadiene
does not ionize even in the presence of Ag+ ion.
2
Explain. [IIT-2004]
19. Convert
&2+ &2+ Sol. is aromatic and hence exists as ion but
the carbocation will be antiaromatic and hence

[IIT-2003]

) will not exists as ion even in presence of Ag+ ion.
STEP–I CHECK YOUR CONCEPT &+

(a) +&
1. Write the major product of the following reaction:
&1
+& %UKHDWOLJKW
1D&1 " (b) +&
&+ &1
(c) R 1&²&+ 8. In the Friedel-Crafts synthesis of toluene, reactants in

addition to anhydrous AlCl3 are
&+
(a) C6H6 + CH4 (b) C6H6 + CH3Cl
(d) P1&²&+ (c) C6H5Cl + CH3Cl (d) C6H5Cl + CH4
&+ 9. Which of the following compounds will be most
easily attacked by an electrophile?
2. Toluene, when treated with Br2/Fe, gives p-bromotol-
12 &O
uene as the major product because the –CH3 group
(a) is ortho-para directing. (a) (b)
(b) is meta directing.
(c) activates of the ring by hyperconjugation. 1+ &+
(d) deactivates the ring. (c) (d)
3. Identify the correct order of reactivity in electrophilic
substitution reactions of the following compounds: 10. In Friedel Craft’s alkylation, besides AlCl3, the other
&+ &O 12 reactants are
(a) C6H6 + NH2 (b) C6H6 + CH4
(c) C6H6 + CH3Cl (d) C6H6 + CH3COCl
11. The reaction,
Benzene + Methyl halide  
anhyd. AlCl3
→ toluene, is
(a) 1 > 2 > 3 > 4 (b) 4 > 3 > 2 > 1 known as
(c) 2 > 1 >3 > 4 (d) 2 > 3 > 1 > 4 (a) Kolbe reaction (b) Wurtz reaction
(c) Perkin reaction (d) Friedel-Crafts reaction
4. Which one of the following is a free radical sub-
stitution reaction? 12. Benzene does not undergo addition reactions easily
&+ because
$QK$O&O
(a) +&²&O (a) it has a cyclic structure.
(b) double bonds in it are very strong.
&O (c) resonance stabilized system is to be preserved.
(b) $J12 12 (d) it has six hydrogen atoms.
13. The melting points of isomeric xylenes are in the
2+ order:
(c) +& +&1 +& (a) p-xylene > o-xylene > m-xylene
2 &1 (b) p-xylene > m-xylene > o-xylene
(c) o-xylene > m-xylene > p-xylene
&+
%RLOLQJ &O (d) p-xylene > p-xylene > m-xylene
(d) &O
14. The correct order of C – C bond lengths in benzene
(I), ethane (II), ethylene (III) and acetylene (IV) is
5. The ortho/para directing group among the following is
(a) II > III > IV > I (b) IV > III > II > I
(a) –COOH (b) –CN
(c) II > I > III > IV (d) IV > III > I > II
(c) –COCH3 (d) –NHCOCH3
15. Which of the following groups is ortho and para
6. The treatment of benzene with isobutene in the
directing?
presence of sulphuric acid gives
&O
(a) isobutyl benzene (b) tert-butyl benzene
(b) n-Butyl benzene (d) No reaction (a) (b) –– CHO
7. Benzoic acid, when heated with soda lime yields 2
&+
(a) benzaldehyde (b) benzene
(c) toluene (d) benzylalcohol (c) –– OH (d)
(e) cyclohenxane 2
6. The most reactive compound for electrophilic

nitration is
1. The reaction of (a) Benzene (b) Nitrobenzene
+& (c) Benzoic acid (d) Toluene
2+ with HBr gives 7. The function of AlCl3 in Friedel Crafts reaction is
(a) to absorb water.
%U (b) to absorb HCl.
+& (c) to produce electrophile.
(a) 2+ (d) to produce nucleophile.
8. Which one of the following compounds will be most
+& easily attacked by an electrophile?
(b) 2+ &O
%U (a) (b)
%U
2+ &+
+ &
(c) (d)
(c) %U
+ & 9. Benzene reacts with CH3COCl gives

(d) %U (a) Chlorobenzene (b) Toluene
%U (c) Benzyl chloride (d) Acetophenone
10. Which of the following will have fastest rate of
2. The correct order of reactivity towards the electrophilic
reaction with Br2/FeBr3?
substitution of the compounds, aniline (I), benzene
(II) and nitrobenzene (III), is 12
(a) (b)
(a) II > III > I (b) I > II > III
(c) I > II > III (d) III > II > I &+ 2
3. Among the following compounds, the decreasing (c) (d) &+
order of reactivity towards electrophilic substitution
is 11. Among the following compounds (I–III), the correct
order in reaction with electrophile is
&+ 12
&+ 2 &)
+ &
, ,, ,,, ,9 , ,, ,,,
(a) III > I > II > IV (b) IV > I > II > III (a) II > III > I (b) III > I > II
(c) I > II > III > IV (d) II > I > III > IV (c) I > II > III (d) I = II > III
4. A group which deactivates the benzene ring towards 12. What is the end product obtained by nitration of
electrophilic substitution but directs the incoming toluene?
group towards o- and p-positions is (a) o-Nitrotoluene
(a) –NH2 (b) –Cl (b) p-Nitrotoluene
(c) –NO2 (d) –C2H6 (c) 2,4-Dinitrotoluene
(d) 2,4,6-Trinitrotoluene
5. Which species represents the electrophile in aromatic
nitration? 13. Ozonolysis of p-xylene gives
(a) NO -2 (b) NO +2 (a) Glyoxal (b) Methyl glyoxal
(c) NO2 (d) NO3- (c) Both of these (d) None of these
14. In the reaction, 2 2

)H&O
&O &O+&O 2
$ %
the attacking species is 2
(a) Cl2 (b) Cl+
(c) Cl– (d) FeCl-4
&
15. During electrophile substitution in benzene, the 2
intermediate species involved is 2
(a) Carbocation (b) Carbanion (a) B < A < C (b) B < C < A
(c) Free radical (d) None of these (c) A < B < C (d) A < C < B
&+
STEP–III CHECK YOUR EXPERTISE
4.
Confront the Conceptual Questions as Present JEE Pattern
1

MCQs with Only One Correct Answer
+
1. Increasing order of rate of reaction with Identify the position where E.A.S. (Electrophilic
2 2 2 Aromatic Substitution) can take place.
2 (a) 1 (b) 2
2
2 2 2 (c) 3 (d) 4
L LL
+ +12
2 2 5. $ %.
2 2 ' '
Product (B) in the above reactions is:

LLL 12
(a) iii < ii < i (b) ii < iii < i
(c) i < iii < ii (d) i < ii < iii (a)
2. Increasing order of rate of reaction with Br2/AlCl3
is:
2+ 2+
(b) 12
L LL
2 2+ (c)
2
12
LLL LY
(a) iii < i < ii < iv (b) iv < ii < i < iii
(c) ii < iv < iii < i (d) iv < ii < iii < i (d)
3. Rank in order of increasing rate of reaction towards
EAS with bromine in presence of FeBe3.
12
2 2 &+
&
6. 1+²&²&+
&+ (b)
& $
% (c)
Identify the position where electrophilic aromatic
substitution (EAS) is most favourable. &
(a) A (b) B &+
2
(c) C (d) A and C
(d)
7.
&
2 &+
D E F G
Decreasing order of rate of electrophilic aromatic sub- 10. Arrange the rate of electrophilic Aromatic substitution
stitution is: in their decreasing order:
(a) a > b > c > d
(b) a > c > b > d
(c) b > a > c > d
(d) b > c > a > d
8. Arrange the following in decreasing order of rate of
Nitration.
0H ' 12 &O L LL LLL
' ' (a) i > ii > iii
(b) iii > ii > i
(c) iii > i > ii
' ' (d) i > iii > ii
' 11. In which of the following compound electrophilic
D E F G H aromatic substitution take place in phenyl ring present
(a) b<c<a<d<e in left hand side?
(b) d<e<a=c<b 2
(c) d<a=c<e<b
(d) a<c<b<e<d (a) &²2
9. The major product of the reaction is
2
&+&2&O$O&O (b) &²1+

3URGXFW
+2
(c) &+²2
2
(a) &+²&
(d) &+²&
2
12. Which position will be attacked most rapidly by the 2

nitronium ion (–NO2)+ when the compound undergoes
nitration with HNO3/H2SO4 17. &O²& &O $O&O $ unknown (A) is:
$ % & '
2
&+
(a) A (b) B
(c) C (d) D
(a) (b) & 2
13. All the hydrocarbons shown are very weak acids.
One, however, is far more acidic than the others.
Which one is the strongest acid?
& 2
(a) (b) &O
&O
(c) (d)
2
14. Nitration takes place at the which position of the
given compound? (c) & 2 (d) 3K²&²3K
&0H
' $
&
% &+0H &O
(a) A (b) B 18. In the reaction given below, the major product formed is
(c) C (d) D 2
+) %U PROH
15. Suitable product of this 1 )H
3URGXFW
'
reaction is: 2
%U
(a) 1
2
(a) (b)
(b) 1
%U
2
(c) (d)
(c) 1
16. In nitration of benzene by mixed acid the rate of
reaction will be: %U
(a) C6H6 = C6D6 = C6T6 2
(b) C6H6 > C6D6 > C6T6
(c) C6H6 = C6D6 > C6T6 (d) 1 %U
(d) C6H6 < C6D6 < C6T6
19. Which one of the following compounds undergoes Identify the position where the nitration take place.
bromination of its aromatic ring (electrophilic aro- (a) 1 (b) 2
matic substitution) at the fastest rate? (c) 3 (d) 4
(a) (b) 23. Which one amongst the following carbocations is

most stable?
1 ⊕
+ (a) C6 H 5 - CH - C6 H 5
(c) (d)
1+ 1+
(b)
2
%U
12 (c) &+&&+
+2± &+
20. $ Product of the given reaction is:

%U
(d) &
%U 2+
12 12
$ %
(a) (b)
24. 12
2+ %U &
%U %U '
+2 12 12 (a) A (b) B
(c) C (b) D
(c) (d)
Identify the site where EAS (Electrophilic aromatic
+2 substitution) take palce:
%U
25. The decreasing order of reactivity of given compound
21. What is correct order of rate of nitration of the towards nucleophilic substitution with aqueous NaOH
following compounds? is
%U %U
C6 H 5 CH 3 C6 H 6 C6 D 6 C6 D 6
A B C D 21 12
+
C6 H 5 Br3 C6 H 5 N R 3 C6 H 5 NMe 2
E F G
12
(a) G>A>B>C>D> E>F
(b) G>B>C>D>A>F 12
(c) G>A>B=C=D>E>F , ,,
(d) G>A>B>C=D>E>F %U %U
12

22.

1+ 12 12
,,, ,9
(a) I > II > III > IV (b) II > IV > III > I
2 (c) IV > II > III > I (d) II > IV > I > III
26. Identify the end product (B) of the following sequence D

of reactions
2+
28.
FRQF+62 %U+2
$ % F
& H[FHVV G
E
2+ 2+ Identify the position where E.A.S. will take palce.
%U %U %U %U (a) a (b) b
(c) c (d) all the position are identical
(a) (b)
%U 29. Which of the following compounds forms ortho-
benzenedicarboxylic acid when oxidized by hot
62+
aqueous potassium permanganate?
2+ 2+
(a) (b)
62+ %U %U
(c) (d)
(c) (d)
%U %U
30. Which of the following alcohols would you expect
to form a carbocation most readily in sulphuric
27. Major product obtained in given reaction is acid?
+62
2+ 2+

(a) (b)
PROH
2+ 2+
2
(c) (d)
(a) (b) 2+
31. Which of the following will accept H+ ion with fastest

rate?
(a) (b)
1 1
1+ 1+
(c) (d)
(c) (d)
1
1+
32. Give the order of decreasing reactivity towards an %U

electrophilic reagent.
2+ &+ 12 %U
(a) &+
&22+ 1+ %U

%U
(a) 3 > 2 > 1 > 4 > 5 (b) 2 > 3 > 1 > 5 > 4
(c) 1 > 3 > 4 > 5 > 2 (d) 1 > 2 > 3 > 4 > 5
(b) &+
33. Give the order of decreasing reactivity towards an
electrophilic reagent.
&²1+ %U
&+&O &+) &+ &+&O
2
%U

(a) 1 > 3 > 2 > 4 (b) 3 > 4 > 1 > 2 (c) &+
(c) 2 > 4 > 3 > 1 (d) 4 > 2 > 1 > 3
34. Nitration of the following compound 1+ %U
2
%U
&+ 1 gives:
(d) +1 &+
2 12
&22+ 1+
(a) &+ 1
2
12
2 %U)H
36. 1 HT
(b) &+ 1
%U
12 2 2
(c) &+ 1 (a) 1
12
%U
2
2
(d) &+ 1
(b) 1 %U
&+
35.
(c) 1 %U
&²1
2 +
%U)H +2' PRQREURPLQDWLRQ (d) 1
PRQREURPLQDWLRQ 3LV
37. Amongst the following which one will undergo the &+ 2+
fastest SN reaction?
%U&&O
&O &O 40. &+ &+
The product is:

(a) (b)
&+
0H 0H 2+ 2+
12 12
(a) (b)
&O &O
%U &+ %U &+
&+ &+
(c) (d)
12
1+
38. In which case SN2 Ar reaction is fastest? &+ &+

&O &O 2+
12
(c) (d)
(a) (b)
%U &+ %U
&+ &+
12 2+
%U &O
12
(c) (d)
&O
&O
1+ 12 41. 1D2+
'
1
12 2+
&O &O
(W21D
39. The product is (a) (b)
PRO '
&O 1 1
2+
&O
2+ &O
12 12 2+
&O
(c) (d)
(a) (b) 1 &O 1
&O
2(W 2(W
2
12 12 FRQF+12
42. In the following reaction, 1 FRQF+62
;
+
(c) (d)
(W2 &O 2(W →

conc. HNO3
conc. H 2 SO 4
X the structure of the major product
&O &O ‘X’ is
2
12
(a) 1
+
21
2
(b) 1 45. The correct sequence of reagents of prepare m-bromo

+ iodobenzene from nitrobenzene is
(a) 
(1) NaNO2 /HCl
(2) KI
→ 
Sn/HCl
→ 
Br2 /FeBr3
→
2 (b) 
Sn/HCl
→ 
Br2 /FeBr3
→ 
(1) NaNO 2 /HCl
→
(2) KI
(c) 1 (c) 

Br2 /FeBr3
→ 
Sn/HCl
→ 
(1) NaNO 2 /HCl
→
(2) KI
+
12 (d) 
Br2 /FeBr3
→ 
(1) NaNO 2 /HCl
(2) KI
→ 
Sn/HCl
→
2
FRQF+62
46.
(d) 21 1 62+
+
Mark out the incorrect statement:
(a) Hexa deuterated benzene gets sulphonated slower
43. Arrange in the increasing order of boiling points than simple benzene.
⊕
2+ 2+ 2+ 2+ (b) Electrophile in the reaction is SO3 H .
2+ (c) Dilution of acid during reaction promotes reversal
(desulphonation).
(d) Polysulphonation is hard to proceed.
2+
2+ 2
, ,, ,,, ,9
0H&²&²&O
(a) I < IV < III < II 47. 3URGXFW
$O&O
(b) IV < III < II < I
(c) I < II < III < IV The final product is
(d) I < II < IV < III 2
& &0H
(a)
&+&2&O 1+1+
44. $O&O
$ .2+'
% (b) is 2
& &0H &0H

(b)
2 2 &²&0H
(a) (b) &0H

(c)
(d) None of these

2 &+
48. 0H2 2+&O 6 0H 0H&±&O 3K±&2&O %U$O&O

50. Product is
$O&O $O&O
2
+&O %U )H +
2 2
0H 0H
The major product is &±3K %U &±3K
%U (a) (b)
(a) 0H2
& 0H
%U
2 2
0H 0H
(b) 0H2 2+
&±3K &±3K
(c) (d)
%U
%U
(c) 0H2 %U & 0H
51. The end product of the following reaction sequence is

(d) 0H2 2+
2&+
2
%U
'U\$O&O =Q±+J+&O'
2
2+ 0H
2
$J12 62&O3\ULGLQH 'U\$O&O 2+Ւ WDXWRPHULVHV
49. 3K & & 3K "
$ +2
0H ,
2&+ 2+
Major product is
2+ 12
(a)
(a) 3K & & 0H
2&+
&+ 3K 2+
0H
(b)
(b) 3K & & 0H
&+2 2+
3K 2
(c)
0H
2+
(c) 3K & & 0H
&+2
2 3K (d)
(d) None of these
52. Which of the following is best sequence of reagents X Y Z

for the conversion of &+ 12+ &21+
&+ &O
(a)
20H
%U 20H 20H
⊕
12 &O &21+
(a) 
Br2 /Fe
→ →
conc. H 2SO4
D

CH3Cl/AlCl3
→ 
H 3O
D
→
⊕
(b) 
CH3Cl/AlCl3
→ →
conc. H 2SO 4

Br2 /Fe
→ 
H 3O
D
→ (b)
3Cl2 /hυ
(c) 
CH3Cl/AlCl3
→ → 
Br2 /Fe
→ 
Zn /HCl
→
20H 20H 20H
(d) 
HNO3 + conc. H 2 SO 4
→ 
CH3 Cl/AlCl3
→
&21+ &1 12

Sn /HCl
→ →
NaNO 2 /HCl

CuBr
→
(c)
53. The major product of the following reaction sequence
will be 0H2 0H2 0H2
3K&2&O3\ULGLQH &+&2&O$O&O &1 &22± 1+ &O

2+
=Q±+J+&O' %U)H (d)

20H
(a) &+&+ 2 & 20H 20H
2 %U 55. Which of the following is regenerated at the end of the

reaction
(b) + &²&+ 2 & &+ 621D2+ 6Q+&O

S±1LWURSKHQRO

;
%U 2 1D12+&O &+2+ 1D2+&+%U 6Q+&O
&+²&+ < =

1D12+&O 1D12 +,
(c) %U 2 & : "
&X12

2
(a) X (b) Y
(c) Z (d) W
(d) &+²&+ 2 &+
56. The products R and S are respectively
%U
12 .0Q22+Ւ' %U)H
54. In the following reactions X, Y and Z are respectively ; : 5
6Q+&O
1+
.0Q22+Ւ' %U)H
< = 6
+1L %U.2+'
; =
1+
+22& %U +22&
20H (a) DQG
1D1+1+ O
+22& +22&
< %U
+22& %U
(b) 5DQG6DUHVDPHSURGXFWV
+22& +3G&
(b)
12
+22& +22& %U
(c) DQG
+22& %U +22&
12 12
+22& +22& EXWQRW
(d) DQG
+22& %U +22&
%U 2 2 2
1 1 1
MORE THAN ONE CORRECT ANSWER 12
FRQF+62FRQF+12
(c)
1. Friedal craft acylation can be used to obtain:
2 2
12
& &+ & &+
12 12
(a) (b)
FRQF+62FRQF+12
(d)
+&2 + & 12
2 2
& &+ 0H
& &+ 12
6Q &+&2 2 +12 2+±
3. $ % & '
(c) (d) +&O +62
&O
6Q+&O2+± 1D12+&O
2 1 1 * +12
) &X&O'
(
+32
+& &+
The compound B, E G are
2. Explain the following observations.
0H
) 2+
2+Ւ 1+&2&+
(a) )±
(a) %
2 1 21
&+ &+
0H
)
2+Ւ &O 1+
1RUHOHDVHRI)±
(b) *
12
21
0H P Q
1+ &22+ &22+
(c) (
(a)
12
12 12
0H
&O &22+ &22+
(d) *
(b)
&O
0H 12 12
+12 .0Q2 6Q+&O +2' &22+ &22+

4. $ % &
+62 + 2+Ւ
12
±&2 (c)
' (%&(PD\EH
&22+ 12
21 12 &22+ &22+
(a) %
(d)
12
12
&22+ 12
1+ 1+
(b) & 12
6Q+&O
.0Q2
µ[¶
6. % $
1+ .0Q2
>2@
µ\¶
&22+
1+ 1+ ‘x’ and ‘y’ are respectively
(c) ( 12
&22+ &22+
1+ (a) % DQG $
&22+ &22+
+2 +2
(d) ( 1+
&22+ &22+
+2 (b) $ DQG %
5. Considering the following reactions, P and Q will be: &22+ &22+
&+ 1+ 12

.0Q2 +12+62
;
3 &22+ &22+
(c) $ DQG $
+12+62 .0Q2
< ' 4 &22+ &22+
&22+ &22+ 8. Which of the following reactions give alkylation

(d) % DQG %
product?
2+
&22+ &22+
+
(a)
7. Which of the following electrophilic substitution
reaction represent correct product?
(b) +

12
%U)H%U $O&O
(a) (c) &+&2&O
2&+
12 $O&O
(d) 0H&²&2&O
%U
2&+ ASSERTION AND REASON TYPE
1. Statement-1:
+
%U)H%U & is less Acidic than

(b)
2 2
7ULSKHQ\OPHWKDQH
%U
+
2 2 &
)OXRUGDQH
&22&+
%U)H%U
(c) 2&+
Statement-2: coplanar arrangement of three rings in
&22&+ tluordane, allows more extensive delocalization in
conjugate anion.
2&+ (a) Statement-1 is True, Statement-2 is True; State-
(b) Statement-1 is True, Statement-2 is True;
%U
Statement-2 is NOT a correct explanation for
Statement-1.
%U)H%U (c) Satement-1 is True, Statement-2 is False.
(d) & &+
(d) Statement-1 is False, Statement-2 is True.
2
2. Statement-1: Polycylation in benzene does not occur
&²&+ during friedel Craft’s acylation.
2 Statement-2: As the product ketone is much more re-

%U active than starting material.
(a) Statement-1 is True, Statement-2 is True; State- &O&+&+&O &+&+&+&O

ment-2 is a correct explanation for Statement-1. 1. µ$¶ µ%¶
$O&O $O&O
(b) Statement-1 is True, Statement-2 is True; State-
ment-2 is NOT a correct explanation for State- ‘A’ and ‘B’ are respectively:
ment-1.
&+ &+
(d) Staternent-1 is False, Staternent-2 is True. &+&O &+ &+
(a) $ %
3. Statement-1: 1, 3, 5 trihydroxybenzene reacts with
NH2OH to give oximino derivative where as 1, 3
dihydraxy benzene do not. &+&+
(b) $
2
&+
Statement-2: Former exist in which &+ &+
2 %
2
12+ &+
&+&+&O &+ &+
gives where at later exists in (c) $ %
12+
12+
&+&+&O &+&+&+
2+ (d) $ %
no substantial keto form is present

2+ 2.
)&+&+&+&O
3URGXFW
which can give oximino derivative. %&O
(a) Statement-1 is True, Statement-2 is True; State- Predominant product is:
(b) Staternent-1 is True, Statement-2 is True; State- &+&+&+)
(a)
ment-2 is NOT a correct explanation for State-
ment-1.
(c) Satement-1 is True, Statement-2 is False. &+&+&+
(d) Statement-1 is False, Statement-2 is True. (b)
COMPREHENSION TYPE &+&+&+&O

(c)
COMPREHENSION-I
Alkylation of aromatic rings, called Friedel-Craft’s &+
alkylation. Most important reagents are alkyl halides, &+ &+)
olefins and alcohols. When alkyl hatides are used, the (d)
reactivity order is F > Cl > Br > 1. Di and trihalides, when
all the halogens are at same, usually react with more than
one molecule of aromatic compound. It is usually not 3. Which of the following statement is incorrect?
possible to stop reaction earlier. Reaction proceeds through (a) Friedel-Craft reaction (alkylation) with respect to
carbocation formation. When R-X is primary halide, a simple olefins is electrophilic addition of ArH.
carbocation doesn’t form. A complex with Lewis acid forms (b) In Friedel-Craft alkylation mainly alkyl halides,
in which the carbon-halogen bond is nearly broken and in olefins and alcohols are used but other types
which carbon atom has a considerable positive charge. So, of reagents e.g., ethers, thiols, sulphates,
rearrangement mostly possible. Alkylation activates the sulphonates, alkyl nitro compounds even alkanes
benzene ring, while acylation deactivates the ring. and cycloalkanes have been employed.
(c) Alkylation (CH3–CHCICH2CH3, AICI3) with HT+1O

respect to alkylhalide proceeds through SN1, 2. 3
racemisation occurs.
(d) Friedel-Crafts alkylation is electrophilic substitu- P will be
tion, thus reaction proceeds most efficiently with
highly activating groups .e.g., NH2, NHR, OH, etc. (a)
COMPREHENSION-II
(b)
Aromaticity is a chemical properly in which a conjugated
ring of unsaturated bonds, lone pairs or empty orbitals
exhibit a stabilization stronger than would be expected (c)
by the stabilisation of conjugation alone. It can also be
considered a manifestaion of cyclic delocalisation and
of resonance. An aromatic compound contains a set of
(d)
covalently bound atoms with specific characteristics.
(i) A delocalized conjugated system, most com-
monly an arrangement of alternating single and 2
double bond. G
(ii) Coplanar structure with all the contributing F %U)H
atoms in the same plane. 3. 3URGXFW
E '
(iii) Contributing atoms arranged in one or more rings.
D
(iv) A number of p delocalized electrons that is even,
but not a multiple of 4. This is known as Huckel’s In the product Br will be primarily at
rule. Permissible number of p electrons include (a) a and b (b) a and c
2, 6, 10, 14 and so on. (c) a and d (d) c and d
(v) Special reactivity in organic reactions such
as electrophilic aromatic substitution and COMPREHENSION-III
nucleophilic aromatic substitution. Whereas
&22+
benzene is aromatic, cyclobutadiene is not.
Aromatic compounds typical display enhanced 62&O 6ROLG12 &+ &X/L
chemical stability as compare to similar non- 4 5 6
aromatic molecules. )H+
L 1D12+
7 LL 3K2+2+Ւ
8
1. Aromatic among the following compounds is/are
1 1. The product U is
1
1
, ,, ,,, &+
1 1
1 1 1 (a) &
2
+ 1 1 2+
,9 9 9, 0H
1 2
1
0H
Ւ (b) +& & 1 1 2+
9,, 9,,,
(c) 1 1 2+
(a) I, II, III, IV, V, VI
(b) I, II, III, IV, V, VI, VII +& &
(c) I, III, V, VI, VII, VIII
(d) I, II, III, IV, V, VII 2
(d) 1 1 2+ (c) (d)
&+&+ 3K 3K
2. S on reaction with Cl2/NaOH or on reaction with 2. What product is obtained when (X) is heated with
Cl2/NaOH followed by acidification will not give conc. H2SO4?
which of the following?
2
12 12
(a)
(a) (b)
&221D &+&221D
12 2
2
(c) CHCl3 (d)
&22+ (b)
3. T on reaction with NaNO2/HCl followed by reaction

with H3PO2 will give 2
&+&2&+ &2&+ 2
(a) (b) (c)
&+ 2
2
&2&+ &2&+ 2
(c) (d) (d)
2+
COMPREHENSION-IV 3. What product is obtained when W is heated with

&+ &2 KMnO4/OH?
$O&O =Q +J +&O'
2 &+2 &22+

&+ &2 ;
(a)
62&O $O&O +3W
&+2 &+2&O &+2 &22+

< = :
&22+
+62' 3WKHDW (b)
&+2 &+ &+ + &22+

5 6 7
1. What product will be obtained if ‘W’ is treated with (c) 2

C6H5MgBr followed by D3O and then by heating?
2
(a) (b)
3K (d) 2
2' 2'
MATRIX MATCH TYPE 3. Match the following:

Column-I Column-II
H
Column-I Column-II
(a) H

(p) Aromatic (p) Anti aromatic
(a)
1RQ3ODQDU

(b) (q) Aromatic

Ւ
(b) (q) Anti aromatic H
(c) (r) Non aromatic
Ւ
3ODQDU
Ւ

(c) (r) Non aromatic (d) (s) G.F = CnHn
3ODQDU
Պ
12
(d) (s) (4n + 2)p e– 6Q+&O
&+&2 2 +12 'LO
4. $ % &
Ւ +62 +62
%U
2. Match the following: &X%U
+32 6Q+&O 1D12
Column-I Column-II * ) ( '
1D12+62 +62
+ +%)'
% +
Write the correct combinations.
(a) (p) Aromatic
Column-I Column-II
%U
2 %U %U
(b) (q) Nonromantic (a) A (p)
+ %U
%U %U
%
(b) B (q)
+1 1+
(c) (r) Antiaromatic
+% %+ )
1 (c) G 1+&2&+
%+
(r)
(d) (s) Inorganic benzene
2 12
1+&2&+ 4. Indicate the most probable sites for ArSE reaction.

2
(d) H (s)
(a) & 2

SUBJECTIVE ANSWER TYPE
12 (b) 12

&+ 62 =Q+&O' 1D12+&O
1. , ,, ,,, 12
Ւ
2+ &
3KHQRO %U+2
2+ ,9 9 (c) &+
1D2+

The steps involved in the above reaction can be
arranged as,
(d)
Electrophilic substitution = step (w)
Nucleophilic substitution = step (x)
Reduction reaction = step (y)
Diazocoupling reaction = step (z) 1+&2&+
Assign the correct numbers to the type of reactions as
follows w x y z (e)
1+
2. Observe the following reaction sequence 1+ 2
1D2+ HT +&1+&O$O&O
3KHQRO ; <
0H
2
' ,
+ 2
1+±1+3K
= & $O&O'
&O $
&+ &O
Answer the following questions in the given format 5. &
P Q R S
2
P = Number of organic products formed in step-1 1D&+2+ '
Q = Number of organic products formed in step-2 % &
(significant products)
R = Number of organic products formed in step-3 6H'
(significant products)
S = In which step aromatic electrophilic substitution '
has taken place
Find the molecular weight of the compound
&+&O$O&O %UKY HT 1DHWKHU C and D.
3.

%UKY HT 6. In the following sequence of reaction how many
PRQREURPLQDWLRQ nucleophilic substitution taking place.
2
DOF.2+' 2+
62&O DOF.2+ &O±&±&O
L 2 $O&O
3
LL =Q&+&22+
PROHV &+0J%U +%U
Find the structure formula and molecular weigth ‘P’. +
ANSWER KEYS
STEP-I
1. (a) 2. (a, c) 3. (c) 4. (d) 5. (d) 6. (b) 7. (b) 8. (c) 9. (c) 10. (c)
11. (d) 12. (c) 13. (a) 14. (c) 15. (c)
STEP-II
1. (b) 2. (c) 3. (a) 4. (b) 5. (b) 6. (d) 7. (c) 8. (c) 9. (d) 10. (d)
11. (c) 12. (c) 13. (c) 14. (b) 15. (a)
SOLUTIONS
STEP-III 8. (b) s – complex formation is r.d.s.
1. (d) 9. (c) On the basis of hyperconjugation

2+ 2+ 6' ∴ isotope has no effect on rate of reaction.
2. (a) 10. (b)
:: :'
2
:' :' Į
L LL 11. (d) &+ &
+ ±0
2 2+ 6'
2
0RUHHOHFWURQULFKULQJ
6: 6'
12. (b) On the basis of p-Complex stability
:' :'
LLL LY Ւ
SD = strong donating 13. (c)
WW = weak withdrawing ∴ iv > ii > i > iii
WD = weak donating $URPDWLF
3. (a) C > A > B 14. (b) –CHMe2 (Hyperconjugation)

+M +M –M
+H –M +H
+H = hyperconjugation
+±)
15. (b)
4. (a) More activated ring will undergo electrophilic
attack. )ULHGHO&UDIWDON\ODWLRQ
5. (b) Intramolecular electrophilic aromatic substitution
then nitration with respect to phenyl ring. 16. (a) R.D.S. is < s – complex formation
∴ C6H6 = C6D6 = C6T6
2
17. (c)
6. (b) 1+ & &+ 0JURXS (More acti-
18. (d) More activated ring undergo electrophilic aromatic
vating group) substitution.
7. (b) 19. (b) +M of –NH
20. (b) –NO2 is ortho-para director for SNAr 12 2

21. (c) s–complex formation is reductions
∴ C6H6 = C6D6 = C6T6 &+ 1
electron donating group increases rate
electron withdrawing group decreases rate. %U)H
35. (a) &+
22. (a) PRQREURPLQDWLRQ
23. (d) very stable carbocation. & 1
24. (b) At meta of NO2, benzene does not show resonance. 2 +

%U
25. (b)
2+ 2+
&+
%U %U
26. (d) (a) (b) & 1+
2
62+ %U
36. (b)
27. (b) 28. (b) 37. (b) –NO2 is deactivating group
Į &2+ 38. (b) 39. (a) 40. (b)
.0Q2
29. (b) &O 2+
Į &2+ &O &O
1D2+
41. (b)
2+ PRO '
1 1
+ ±+2 42. (b)
30. (b)
+62 2+

43. (c) h as highest boiling point due to maximum
intermolecular H-bonding
Stable carbocation (The central ring has also become 2+

aromatic and an tropylium cation is formed.) (Due to 44. (b)
formation of more stable carbocation) 12 12 1+
1+ 1+
%U)H%U 6Q+&O
+ 45. (c)
31. (d)

1 1 %U %U
O
+
The lone pair at N is not delocalized in the ring. : NH2 1D12+&O
group exerts +m effect. .O
32. (b) 33. (b) %U

34. (c) 2
46. (b)
12
&+ 1
47. (c)
OHVVDFWLYDWLQJ PRUHDFWLYDWLQJ
48. (d)
RSGLUHFWLQJ
2 2&+
0H2 2 +&O 6 0H =Q±+J+&O

&OHPHQVHQ¶V
2 5HGXFWLRQ
2 2
&+
±+&O 3\62&O
0H2 2 6 0H &+ &+ & 2+

2&+
2
2 'U\$O&O
%U)H
0H2 2 6 0H 2

2 &+±&+ &+ & &O

%U
2
2&+ 2&+
+
0H2 2 ++2 6 0H
2+±+2
2 2+ WDXWRPHUL]DWLRQ 2
%U
+
2+ 0H 2+ 0H
+
3KVKLIW
49. (b) 3K & & 3K & & 3K &+ &&O

0H 0H 3K &+&O$O&O &OKY
52. (c)
0H
±+
3K & & 0H &&O &+
%U)H =Q+&O
3K 2
0H 0H
%U %U
50. (c) 0H&±&O 3K±&2&O
53. (b)
3K&2&O
$O&O $O&O 3K&2&O
3\ULGLQH
2+ 3\ULGLQH 2 &
2+ %HQ]R\ODWLRQ
%HQ]R\ODWLRQ
2 &
&0H 2
2 2 2
0H 0H
&+&2&O$O&O
&+&2&O$O&O + & & 2 &
&±3K &±3K + & & 2 &
%U$O&O
,362DWWDFN 2 2
2 2
&OHPPHQVHQ
&OHPPHQVHQ
UHGXFWLRQ
&0H %U UHGXFWLRQ
51. (d) =Q±+J+&O

+ & &+ 2 & =Q±+J+&O
'
2&+ 2&+ + & &+ 2 &
2 '
'U\ 2
$O&O 2
2 %U
%U
%U)H
2 &+ &+ 2 & %U)H
2 & &+ &+ 2 &

2 &+ &+ & 2+ 2
2
2 56. (c)
12 1+ &1+

54. (b) +1L %U.2+'
12
12
1+
20H 20H 20H
12 6Q+&O .0Q22+Ւ'
; ; ; 1+
12
1D1+1+ р 6Q+&O < .0Q22+Ւ'

; &22+
R[LGDWLRQ .0Q22+Ւ'
&O <
R[LGDWLRQ .0Q22+Ւ' &22+
=
PRUHH±ULFK
ULQJLVR[LGL]HG
&22+
=
20H %U±ULFK
PRUHH )H
ULQJLVR[LGL]HG
<
12 12%U )H
2+ 2&+ 2&+
+22& +22&
%U)H
55. (a) 12
12
+22& +22& %U
: %U)H 5
12 12 1+ PRUHH±ULFKULQJ
+22&
LVR[LGL]HG +22& %U %U
; < : 5 &22+
2&+ PRUHH±ULFKULQJ
LVR[LGL]HG %U &22+
6
2&+ 2+ &22+
6
1

1
1+ 12
: ;
2+
=
MORE THAN ONE CORRECT ANSWER
1. (a, b, d) 2. (a, b, c) &22+

3. (a, c, d) 4. (a, b, c)
5. (c, d) By process (X), –CH3 group is first oxidised 3
to –COOH which is m-directing. Hence, P is 12
m-nitrobenzoic acid.
By process (Y), –CH3 group is O – and p-directing COMPREHENSION TYPE -I

and –CH3 group is oxidised to –COOH. Hence, Q is a 1. (c) 2. (c) 3. (a)
mixture of O- and p-nitrobenzoic acid.
COMPREHENSION-II
&22+ &22+ 1. (d) 2. (b) 3. (b)
12
COMPREHENSION-III
4
1. (c) 2. (b) 3. (c)
62&O 1 2
12

6. (a) The electron-attracting -NO2 stabilizes ring A of +22& &O±&

1-nitronaphthalene to oxidation, and ring B is oxidized 2
to form 3-nitrophthalic acid. By orbital overlap, – 3 4
••
N H 7 releases electron density, making ring A more
susceptible to oxidation, and a-naphthylamine is &+ &X/L
12 12
oxidized to phthalic acid. The NO2 tables one ring and
+&
establishes the presence of two fused benzene rings in &2&O &
naphthalene.
2
5 6
7. (a, b, d)
8. (a, b, d) )H+ L 1D12+

2+ 1+
LL 3K2+2+Ւ
+&
(a) &
2 7
1 1 2+
+&
&
2
(b)
COMPREHENSION-IV
1. (c) 2. (c)
2
3. (d) L 3K0J%U
& LL '2 +
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3. (A → r, s); (B → r); (C → q, s); (D → s) +&±1+ +&±1+ &+ 2
< RS
3. (A → s); (B → r); (C → p); (D → q) 2+ 2±+
&+
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Ans.
5 1 2 4 Ans. M.F. (P) = C7H6O; M.W. (P) = 84 + 6 + 16 = 106.
4. (A) p-airing-2, (B) p-at ring-1, (C) p-at ring-2, 6.

(D) o-at ring-2, (E) o-wrt NHCOCH3P
2+ &O
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PREVIOUS YEARS’ AIEEE QUESTIONS
1. The electrophile, E⊕ attacks the benzene ring (d) deactivates the ring towards electrophilic substi-
to generate the intermediate s-complex. Of the tution.
following, which a-complex is of lowest energy?
3. The reaction of toluene with Cl2 in presence of FeCl3
[2008] gives predominantly [2007]
12
+ (a) benzoyl chloride
(a) (b) (b) benzyl chloride
(
(c) o-and p-chlorotoluene
(d) m-chlorotoluene
+ (
4. In the chemical reactions, (2010)
12 12
+ 1+
(c) ( (d) + 1D12 +%)
( +&O.
$ %
2. Presence of a nitro group in a benzene ring [2007]
(a) activates the ring towards electrophilic substitu- the compounds 'A' and 'B' respectively are
tion. (1) nitrobenzene and fluorobenzene
(b) renders the ring basic. (2) phenol and benzene
(c) deactivates the ring towards nucleophilic substitu- (3) benzene diazonium chloride and fluorobenzene
tion. (4) nitrobenzene and chlorobenzen
ANSWERS KEYS
1. (b) 2. (d) 3. (c) 4. (c)
SOLUTIONS
: +
+
(
( 0
:
+
+
1. (
(
+
0 HOHFWURQUHOHDVLQJJURXS
( (
: HOHFWURQZLWKGUDZLQJJURXS
5HDFWLRQFRRUGLQDWH
Electron withdrawing group destabilises the arenium ion s-complex.

Պ Ւ
2 1+ 1&O
1
2.
2
1D12 +%)
4.
+&O.
—NO2 group withdraw electron from the ring, shows
–M effect, makes ring electron deficient, thus deacti- $
EHQ]HQHGLD]RQLXP
vates ring for electrophilic substitution. FKORULGH
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3.
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CRACK THE IIT-JEE QUESTIONS PREVIOUS YEARS’ IIT-JEE QUESTIONS
STRAIGHT CONCEPTUAL TYPE &+ &O 12
1. Identify the correct order of reactivity in electrophilic

substitution reaction of the following compounds:
(2002)
(a) 1>2>3>4 &+&+&+ &+2

(b) 4>3>2>1 (b) , ,
(c) 2>1>3>4
(d) 2>3>1>4 3 4
2. The major product obtained when Br2/Fe is treated CH3CH2OH

with (R)
2
+1 &+ &+
2+
+ & &+ is (2004) (c) , ,
3 4
2 CH3COCH3
+1
(R)
+& &+
(a) &+ &+ 2+

%U (d) , ,
2
+1 3 4
+& &+
CH3CH(OH)CH3
(b)
(R)
%U 4. In the following reaction, (2007)

2
+1 2
+& &+
(c) 1 FRQ+12
+ FRQ+62
;
the structure of the major product ‘X’ is

%U
2 2
+1 (a)
12
+& &+ 1
(d) +
%U
21
2
3. Identify the major products P, Q and R in the following (b)
reaction. (2006) 1
+
DQK\GURXV L 2
&+&+&+&O 3 45
$O&O LL +2'
2
(c)
&+&+&+ &+2 1
+
(a) , ,
12
3 4
&22+ 2
(d) 21 1
+
5
5. The compounds P, Q and S (2010)

&22+ 2&+
&22+ 2&+
(c) +2 +& 12
+2 +& 12
3 4
2 12
2
&
& 2
2
6
were separately subjected to nitration using HNO3/ &22+ 2&+
H2SO4 mixture. The major product formed in each
case respectively, is (d) 12
+2 + &
&22+ 2&+
12
(a) +2 + & 2
12 12
&
2 2 12
&
2
21 SHORT ANSWER TYPE
&22+ 2&+ 1. Give reasons for the following: (2000)

tert-Butylbenzene does not give benzoic acid on
(b) +2 12 + & treatment with acidic KMnO4.
12 2. Normally, benzene gives electrophilic substitution
reaction rather than electrophilic addition reaction
2
although it has double bonds. (2000)
& 3. 7-bromo-1,3,5-cycloheptatriene exists as an ion
2
whereas 5-bromo-1, 3-cyclopentadiene does not form
12 an ion even in the presence of Ag+. Explain. (2004)
ANSWER KEYS
1. (d) 2. (b) 3. (c) 4. (b) 5. (c)
Short Answer Type substitution reactions in which hydrogen atom

1. T he first step in the oxidation of side alkyl chain attached to carbon atom is replaced by another atom
is to abstract a benzylic hydrogen. Since no such or group of atoms.
hydrogen atom is present in tert-butylbenzene, it is 3. The structure of 7-bromo-1,35-cycloheptatriene is
resistant to side-chain oxidation.
2. The typical reactions of the benzene ring are those %U
in which the p-electrons serve as a source of
electrophilic reagents. Because of delocalization +
of p-electrons benzene does not show additional In the presence of Ag+ in solution, bromine gets
reactions as in the case of alkenes but undergoes precipitated as AgBr giving a stable cycloheptatrienyl
carbocation due to its aromatic character (six p he bromine in this case is not precipitated in the
T
electrons delocalized in seven overlapping p orbitals). presence of Ag+ ions because the cyclopentadiene
carbocation will not be stable as it is not aromatic
%U
$Jĺ $J%U (4p electrons distributed over 5p orbitals). It is for
+ this reason, the carbocation is not formed.
The structure of 5-bromo-1, 3-cyclopentadiene is
%U +
HINTS AND SOLUTIONS
1. Methyl group activates benzene ring towards 4. The benzene ring attached to —NH— group gets
electrophilic substitution. activated and thus will undergo nitration at the para
Chlorine deactivates benzene ring less than the nitro position in preference to ring attached to —CO—
group. group.
2. The phenyl group attached to the —NH— 5. In the compound P, —OH is the controlling substituent.
group gets activated and thus bromination The compound obtained will be
at the para position occurs in this phenyl
group.
+2 &22+
3. The given reaction proceeds as follows:
12
±
&+&+&+&O$O&O &+&+&+$O&O
&+&+&+ In the compound Q, —OCH3 is the controlling sub-
5HDUUDQJHPHQW
stituent. The compound obtained will be
&+ &+

&+ &+ +& 2&+
3
&+ 12
&+ &+ & 2 2 +
L 2 the compound R, the benzene attached to O will be
&+ nitrated. The compound obtained will be
3 2 12
2+
LL +2
&+&2&+ &
' 2
5
4
Analysis of Organic
Compounds
5
Introduction
When we study an organic compound first of all we purify it, there after we analysis it and fmally we derive its structure.
Therefore, the process involves:
1. Purification of compound
2. Qualitative analysis
3. Quantitative analysis
4. Determination of molecular mass
5. Determination of structural formula by physico-chemical and spectroscopic methods.
It is essential to obtain a compound in its purest form before studying its properties and investigating its structure.
PURIFICATION OF ORGANIC COMPOUNDS

The various methods used for purification of organic compounds are The choice of method, however, depends upon the
nature of substance (whether solid or liquid) and the type of impurities present in it.
Following methods are commonly used for this purpose:
(i) Filtration
(ii) Crystallization
(iii) Sublimation
(iv) Distillation
(v) Differential extraction
(vi) Chromatography
After the purification, its purity is verified by measuring certain physical properties such as melting point, boiling point,
refractive index etc.
Filtration
This method is used to separate an insoluble solid component from the soluble component of the mixture in a given
solvent.
(a) Ordinary filtration: This process is useful when one of the components is insoluble in a liquid, solvent but the other
is soluble and is carried out with the help of a filter paper which is placed in funnel. The mixture is dissolved in a
5.2 Analysis of Organic Compounds
suitable solvent and is filtered with the help of filter paper. The liquid containing soluble component passed through
the filter paper and insoluble solid is retained on the filter paper. Filter is evaporated to regain the soluble part. e.g.,
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A mixture containing naphthalene and urea, sugar and charcoal etc.

Some time the filtration is carried out in a fluted filter paper placed in a glass funnel. The use of fluted filter paper
makes the- filtration rapid.
(b) Warm filtration: Applicable in the cases if one of the component is soluble at high temperature but almost insoluble
but almost insoluble at low temperature. It is carried out in a hot water funnel.
eg.: A mixture of benzoic acid and anthracene.
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(c) Filtration under reduced pressure: If the process of filtration is very slow, it is carried out under reduced pres-
sure using Buckner funnel.
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Analysis of Organic Compounds 5.3
Crystallization
(a) Simple Crystallization
It is a process of solidification of a pure substance from its dissolved state. It is the most common method of purifying
organic solids and is based upon differences in their solubilities in a given solvent or a mixture of solvents.
It is used for the purification of solid organic compounds. This process is mainly used when solid is present with low
percentage of impurities. The basis of this process is that the solubility of organic compounds usually increases greatly
with increasing temperature. Therefore, when saturated solution of a solid in a suitable solvent at its boiling point is
cooled, crystals of the solid come down. As the fitting of molecules in a crystal lattice involves highly selective forces,
usually very pure crystals are obtained by crystallization.
The process of crystallization can be broken into seven discrete steps: choosing the solvent, dissolving the solute,
decolourising the solution by the use of activated charcoal, removing suspended solids, crystallising the solute, collecting
and washing the crystals and drying the product.
This method involve the following steps:
(a) Selection of solvent: A small quantity of the substance, is heated with 2-3 ml of the solvent under the examination.
When partial or complete dissolution has taken place, the solution is cooled. If a considerable proportion of the dis-
solved substance separates out in the form of crystals, the solvent is considered suitable. Thus suitable solvent is one
in which:
(i) The solvent should not react chemically with the substance.
(ii) The organic substance should be sparingly soluble at room temperature but appreciably soluble at high temperature
and readily crystallises on cooling.
(iii) Either it should not dissolve impurities or their solubilities is much more than the substance to be purified so that
during crystallization, they should be left in the mother liquor.
The choice of solvent is very important.
e.g., To separate sugar and salt alcohol is used as it does not dissolve common salt. Similarly, hot water is a good choice
to dissolve benzoic acid from its mixture with naphthalene.
The solvents commonly used are given below:
(1) Water
(2) Rectified spirit
(3) Absolute alcohol
(4) Acetic acid
(5) Acetone
(6) Methyl alcohol
(7) Chloroform
(8) Benzene
(9) Carbon tetrachloride
(10) Ethyl acetate
Mixed solvents are also used for the purpose.
(b) Preparation of the solution: The impure substance is powdered and heated with the solvent in a flask. The amount of
solvent, should be just sufficient to dissolve the substance on heating. In case of the solvent with low boiling points,
the heating must be done carefully by using either an air condenser or water condenser. So that the vapour of the sol-
vent may not come in the contact with the flame.
(c) Filtration of the solution: The hot saturated solution is filtered preferably through a fluted filter paper placed in a glass
funnel. If the crystallization of organic compound takes place during filtration then a hot water funnel is employed for
filtration.
(d) Crystallization: The warm filtrate is allowed to cool slowly and undisturbed in a beaker or in a crystallising dish.
After sometime the crystals of pure compound are formed. Some times crystallization can be induced with either by
scratching the walls of the container with glass rod or by seeding with small. crystal of the same substance. The
process of inducing crystallization by adding a crystal of the pure substance into its saturated solution is called
seeding.
(e) Separation of crystals: The crystals formed are separated from the mother liquor by filtration. The filtration is nor-
mally done by using Buckner funnel and a suction pump. The crystals are washed 2-3 time with small quantities of
pure solvent.
(f) Drying of crystals: The crystals are dried by pressing between the folds of filter paper and then placed in a steam or
air oven for some time. The crystals are finally dried over sulphuric acid or calcium chloride in a desiccators.
(g) Removal of colour: Some times the crystals obtained are slightly coloured due to the presence of some coloured
impurities. These are removed by adding a pinch of animal charcoal which absorbs all the coloured impurities and the
crystals now obtained are colourless.
If the substance contains impurities of comparable solubilities, it can be purified by repeated crystallization.
(b) Fractional crystallization

This method is used to separate and purify two or more compounds which have different solubilities in the same solvent.
The hot solution of the mixture in a suitable solvent, is cooled slowly. The compound having less solubility crystallises
out first at a certain temperature. It is filtered at this temperature. The other component will crystallise on further cooling.
The process is repeated several times for the complete separation. The separation of the components of a mixture becomes
more and more difficult when there is little difference in their solubilities.
Thus, the process of separation of different components of a mixture by repeated crystallization is known as fractional
crystallization.
Process
The impure substance is heated gently in a china dish over a sand bath. The china dish is covered with a perforated
filter paper over which an inverted funnel is placed. The stem of the funnel is plugged with cotton to prevent escape
of vapours. The vapours pass through the holes of the filter paper and condense on the cooler parts of the funnel
walls.
 The filter paper is used to prevent the sublimed substance to fall back into the China dish and to cut of the direct heat
from the dish.
 Sublimation can also be done under reduced pressure to avoid decomposition of the organic compound.
Sublimation
Sublimation is the process whereby a solid evaporates from a warm surface and condenses on a cold surface, again as
solid. This technique is particularly useful for the small-scale purification of solids because there is so little loss of mate-
rial in transfer. Sublimation is preferred over crystallization when the amount of material to be purified weighs less than
100 mg.
Sublimation can occur readily at atmospheric pressure. For substances with lower vapour pressures vacuum sublima-
tion is used. At very low pressure the sublimation becomes very similar to molecular distillation.
The process of sublimation is very useful in the purification of such solids which sublimate on heating and are associ-
ated with non-volatile impurities.
Camphor, naphthalene, anthracene, benzoic acid, p-dichlorobenzene, iodine, ammonium-chloride anthraquinone,
indigo, phthalic anhydride, etc. are purified by this process.
Distillation
It is the process of conversion of a liquid into vapours by heating followed by condensation of vapours so produced by
cooling. This method used for purification of liquids which boil without decomposition and are associated with non-
volatile impurities.
Distillation is a process which involves two stops:

1. Vaporization: Volatile Liquid is converted into vapours and nonvolatile compounds are left behind.
2. Condensation: Vapours of volatile liquid are condensed again to pure liquid.
(a) Simple distillation The method is commonly used for those liquids which are sufficiently stable at their boiling
points and which contain non-volatile impurities.
Procedure
The impure liquid is taken in a distillation flask which is connected to a Liebig’s condenser. The flask is kept in a water
bath if the boiling point of the liquid is below 100°C, otherwise on a sand bath. A few glass beads or porcelain pieces
are, put in the flask to prevent bumping of the liquid during heating. A thermometer is fitted in the neck of the distillation
flask in such a way that the bulb of the thermometer is near the side tube of the distillation flask. The flask and the
condenser are clamped. The liquid vaporises at its boiling-point and the vapours are condensed as they pass through the
condenser. The pure liquid is collected the receiver while the non-volatile impurities are left behind in the distillation flask.
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This method can also be used for separating liquid having sufficient difference in their boiling points. For example,
(i) benzene (b.pt. 80°C) and aniline (b.pt. 184°C)
(ii) chloroform (b.pt. 61 °C) and aniline (b.pt. 184)
(iii) ether (b.pt. 35’C) and toluene (b.pt. 110°C)
Nitrobenzene prepared in the laboratory can also be purified by distillation.
(b) Fractional distillation This method is used for the separation and purification of organic liquids from non-
volatile impurities or for separating two or more volatile liquid mixture which have boiling points close to each
other.
When the boiling points of the component liquid differ by 40°C or more, the distillation is carried out in a
distillation apparatus. The liquid with a low boiling point vaporise first, gets condensed again and becomes constant,
the second component vaporises, which is collected in a second receiver. When the liquids present in the mixture have
their boiling points close to each other, the, separation into pure liquids is difficult. The fractions collected are always
contaminated. The fraction are further purified by repeated distillations. To decrease the number of distillations, the
separation is-done by fitting the distillation flask with fractionating column which in turn is connected to the condenser.
A fractionating column provides many surfaces for heat exchange between the ascending vapours and the descending
condensed liquid. Some of the condensing liquid in the fractionating column obtains heat from the ascending vapours
and revaporises. The vapours thus become richer in low boiling component. The vapours of low boiling component
ascend to the top of the column. On reaching the top vapours become pure in low boiling component and pass through
the condenser and the pure liquid is collected in a receiver. After a series of successive distillations, the remaining
liquid in the distillation flask gets enriched in high boiling component. Each successive condensation and vaporization
unit in the fractionating column is called theoretical plate. Commercially, columns with hundred of plates are
available.
Technological applications of fractional distillation is to separate different fractions of crude oil in petroleum
industry.
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(c) Distillation under reduced pressure (Vacuum distillation)

Normal boiling point of a liquid is that temperature at which its vapour pressure is equal to atmospheric pressure. If
atmospheric pressure is reduced, the liquid will boil earlier than its normal boiling point. This principle is used in the
purification of those compounds which decompose at their normal boiling points, i.e., by carrying out distillation under
reduced pressure.
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A special apparatus is used for this purpose. It consist of a Claisen’s flask which has two necks. In one
of the necks a thermometer is fitted while in the other a capillary tube whose lower end is dipped in the liquid and
upper end is closed by means of a rubber tubing and a screw-clip through which a very slow current of air is
admitted.
The pressure is reduced by suction pump and the distillation is carried out at lower temperature as a glycerine can be
distilled at 180°C (normal b.p 290°C) Under a pressure of 10–12 mm. Cane juice can also be concentrated by this method.
This technique can be used to separate glycerol from spent lye in soap industry.
(d) Steam distillation: This method is used for the purification of organic compounds (solids or liquids) which
(i) are insoluble in water.
(ii) are steam volatile, i.e., vaporise at the steam (100°C) temperature.
(iii) are associated with impurities which are non-volatile in steam.
(iv) possess high molecular weight, and
(v) have high vapour pressure (10–15 mm) at the boiling point of water (100°C) i.e., unstable at their boiling point.
Procedure
Steam from a steam generators passed through a heated flask containing the liquid to be distilled. The mixture of steam and
the, volatile organic compound is condense and collected. The compound is later separated from water using a separating
funnel. In steam distillation, the liquid boils when the sum of vapour pressure due the organic liquid (p1) and that due to
water (p2) becomes equal to the atmospheric pressure (p) i.e. p = p1 + p2. Since p, is lower than the organic liquid vapourises
at lower temperature than its boiling point.
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Steam distillation can be used for the purification of nitrobenzene, aniline, essential oils, separation of mixture of
o-nitrophenol and p-nitrophenol.
Differential Extraction
The process of separation of an organic compound from its aqueous solution by shaking with a suitable organic solvent is
termed differential extraction.
Procedure
The aqueous solution is taken in a separating funnel. A small quantity of the solvent is added to it. lt will form
a separate layer as being imiscible with water. The mouth of the funnel is closed and the contents are shaken.
The organic substance being more soluble in the solvent is transferred from aqueous layer to solvent layer.
The separating funnel is kept stationary for some time during which two distinct layers are formed. The lower
layer is taken out by opening the tap of the funnel. The orgaic substance is recovered from the solvent layer by
distillation.
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Chromatography
Chromatography is a modern technique which is employed for the separation, purification, isolation and identification
of the organic compounds. The name chromatography owes its origin to the fact that Micheal Iswett (1906) first used it
for the separation of coloured substances from plants (Greek: chromos means colour and grophy means writing). Since
the scope of this technique has been widely extended to include colourless mixtures, the idea of colour is no longer
connected with the concept.
In this method two mutually immiscible phases are brought into contact with each other wherein one phase is
stationary (fixed phase) while the other is mobile (moving phase). The stationary phase can be either solid or tightly
bound liquid on a solid support while mobile phase can be either liquid or a gas. Depending upon the nature of the
stationary phase and the mobile phase, the different types of chromatographic techniques commonly used are as
follows:
(1) When stationary phase is solid the chromatography is known as adsorption chromatography. Adsorption
chromatography is further classified into following categories. This classification depends on the nature of the mobile
phase.
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(2) When stationary phase is liquid the chromatography is known as partition chromatography. Partition chromatography
is further classified in different categories. This classification depends on the nature of the mobile phase. A
Logical Approach to Modem Organic Chemistry
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Principle of Chromatography:
Chromatography is based on the general principle of distributing the components of a mixture between stationary phase
and the mobile phase.
Different components of mixture migrate at different rate through the stationary phase and this causes separation of
components present in the mixture.
Adsorption Chromatography
This is based on adsorption (or surface) phenomenon. The extent of adsorption of different constituents present in mobile
phase varies with a given adsorbent (stationary phase). Thus, the separation is achieved on the basis of the relative binding
power of different compounds to the adsorbent. Thus, this Chromatography is based upon the differential, adsorption
of the various compounds of a mixture on a stationary phase. Since some compounds are more strongly adsorbed that
the other, they will travel on the stationary phase at different rates and thus get separated. The forces which determine
the relative binding power (i.e., differential adsorption) of the cpmpounds are van der Waal’s forces dipole-dipole
attraction, co-ordination interactions and hydrogen-bonding. The most common examples of adsorption Chromatography
are:
(i) Column Chromatography and
(ii) Thin layer Chromatography.
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(a) Column chromatography

Adsorbent: A large number of adsorbents have been used for column Chromatography. The adsorbents are cellulose, starch,
sucrose, inorganic carbonates, alumina and silica gel: Alumina and silica gel are the most commonly used adsorbents.
Alumina (or aluminium oxide) is used in the majority of chromatographic separations involving compounds that are non-
polar or of medium polarity. Polar organic compounds such as carboxylic acids, amines, phenols and carbohydrates are
separated by the use of less polar adsorbent silica gel.
Choosing column: After deciding which adsorbent to use for a separation you need to decide how much adsorbent to
use. This depends on sample amount and dimension of the column as follows:
Amount of mixture Amount of adsorbent Column dimensions (diameter × height cm)

10g 250g 3.4 × 27 cm
2–3g 60g 2.0 × 19 cm
Making column: After you have chosen a chromatography column and weight out the adsorbent that you need, you can
prepare the column for use. A chromatographic column in operation is shown below in Figure.
Clamp the glass chromatography tube (i.e., column) in a vertical position onto a ring stand, and fill approximately one-
half of it either with the first developing solvent that you plan to use or with a less polar solvent (n-hexane in most of the
cases). Add a small piece of glass wool as a plug and push it to the bottom of the column with a glass rod, making sure all
the air bubbles are out of the glass wool. Cover the plug with approximately 6 mm of white sand. The plug and sand serve
as a support base to keep the adsorbent in the column and prevent it from clogging the tip. Pour the adsorbent powder
slowly into the solvent-filled column with the stopcock closed. After all the adsorbent has been added carefully pour ap-
proximately 4 mm white sand on top. The column must not be allowed to dry out once it is made; the solvent level should
never be allowed to go below the upper level of the adsorbent
Pure solvent is taken in a dropping funnel and is poured slowly at the top of the column. As the solvent passes through
the top layer, it dissolves the mixture adsorbed in this layer and the solution so formed flows down. As the solution moves
down the components of the mixture in solution are adsorbed by the adsorbent at different speeds. Those which are less
strongly adsorbed, move more rapidly than the more strongly adsorbed ones. Consequently the original layer of various
components separates into a number of individual layers called bonds in the adsorption column. Each band is called chro-
matogram. These bands are further separated by running more of the pure solvent down the column. The most strongly
adsorbed component is present in the band near the top while the weakly adsorbed constituent is to be found in the band
near the bottom
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Packing of the column.

Elution: It is the process of extraction of the adsorbed components from the adsorbent with the help of solvents of increas-
ing polarity. The solvents usually employed in the increasing order of polarity are hexane, carbon tetrachloride, dichloro
methane, benzene, chloroform, ethyl acetate, acetone, alcohol, etc.
A solvent or a mixture of solvents which is used to extract the column constitutes the mobile phase and is usually called
an eluent.
The rate at which materials are eluted is controlled by the activity of the adsorbent and by the polarity of the solvent.
In this way, the various components of the mixture can be separated into different fractions. Distillation or evaporation of
solvent from different fractions gives the various components of the mixture in pure form.
(b) Thin layer chromatography
Thin layer chromatography is simple, inexpensive, fast, sensitive and efficient. It is especially useful in determining the
number of components in a mixture and in establishing whether two compounds are identical or have different structures.
TLC involves using a thin layer of an adsorbent on a glass, metal or plastic plate. A small amount of the mixture is ap-
plied or spotted on to the adsorbent close to one end of the plate and then placed vertically in a suitable solvent in a closed
tank, but the spot is not covered by the solvent. As the solvent ascends the plate by capillary movement, the sample is
distributed between the moving liquid phase and the stationary solid phase. This is called developing the chromatogram.
The separation during the development process occurs due to the compounds many equilibrations between moving and
stationary phases.
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If the components of the mixture are coloured, the spots are readily located. If the components are colourless, the dried
plate is sprayed with iodine vapour or with a solution of a suitable compound. In this way, the position of the components
are revealed Fig. 9. Identification is made from the Rf values.
Rf value: Under a definite set of experimental conditions, a given compound will always travel a fixed distance relative
to the distance travelled by the solvent front. This ratio of distances is called the Rf. The term Rf stands for “ratio to the
front”. It is expressed as a decimal fraction:
distance travelled by compound A
Rf = =
distance travelled by developing solvent front B
Distance moved by the substance from base line (x)

or, R f =
Distance moved by the solvent from base line (y)
The Rf value for a compound depends on its structure and is a physical characteristic of the compound, just as a m.p.
Partition Chromatography
Partition chromatography is a technique in which mixture of substances are separated by means of partition be-
tween mobile phase and stationary liquid phase. The most important example of partition chromatography is paper
chromatography.
Paper Chromatography
Paper chromatography was first introduced by Schobein in 1865. It is considered to be the simplest and most widely
used chromatographic techniques because of its applicability to isolation, identification and quantitative determination of
organic compounds. Introduction, Purification of Analysis of Organic Compounds
In paper chromatography separation of a mixture of substances is mainly done by the flow of solvents (mobile phase)
on a stationary phase which is a Whatman chromatographic paper. The stationary phase is the water present in the cel-
lulose of the filter paper and the mobile phase is an organic solvent which is either immiscible or partially miscible with
the stationary phase (i.e., water). The mobile phase rises by the capillary action and by adsorption on the filter paper. The
separation is achieved by ‘the differential migration of the different components which occurs due to the differences in
partition coefficients.
In this technique, a drop of the solution containing the mixture is placed on the paper strip, either near one corner or
in the middle of one edge, and the strip is then dried. The moving phase either ascends or descends the paper strip. The
dried paper strip is placed in a suitable glass vessel containing the organic solvent that has been previously saturated with
water. One edge of the paper strip is placed just below the level of the solvent, and when the solvent front has progressed
a suitable distance, the distance moved by the solvent is marked and the paper strip is then allowed to dry in air. If the
solutes are colourless, the paper is sprayed with a solution of a suitable compound which reacts with the various compo-
nents to form coloured spots, where these coloured spots appear indicates the position of each component on the paper
strip.
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Apparatus for paper strip chromatography. The lower edge of paper strip is
dips into solvent in asending paper chromatography.
Paper chromatography is very useful for the identification of amino acids and sugars.
Solubility Behaviours
It is convenient to summarize the solubility characteristics of the commoner classes of organic compounds into seven
groups as specified in Table 1. The compounds are grouped according to: (a) their solubility towards the reagents specified
above, and (b) the elements, other than carbon and hydrogen, that they contain.
1. Compounds soluble in both water and ether This includes the lower members of the various homologous
series (4-5 atoms in a normal chain) that contain oxygen and/or nitrogen in their structures: they are soluble in water
because of their low carbon content. If the compound is soluble in both water and in ether, it would also be soluble
in other solvents so that further solubility tests are generally unnecessary: the aqueous solution should be tested with
indicator paper. The test with sodium hydrogen carbonate solution should also be performed.
2. Compounds soluble in water but insoluble in ether These compounds with the exception of salts, are
usually also soluble in dilute alkali and acid. The behaviour of salts to alkaline or acidic solvents may be informative.
Thus, with a salt of a water-soluble base, the characteristic odour of an amine is usually apparent when it is treated
with dilute alkali: likewise, the salt of a water soluble, weak acid is decomposed by dilute hydrochloric acid or by
concentrated sulphuric acid. The water-soluble salt of a water-insoluble salt of a water-insoluble acid or base will give
a precipitate of either the free acid or the base when treated with dilute acid or dilute alkali. The salts of sulphonic
acids and of quaternary bases are unaffected by dilute sodium hydroxide or hydrochloric acid.
3. Compounds insoluble in water, but soluble in dilute sodium hydroxide It should be recalled that some
of the compounds belonging to this group are sufficiently strong acid to release carbon dioxide from sodium hydrogen
carbonate (e.g., carboxylic acids, sulphonic and sulphinic aids, and certain substituted phenols, see below).
Table .5 Classification of Organic Compounds According to Solubility Behaviour
(1) (2) (3) (4) (5) (6) (7)

Soluble in Soluble in Soluble in Soluble Not Not Neutral
both ether water but 5% sodium in 5% containing N containing compounds
and water insoluble in hydroxide hydrochloric or S. Soluble N or S. containing N or S
ether solution acid only in Insoluble in
concentrated concentrated
sulphuric acid sulphuric acid
The lower Polybasic Acids. Phenols. Primary Unsaturated Saturated Nitro compounds
members acids and Imides. Some amines. hydrocarbons. aliphatic (tertiary). Amides
of the hydroxyl primary and Secondary Some hydrocarbons. and derivatives
homologous acids. secondary nitro aliphatic and polyalkylated Cycloalkanes. of aldehydes and
series of; Glycols, compounds; aryl-alkyl aromatic Aromatic ketones. Nitriles.
Alcohols; polyhydric oximes. amines. hydrocarbons. hydrocarbons. Negatively
Acids; Estrs; alcohols, Thiols and Aliphatic Alcohols. Halogen substituted
Phenols; polyhydroxy thiophenols. and some Aldehydes. derivatives amines. Nitroso,
Anhydrides; aldehydes Sulphonic aryl-alkyl Ketones. of the above azo, hydrazo and
Amines; and ketones acids, sulphinic tertiary Esters. hydrocarbons, other intermediate
Nitriles; (sugars). acids, amines. Anhydrides. Diaryl ethers.. reduction
Polyhydro- Some amides, aminosulphonic Hydrazines. Etehrs and products of nitro
xyphenols. amino acids, acids and acetals. compounds.
di- and sulphonamides. Lactones. Sulphones,
polyamino Some diketones Acyl halides. sulphonamides
compounds, and b-keto of secondary
amino esters. amines, sulphides,
alcohols. sulphates and
Sulphonic other sulphur
acids. Salts. compounds.
4. Compounds insoluble in water, but soluble in dilute hydrochloric acid It should be remembered that the
hydrochlorides of some bases are sparingly soluble in cold water and one should therefore not be misled by an appar-
ent insolubility of a compound (containing nitrogen) in dilute hydrochloric acid. The suspension in dilute hydrochloric
acid should always be filtered and the filtrate made alkaline. A precipitate will indicate that the compound is indeed a
base and should be included in this group.
5. Water-insoluble hydrocarbons and oxygen compounds that do not contain N or S and are soluble
in cold concentrated sulphuric acid Any changes – colour, excessive charring, evolution of gases or heat,
polymerization and precipitation of an insoluble compound – attending the dissolution of the substance should be
carefully noted.
` Alcohols, esters (but not ethyl benzoate, diethyl malonate or diethyl oxalate), aldehydes, methyl ketones and
cyclic ketones containing less than nine carbon atoms as well as ethers containing less than seven carbon atoms are
also soluble in 85 per cent phosphoric acid.
6. Compounds, not containing N or S, insoluble in concentrated sulphuric acid This test provides for
a differentiation inter alia between alkanes and cylco-alkanes and also simple aromatic hydrocarbons which are
insoluble, and unsaturated hydrocarbons which are soluble in the reagent.
7. Compounds that contain N or S which are not in groups 1–4 Many of the compounds in this group are
soluble in concentrated sulphuric acid. It will be observed that halogen compounds are not listed separately, but appear
in each of the seven categories in accordance with their solubility behaviour.
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Methods of Separation of Mono-Functional Organic Compounds from Binary Mixtures

This separation is based on Differences in the Chemical Properties of the Compounds
1. Toluene and Aniline A mixture of toluene may be separated by extraction with dilute HCl; the aniline passes into
the aqueous layer in the form of the salt aniline hydrochloride and may be recovered by neutralization.
2. Phenol and Toluene They can be separated by treatment with dil. NaOH
3. Dibutyl Ether and Chlorobenzene Concentrated H2SO4 dissolves only the dibutyl ether and it may be recovered
from solution by dilution with water.
The above examples are simple applications of the fact that the various components fall into different solubility
groups.
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4. Phenols and any compound containing -C-OH group (e.g., o-cresol from benzoic acid) Phenols may
be separated from acids by a dilute solution of NaHCO3; the weakly acidic phenols (and also enols) are not converted
into salts by this reagent and removed by ether extraction; the acids pass into solution as the sodium salts and may be
recovered after acidification.
5. Separation of mixture of amines Mixture of primary, secondary and tertiary amines can usually be sepa-
rated by Hinsberg method. The mixture of amines is treated with NaOH solution and toluene-p-sulphonyl chloride is
warmed in a water bath and finally acidified with dil. HCl, the sulphonamides of primary and secondary amines are
precipitated. The solid is filtered and washed with a little cold water, the tertiary amine will be present in the filtrate.
The solid is then treated with alkali again. The sulphonamide from the primary amine goes into solution and the pre-
cipitate of the sulphonamide of the secondary amine is filtered off. The filtrate is acidified with dil. HCl to precipitate
the derivative of the primary amine.
6. Aldehydes and Ketones from other liquid hydrocarbons and other neutral liquid compound (e.g.,
ethanal and ethanol) The mixture is shaken with a solution of NaHCO3, the carbonyl compound forms a solid
bisulphite compound which is filtered off and decomposed with dil. acid in order to recover the aldehyde or ketone.
Separation based on Differences in the volatilities of the component in aqueous solution
1. Diethylamine and butan-1-ol They can be separated by adding sufficient dilute H2SO4 to neutralise the base;
steam distillation will remove the alcohol. The amine can be recovered by adding NaOH to the residue and repeating
the distillation.
2. Diethyl Ketone and Acetic Acid The mixture is treated with sufficient dilute NaOH solution to transform the
acid into sodium acetate and distilling the aqueous mixture. The ketone will pass over in the steam and the non-volatile
stable salt will remain in the flask. Acidification with dilute H2SO4 liberates acetic acid which can be isolated by steam
distillation or by extraction.
QUALITATIVE ANALYSIS
Identification of Organic Compounds
The identification of organic compounds differs from that of the inorganic salts in the respect that inorganic salt analysis is
very systematic while there is no such systematic scheme for the analysis of organic compounds. However, the following
operations are generally useful for the identification of unknown organic compounds:
(i) Preliminary tests
(a) Physical state
(b) Colour
(c) Odour
(d) Ignition test
(e) Saturation test
(f) Solubility
(ii) Detection of elements
(iii) Detection of functional group
(iv) Qualitative elemental analysis
Detection of Elements
Organic compounds consist mainly of carbon, hydrogen and oxygen. Hence, detection of these elements are not necessary.
In addition to the above elements, organic compounds often contain nitrogen, halogens, and sulphur. Hence identification
of organic compounds means detection of nitrogen, halogens and sulphur only.
Detection of Elements in Organic Compound: Besides carbon and hydrogen, an organic compound may also contain
elements like nitrogen, sulphur, halogens, oxygen and sometimes metals and other non-metals.
(i) Detection of carbon and hydrogen The compound is mixed with dry cupric oxide (CuO) and strongly heated.
C and H present in the compound gets oxidized to CO2 and H2O respectively. CO2 turns lime water milky which
dissolves in excess to form Ca(HCO3)2, whereas water vapours turn anhydrous CuSO4 to blue.
∆
C + 2CuO  → CO 2 + 2Cu
CO 2 + Ca(OH) 2 
→ CaCO3 ↓ + H 2 O
(White)
CaCO3 + H 2 O + CO 2 
→ Ca(HCO3 ) 2
(So lub le)
∆
H 2 + CuO  → H 2 O + Cu
CuSO 4 + 7H 2 O 
→ CuSO 4 + 7H 2 O
(White) (Blue vitriol)
(ii) Detection of nitrogen, halogens and sulphur These elements are detected by means of Lassaigne test.
The Lassaigne solution is prepared by fusing the organic compound with dry sodium pieces (two or three such
fusions are made). The fusions are added in distilled water which is boiled and filtered off. The clear solution
is known as Lassaigne solution (or sodium extract). Under the fusion conditions the following reactions take
place:
Na + C + N 
→ NaCN
Sodium cyanide
Na + Cl 
→ NaCl
Na + Br 
→ NaBr
Na + I 
→ NaI
2Na + S 
→ Na 2S
Unreacted sodium is converted into NaOH solution.
(a) Detection of Nitrogen To a little sodium extract (Lassaigne solution) we add freshly prepared ferrous sulphate
solution. The solution is made alkaline and heated. On addition of dil. H2SO4, if a green or blue colour appears,
nitrogen is present. If no appearance of colour, add a little ferric ion solution. A blue or green colour of ferric
ferrocyanide confirms nitrogen.
FeSO 4 + 2NaOH 
→ Fe(OH) 2 ↓ + Na 2SO 4
(Green ppt.)
Fe(OH) 2 + 6NaCN 
→ Na 4 [Fe(CN)6 ] + 2NaOH
Sodium ferrocyanide
3Na 4 [Fe(CN)6 ] + 2Fe 2 (SO 4 )3 

→ Fe 4 [Fe(CN)6 ]3 + 6Na 2SO 4
or 2Na 4 [Fe(CN)6 ] + 4FeCl3 

→ Fe 4 [Fe(CN)6 ]3 + 12NaCl
Ferric ferrocyanide
(Blue)
If the compound contains both nitrogen and sulphur then there will be sodium sulpho or thiocyanide in the sodium
extract. This on addition of FeCl3 will produce a red colour of ferric sulphocyanide.
Na + S + C + N 
→ NaSCN
3NaSCN + FeCl3 
→ Fe(SCN)3 + 3NaCl
Ferric sulphocyanide
(Red colour)
Diazo compound (—N=N—) do not give test of nitrogen as above, but a mixture of potassium carbonate and
magnesium powder is used in place of sodium for the preparation of extract.
Soda lime test for nitrogen: Many organic compounds on heating with soda lime (CaO + NaOH) give smell of
ammonia.
CH 3CONH 2 + NaOH 
CaO
∆
→ CH 3COONa + NH 3 ↑
Acetamide
NH 2 CONH 2 + 2NaOH 

CaO
∆
→ Na 2 CO3 + 2NH 3 ↑
Nitro and diazo compounds do not give ammonia on heating with soda lime.
(b) Detection of halogens

Lassaigne test: The extract is boiled with conc. HNO3 to expel nitrogen and sulphur, because NaCN and Na2S react with
AgNO3 to give white and black precipitates, respectively.
NaCN + AgNO3 
→ AgCN ↓ + NaNO3
Na 2S + 2AgNO3 
→ Ag 2S ↓ + 2NaNO3
Boiling with conc. HNO3 evolves HCN and H2S as volatile gases.
∆
NaCN + HNO3  → NaNO3 + HCN ↑
(Conc.)
∆
Na 2S + 2HNO3  → 2NaNO3 + H 2S ↑
(Conc.)
Now add AgNO3 solution.

(i) Formation of a curdy white precipitate which is soluble in NH4OH solution shows the presence of chlorine.
NaCl + AgNO3 
→ AgCl ↓ + NaNO3
(White)
(ii) Formation of a light yellow ppt, which is sparingly soluble in NH4OH shows the presence of iodine.
NaI + AgNO3 
→ AgBr ↓ + NaNO3
(Light yellow )
(iii) Formation of a lemon yellow ppt. insoluble in NH4OH shows the presence of iodine.
NaI+ AgNO3 
→ AgI ↓ + NaNO3
(Lemon yellow )
Layer test for bromine and iodine: The presence of nitrogen and sulphur does not interfere in this test. In this test acidify a
little sodium extract with dil. HNO3 or dil. H2SO4 and acid CHCl3 or CCl4 and excess of chlorine water. If organic layer
becomes yellow or brown, bromine is present and if violet, iodine is present.
2NaBr + Cl2 
→ 2NaCl + Br2
→ Yellow or brown layer

CHCl3 + Br2 
2NaI + Cl2 
→ 2NaCl + I 2
→ Violet layer
CHCl3 + I 2 
Beilstein’s Test: Many organic compounds containing halogens impart a green colour to the Bunsen flame when heated on
a copper wire. The green colour is developed due to the formation of volatile halides of copper. However, nitrogen com-
pound urea also imparts green colour to the flame.
(c) Detection of Sulphur The test of sulphur from sodium extract many be done in three ways:
(i) Sodium nitroprusside test: Only a little reagent is added to sodium extract; appearance of purple, pink or violet colour
confirms the presence of sulphur.
Na 2 [Fe(NO)(CN)5 ]+ Na 2S 
→ Na 3 [Fe(O = N — S — Na)(CN)5 ]
Sodium nitroprusside Violet complex
(ii) Lead acetate test: Add a few drops of lead acetate solution to sodium extract; appearance of a black ppt. shows the
presence of sulphur.
(CH 3COO) 2 Pb + Na 2S  → 2CH 3COONa + PbS ↓
(Black )
(iii) Silver coin test: On adding a silver coin to the sodium extract, the coin turns black.
(iv) Oxidation test of sulphur: The unknown compound is heated with fusion mixture (Na2CO3 + KNO3) in an ignition tube
when sulphur is oxidized to sulphate.
Na 2 CO3 + S + 3[O] 
→ Na 2SO 4 ↓ + CO 2 ↑
The fused mass is extracted with hot water, filtered and a few drops of barium chloride solution are added. The
appearance of a white precipitate which is insoluble in conc. HCl or HNO↑3, confirms the presence of sulphur.
Na 2SO 4 + BaCl2 
→ BaSO 4 ↓ + 2NaCl
(White)
BaSO 4 + HNO3 
→ Insoluble
(Conc.)
Test of halogen present in the ionic form: Benzene diazonium halides and halide salts of aliphatic and aromatic amines
contain halide ions. If the aqueous solution of any compound gives a white or yellow ppt. on addition of AgNO3,
halide ions are present.
C6 H 5 N +2 Cl – + AgNO3 
→ C6 H 5 N +2 NO3– + AgCl ↓
Benzene diazonium
chloride
C6 H 5 N 2 Br + AgNO3 
→ C6 H 5 N 2 NO3 + AgBr ↓
C6 H 5 NH 3+ Cl – + AgNO3 
→ C6 H 5 NH 3+ NO3– + AgCl ↓
Aniline hydrochloride
Detection of sulphur present in the side chains: If the addition of BaCl2 solution ot aqueous solution of organic
compound gives white precipitate, it indicates the presence of sulphate ion in it.
C6 H 5 N 2 HSO 4 + BaCl2 
→ BaSO 4 ↓ + HCl + C6 H 5 N 2 Cl
Diazonium Sulphate
(C6 H 5 NH 3 ) +2 SO 2– → 2C6 H 5 NH 3+ Cl – + BaSO 4 ↓

4 + BaCl 4 
Anilinium sulphate
(iii) Test for phosphorus The compound is heated with an oxidising agent (sodium peroxide). The phophorus present
in the compound is oxidised to phosphate. The solution is boiled with nitric acid and then treated with ammonium
molybdate. A yellow colouration or precipitate indicates the presence of phosphorus.
∆
5Na 2 O 2 + 2P  → 2Na 3 PO 4 + 2Na 2 O
Na 3 PO 4 +3HNO3 → H 3 PO 4 +3NaNO3
H 3 PO 4 +12 (NH 4 ) 2 MoO 4 + 21HNO3 →(NH 4 )3 PO 4 .12MoO3 + 21NH 4 NO312H 2 O
Ammonium Ammonium
molydbate Phosphomolybdate
(iv) Detection of oxygen There is no satisfactory qualitative test for oxygen. If the compound on heating in an
atmosphere of hydrogen gives water drops, oxygen may be present.
Formula used in the determination of empirical, molecular and structural formulae
Detection of Functional Groups

Detection of functional groups is an important step in the analysis of organic compounds. It largely depends on the correct
determination of the constituent elements.
(a) Tests for carboxylic group
(i) Litmus test: Place a small quantity of the organic compound or its aqueous solution on a piece of moist blue litmus
paper. If the paper turns red, carboxylic group may be present.
(ii) Sodium bicarbonate test: Add a small quantity of the organic compound to about 5 ml sodium bicarbonate solution
taken in a test-cube. Compound dissolves with brisk effervescences.
RCOOH + NaHCO3 → RCOONa + H2O + CO2↑
(iii) Take a small quantity of the organic compound and add 4-5 ml of alcohol in a test-tube. Add a few drops of conc.
Sulphuric acid and warm on a water bath. A fruity smell indicates the presence of an ester.
RCOOH + R′OH 
H 2SO4
→ RCOOR ′ + H 2 O
Ester
(b) Tests for aldehyde group

(i) Schiff test: Take 5 ml of Schiff’s reagent in a test-tube and shake with organic compound (do not heat). A pink colour
is formed within two minutes.
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(ii) Fehling’s test: Mix equal volumes of Fehling’s (A) and Fehling’s (B) solution in a test-tube. Add a small amount of
the organic compound and boil for some time. A red precipitate of Cu2O is obtained.
RCHO + 2CuO → RCOOH + Cu 2 O↓
Re d
(iii) Tollen’s test: Take about 5 ml of Toolen’s reagent in a test-tube. Add a small quantity of the organic compound and
heat on a water bath. A shining silver mirror is formed on inner walls of the test-tube.
RCHO+ 2[Ag(NH 3 ) 2 ]OH + H 2 O → RCOONH4 + NH3 + 2NH4OH + 2Ag↓

Tollen 's reagent silver mirror
(iv) Benedict’s test: Take 4-5 ml of Benedict’s reagent in a test-tube. Add a few ml of the organic compound (or a solution
prepared in alcohol or water). Heat the mixture to boiling. Formation of red precipitate indicates the presence of
aldehydes.
RCHO + 2Cu(OH)2 + NaOH → Cu2O + RCOO–Na+ + 3H2O
(c) Tests for ketonic group

(i) Ketones, unlike aldehydes, do not restore the pink colour of Schiff’s reagent nor do they reduce Fehling’s solution or
ammoniacal silver nitrate solution. However, they form crystalline precipitate with 2, 4-dinitro phenylhydrazine and
also with sodium bisulphate reagent.
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(ii) Sodium nitroprusside test: Treat 1 ml of the organic compound with 1 ml of freshly prepared solution of sodium
nitroprusside followed by excess of NaOH solution. A wine-red colour is obtained.
(d) Tests for phenolic group

(i) Litmus test: Place a trace of the organic compound on the moist blue litmus paper. It turns red.
(ii) Neutral FeCl3 test: When phenols are treated with neutral ferric chloride solution, they form coloured complexes. The
colour of the complex may be violet, red, blue or green. This is a characteristic reaction of compounds having enolic
group. (= C – OH). All enols respond to this test.
With relatively milder oxidizing agents such as ferric chloride (Fe3 +) a resonance stabilized phenoxyl radical is
formed. This radical soon undergoes dimerization which may take place by ortho-ortho, ortho-para, para-para
coupling reaction.
2+ 2 2 2 2
+ +
)H
)H+
+
2 2 2
+ + +
22 2
+
++
The phenoxyl radicals are highly coloured and therefore, products are also coloured.
(iii) Aniline Dye test: Dissolve a little aniline in dilute hydrochloric acid, cool in ice-cool water and add aqueous solution
of sodium nitrite dropwise. To this cold solution, add organic compound already dissolved in sodium hydroxide
solution. A red or orange precipitate is obtained.
1D12+&Oĺ+121D&O
&O±

1++12+&O & 1{1+2
&O±
1D2+
1{1 2+ 1 1 2+
±1D&O
±+2
%HQ]HQHGLD]RQLXP3KHQROFKORULGH SK\GUR[\D]REHQ]HQH G\H
(iv) Phthalein test (Fluorescein test): Heat gently some organic compound and phthalic anhydride with a few ml of conc.
sulphuric acid in a test-tube. Pour the heated mixture to about 50 ml of water taken in a beaker and then add sodium
hydroxide solution till it became alkaline. A beautiful pink or purple colour appears.
2+ 2+
& 2 +62 &
+2
2 &²2 2+ 2 &²2 2+
2±1D
1D2+
&
2 &²2±1D 2
SLQNRUSXUSOH
(v) Bromine water test: Take aqueous or alcoholic solution of the organic compound in a test-tube. Add excess of
bromine water. A yellowish white precipitate is obtained.
2+ 2+
%U %U
%U
3KHQRO
%U
WULEURPRSKHQRO
(vi) Ceric ammonium nitrate test: Treat a few drops of the ceric ammonium nitrate with 3-4 ml hot aqueous solution of
the organic compound. A green or brown precipitate is obtained.
(NH4)2[Ce(NO3)6] + 2C6 H 5OH→ [Ce(NO3 ) 4 (C6 H 5OH) 2 ] + 2NH 4 NO3
phenol green or brown ppt.
(vii) Liebermann’s test: Take a little amount of the compound and fuse with a few crystals of NaNO2 in a test-tube. Cool
the test-tube and add 1 ml conc. H2SO4. A deep green colour is obtained which changes to purple, to blue and finally,
when poured into large excess of water, to red. When a little NaOH solution is added to the aqueous solution, the
same green, purple or blue colour reappears.
7DXWR
1D12+62 PHUL]H
+2 +2 1 2 2 1±2+
JUHHQFRORXU
3KHQRO 1D2+
2 1 2+ 2 1 2±1D
+62
,QGRSKHQRO UHG ,QGRSKHQRO EOXH
(e) Tests for alcoholic group

Alcohols may be considered as neutral compounds. They are soluble in water or dioxane.
(i) Sodium test: Take 3-4 ml of the organic compound in a test-tube. Add a thin slice of sodium metal. A brisk
effervescence due to the evolution of hydrogen takes place. (Organic compound should be free from water).
2ROH + 2Na → 2RONa + H2↑
(ii) Ester test: Warm the given liquid with acetic acid in presence of sulphuric acid. A fragrant smell indicates the
formation of ester.
ROH + CH3COOH  → RCOOCH3 + H2O
H 2SO4
Alcohols give crystalline esters with 3, 5-dinitrobenzoyl chloride. These esters have sharp melting points and can be
used for testing a given alcohol.
(iii) Oxidation test: Take some organic compound, 5 ml of K2Cr2O7 solution and 2-3 ml of conc. H2SO4 in a test-tube.
Heat the test-tube after fitting a delivery tube. The distillate is passed into another test-tube containing water. Test the
aqueous solution of the distillate for aldehyde group. A positive test indicates the presence of primary alcoholic group
in the given compound.
RCH2OH  [O]
→ RCHO + H2O
(iv) Ceric ammonium nitrate test: Shake a few drops of ceric ammonium nitrate with 1 ml of the organic compound. A
red colour is produced (Phenols give a green or brown colour)
2ROH + (NH4)2[Ce(NO3)6] → [Ce(NO3)4(ROH)2] + 2NH4NO3
Distinction between primary, secondary and tertiary alcohols
Lucas test: Add 3-4 drops of alcohol to 2 ml of Lucas reagent (anhydrous ZnCl2 + conc. HCl) in a test-tube. Shake the
mixture and allow to stand at room temperature. If a cloudy precipitate is obtained immediately then it is a tertiary,
alcohol, if obtained after 2-3 minute then it is a secondary alcohol, while no cloudy precipitate even after long
standing means it is a primary alcohol.
G G±
5 &O
±
5±2+=Q&O 5±2=Q&O 5&O
>=Q 2+ &O@±
+
(f) Tests for primary amines (–NH2)
(i) Carbylamine test: Heat the organic compound with alcoholic KOH and chloroform in a test-tube. A highly offensive
smell is evolved due to formation of isocyanides.
RNH 2 + CHCl3 + 3KOH → R − N → C + 3KCl + 3H 2 O
This test is applicable to aliphatic and aromatic primary amines.
(ii) Dye test: This test is applicable only for aromatic primary amines. Dissolve a small amount of the organic compound in
dil. HCl. Cool it in ice-cold water. Add cold solution of sodium nitrite with constant shaking and then add b-naphthol
prepared in NaOH solution. An orange-red dye is obtained.
1D12+&Oo+121D&O
ĺ
&O±

1++12+&O 1{1+2
2+ 2+
&O ±

1{1 1 1
+&O
EQDSKWKRO 2UDQJHUHGG\H
(g) Tests for secondary amines (– NH –)

(i) Liebermann’s nitroso test: Dissolve some organic compound in 3 ml of conc. HCl and then add 2-3 ml of water.
Cool the solution in ice-cold water and then add 3-4 ml of cold dilute NaNO2 solution. A white or yellow emulsion
is produced. Take 4-5 drops of the above emulsion in a test tube. Add 4-5 drops of phenol and conc. H2SO4. A blue
colour develops. Addition of water changes blue colour to red which again changes to blue on adding NaOH solution.
(h) Tests for nitro group

(i) Reduction test: Take a small amount of the organic compound in a test-tube. Add a few ml of conc. hydrochloric acid
and one or two pieces of granulated zinc or tin. Heat the mixture gently for few minutes. Decant the clear liquid into
a test-tube. Cool it in ice-cold water and then add cold dilute solution of sodium nitrite. Pour this cold solution into
an alkaline of b-naphthol. An orange-red dye is obtained. This test is applicable only to aromatic nitro compounds.
Zn + 2HCl → ZnCl2 + 2[H]

C6H5NO2 + 6[H] → C6H5NH2 + 2H2O
NaNO2 + HCl → HNO2 + NaCl
C6H5NH2 + HNO2 + HCl → C6H5N2+Cl– + 2H2O
2+ 2+
&O ±

1{1 1 1
+&O
EQDSKWKRO 3KHQ\OD]REQDSKWKROG\H
(ii) Mulliken’s test: Take a small amount of the organic compound in a test-tube. Add a few ml of water or alcohol, 1 ml
of calcium chloride or ammonium chloride solution and then a pinch of zinc dust. Boil the mixture for few minutes.
Cool and then filter. Treat this filtrate with ammoniacal silver nitrate solution. A grey or black precipitate is obtained.
Zn + 2H2O → Zn(OH)2 + 2[H]

C6H5NO2 + 4[H] → C6H5NHOH + H2O
C6H5NHOH + Ag2O → C6H5NO + H2O + 2Ag↓
Grey
This test is also applicable for aromatic nitro compounds.
QUANTITATIVE ELEMENTAL ANALYSIS

After determining the constituent elements of an organic compound, the next step is to determine their amounts by quanti-
tative methods. The methods usually involve combustion, oxidation etc., of an organic compound so that they may change
into such inorganic compounds as can be estimated either by volumetric or gravimetric method.
The percentage composition of elements present in an organic compound are determined by the methods based on the
following principles:
Estimation of Elements
1. Liebig’s method for carbon and hydrogen
Both carbon and hydrogen are estimated in one experiment. A known mass of an organic compound is burnt in presence of
excess of oxygen and copper (II) oxide. Carbon and hydrogen in the compound are oxidised to carbon dioxide and water
respectively.
CxHy + (x + y/4) O2 —→ x CO2 + y/2 H2O
The mass of water produced is determined by passing the mixture through a weight U-tube containing anhydrous
calcium chloride. Carbon, dioxide is absorbed in another U-tube containing concentrated solution of potassium hydrox-
ide, These tubes are connected in series. The increase in masses of calcium chloride and potassium hydroxide gives the
amounts of water and carbon dioxide from which the percentages of carbon and hydrogen are calculated.
VDPSOHLQ
SODWLQXPERDW
&X2SDOOHWV
&RPEXVWLRQWXEHU
H[FHVV2
SXUHGU\
DQK\GURXV&D&O .2+VROXWLRQ
R[\JHQ
Estimation of carbon and hydrogen. Water and carbon dioxide formed on oxidation of substance are
absorbed in anhydrous calcium chloride and potassium hydroxide solution respectively contained in U tube.
12 wt. of CO2
%C= x x 100
44 wt. of organic compound
2 wt. of H 2O
%H= x x 100
18 wt. of O.C
Modification under specific conditions
a. Substance containing nitrogen

Under the condition of combustion nitrogen is present will be oxidised which will also be absorbed in KOH. In such cases
reduced copper gauze is placed near the exit end which reduce nitrogen oxide into N2.
b. Substance containing halogen

Halogen if present are converted into cupric halide which decompose to form free halogens. These halogen and cupric
halides also react with KOH.
Cl2 + NaOH —→ NaClO + NaCl + H2O
CuX2 + NaOH —→ Cu(OH)2 + 2NaX
In such cases, a roll of bright silver gauze is placed near the exit end of combustion tube silver gauze will decompose
CuX2 and X2 into (Cu + AgX) and (AgX).
c. Substance containing sulphur or both sulphur and halogen

Under the condition of combustion, sulphur, if present in the organic compound is oxidised to SO2 which will be adsorbed
in KOH. In such cases, an additional, layer of fused lead chromate is placed after the CuO layer or CuO layer is replaced
by PbCrO4.
∆
4 PbCrO 4 → 4PbO + 2Cr2O3 + 3O2
Oxygen produced will oxidise C and H to CO2 and H2O; SO2 and halogen produced react with PbCrO4, to form non-
volatile lead sulphate & lead halide.
∆
4PbCrO4 + 4SO2 → 4PbSO4 + 2Cr2O3 + O2
∆
4PbCrO4 + 4X2 → 4 PbX2 + 2Cr2O3 + O2
PbCrO4 can also react with P2O5 (formed by oxidation group) to form non-volatile lead phosphate.
∆
12 PbCrO4 + 4P2O5 → 4 Pb3(PO4)2 + 6 Cr2O3 + 9 O2
2. Dumas method for estimation of ‘N’ (all organic compound)

In this method the organic compound is heated with copper oxide strongly. Carbon, hydrogen and sulphur are oxidized to
CO2, H2O and SO2 respectively, while nitrogen is set free. These gases are passed through a nitrometer containing 30%
KOH solution. Carbon dioxide and sulphur dioxide are absorbed, steam condenses and nitrogen collects by the displace-
ment of KOH solution. From the volume of the collected nitrogen, the percentage of nitrogen is calculated.
y z
CxHyNz + CuO → xCO2 + H2O + N2 + Cu
2 2
reduced copper
CuO + organic
compound
Coarse CuO
CuO gauze
gauze
nitrogen
CO2
KOH
furnace
mercury seal
nitrometer
Calculation
Let the weight of the sample = Wg
Volume of moist N2 = V cc
Room temperature = t°C
Barometric pressure = P mm
Aqueous tension at t°C = f mm
P1V1 P2 V2
We know, =
T1 T2
or (P − f ) × V 760 × V2 (V2 = volume of N2 at NTP)

=
(273 + t) 273
(P − f ) × 273 × V
V2 = cc
760 × (273 + t)
Volume of N2 at NTP in cc = (P − f ) × 273 × V cc

760 × (273 + t)
Now, 22400 cc of N2 at NTP weigh 28 g

(P − f ) × 273 × V  28(P − f ) × 273 × V 
\ at NTP weigh  760 × 22400(273 + t)  g
760 × (273 + t)  
28(P − f ) × 273 × V
Wg of the substance contain gN 2
760 × 22400(273 + t)
\ 100 g of the substance contains 28(P − f ) × 273 × V × 100

760 × 22400W(273 + t)
28 Volume of N 2 at NTP
Percentage of Nitrogen = × × 100
22400 Weight of substance
3. Kjeldahl’s method for estimation of nitrogen

The compound containing nitrogen is heated -with concentrated sulphuric acid. Nitrogen in the compound gets converted
to ammonium sulphate. The resulting acid mixture is then heated with excess of sodium hydroxide. The liberated ammonia
gas is absorbed in an. excess of standard solution of sulphuric acid. The amount of ammonia produced is determined by
estimating the amount of sulphuric acid consumed in reaction. It is done by the estimating unreacted sulphuric acid left
after the absorption of ammonia by titrating it with standard alkali solution. The difference between the initial amount of
acid taken and that left after the reaction gives the amount of acid reacted with ammonia.
NaOH / ∆
N + H 2SO 4 (conc.) 
→(NH 4 ) 2 SO  →(NH 4 ) 2 SO 4 
NaOH
excess
→ 2NH 3 + 2H 2 O+ Na 2SO 4
2NH 3 + H 2SO 4 
→(NH 4 ) 2 SO 4
n gm equivalent. of acid used with NH3 = ngm equivalent. Acid taken – ngm equivalent acid left unused
N1V1
= − gm equivalent of Base used for unused acid
1000
NV N V
ngm equivalent of NH3 = 1 1 − 2 2
1000 1000
N1 & V1 are Normality and volume of Acid taken initially.
N2 & V2 are Normality and volume of Base used to titrate acid.
If 1gm equivalent of NH3 has 14 gm nitrogen
N1V1 − N 2 V2
Then – ngm equivalent of NH3 will have N1V1 − N 2 V2 × 14 gm of Nitrogen
1000 1000
If the Wt of sample is W gm
(N1V1 − N 2 V2 ) × 14 100
Precentage N = ×
1000 W
14 N(acid) × V(acid used)
Or %N = × ; V = V2 − V1
10 Mass of O.C
Kjeldahl method is not applicable to compounds containing nitrogen in nitro and azo groups and nitrogen present in the
ring (e.g., pyridine) as nitrogen of these compound not change to ammonium sulphate under these conditions
4. Carius method for estimation of halogen.

(i) Carius Method: The compound containing halogen is heated with fuming nitric acid in a sealed tube (Carius tube) in
presence of silver nitrate. Carbon and hydrogen present are oxidized to carbon dioxide and water. The halogens react
with silver nitrate to give the precipitate of silver halide. The precipitate is collected, washed, dried and weighed.
Calculation
Let the weight of the substance be Wg
Weight of the silver halide be yg
Atomic weight of halogen

Weight of halogen = × yg
Molecular weight of silver halide
Atomic weight of halogen 100
\ Percentage of halogen = ×y×
Molecular weight of silver halide W
Estimation of Sulphur through carius method:

A known mass of an organic compound is heated in a Carius tube with sodium peroxide or fuming nitric acid. Sulphur
present in the compound is oxidized to sulphuric acid. It is precipitated as barium sulphate by adding excess of barium
chloride solution. The precipitate is filtered, washed, dried and weighed. The percentage of sulphur can be calculated from
the mass of barium sulphate.
32 wt. of BaSO 4
S% = × × 100
233 wt. of O.C.
Organic compound 
HNO3
∆
→ H 2SO 4 
BaC12
→ BaSO 4 white ppt.
5. Estimation of phosphorous
A known mass of an organic compound is heated with fuming nitric acid whereupon phosphorus present in the compound
is oxidized to phosphoric acid. It is precipitated as ammonium phosphomolybdate. (NH4)3 PO4. 12MoO3, by adding am-
monia and ammonium molybdate. Alternatively, phosphoric acid may be precipitated as MgNH4PO4 which on ignition
yields Mg2P2O7.
∆ ( NH 4 )2 MoO4 + HNO3
L.S + HNO3  → H 3 PO 4  → (NH 4 )3 PO 4 ,12M O O3
Estimation of P
( NH 4 Cl + Mgcl2 )
O.C 
conc.HNO3
∆
→ H 3 PO 4  → MgNH 4 (PO 4 ) white ppt. 
Magnesia Mix.
∆
→ Mg 2 P2 O7
Magnesium Ammonium Magnesium
Phosphate pyrophosphate
At. Wt. of P Wt. of pyrophosphate

%P= ×
M. Wt. of Pyrophosphate Mass of organic compound
62 Mass of Mg 2 P2 O7
%P= × × 100
222 Mass of O.C
6. Percentage of oxygen
The percentage of oxygen in an organic compound is usually found by difference between the total percentage composition
(100) and the sum of the percentages of all other elements. However, oxygen can also be estimated directly as follows:
A definite mass of an organic compound is decomposed by heating in a stream of nitrogen gas. The mixture of gaseous
products containing oxygen is passed over red-hot coke when all the oxygen is converted to carbon monoxide. This mixture
is passed through warm iodine pentaoxide(I2O5) when carbon monoxide is oxidized to carbon dioxide producing iodine.
Compound heat
→ O2 + other gaseous products
1373K
2C + O2 → 2CO
I2O5 + 5CO → + I2 + 5CO2
The percentage of oxygen can be derived from the amount of carbon dioxide or iodine produced.
Let the mass of organic compound taken = gm
Mass of carbon dioxide = M1g
44 g carbon dioxide contains 32 g oxygen
M1 g carbon dioxide contains 32 × m1 g oxygen

44
32 × m1 × 100
Percentage of oxygen = ,
44 × m
Presently the estimation of elements in an organic compound is carried out by using microquantities of substances and
automatic experimental techniques. The elements, carbon, hydrogen and nitrogen present in a compound are determined
by an apparatus known as CHN elemental analyzer.
Determination of Molecular Weight

1. Victor meyer method (Volatile organic compounds)
In this method a known wt of organic compound is vaporized and collected by displacement method at pressure (P1) &
temperature (T1). If volume of vapours is V1 then mass of organic compound-will be
W1
P1V1 = RT
M
W1RT
M.Wt. =
P1V1
b. Volumetric method
This is titration method when gram equivalent of acid will be equal to gm equivalent of base.
Acid + Base 
→ Salt
W1 gm NV
Wt. NV
× Basicity =
M.Wt 1000
 wt. of acid 
M.wt of acid =  × 1000  × basicity
 N × V(ml) of baseused 
 wt. of base 
M.wt of base =  × 1000  × Acidity
 N × V of Acid 
2. Silver salt method for determining molecular weight of organic acids

This method is based on the fact that organic acids form insoluble silver salts which on ignition leave a residue to metallic
silver.
A small quantity of organic acid is treated with water or a suitable solvent and then a slight excess of ammonia solution
added. The solution is boiled to expel excess of ammonia. Excess of silver nitrate solution is added to this solution when a
white precipitate of insoluble silver nitrate solution is added to this solution when a white precipitate of insoluble silver salt
is obtained. The precipitate is filtered and washed successively with water, alcohol and ether and then dried in an air oven.
A known weight of the silver salt is taken in a weighed crucible and ignited till decomposition is complete. The crucible
is cooled and then weighed. Heating, cooling and weighing is continued till the final weight is constant.
Calculation
Weight of crucible + lid = Wg
Weight of crucible + lid + silver salt = W1g
Weight of crucible + lid + residual silver = W2g
Weight of silver salt = (W1 – W) g
And weight of silver = (W2 – W) g
(W2 – W) g of silver is obtained from (W1 – W) g of silver salt.
(W1 − W) × 108
108 g of silver is obtained from g of silver salt.
(W2 − W)
(W1 − W) × 108
Equivalent weight of silver salt =
(W2 − W)
But equivalent weight of acid = Equivalent weight of Ag salt – 108 + 1
= Equivalent weight of Ag salt – 107
 (W − W) × 108 
\ Molecular weight of the acid =  1 − 107 × n (where n = basicity of the acid)
 (W2 − W) 
3. Chloroplatinate salt method

Most organic bases, e.g. amines react with chloroplatinic acid (H2PtCl6) to form salts, chloroplatic acid (H2PtCl6) to form
salts, chloroplatinates, of general formula, B2H2PtCl6 where B is a monoacidic amine. On heating, these salt decomposed
and yield metallic platinum
2RNH2 + H2PtCl6 → (RNH3)2PtCl6
(RNH2)2H2PtCl6 ignite
→ Pt
The salt formed with H2PtCl2 and diacidic amine, B would be B2(H2PtCl6)2 and with triacidic amine. salt formed would
be B2(H2PtCl6)3 and that will amine of acidity n, it would be B2(H2PtCl6)3 and that will amine of acidity n, it would be
B2(H2PtCl6)n.
Let the mass of organic compound taken n = m g
Mass of chloroplatinate salt taken = m1 g
Mass of metallic platinum formed = m2 g
One gram atom of platinum will be obtained from 1 gram mole of chloroplatinate salt.
\ 195 g (atomic mass of Pt) of Pt is obtained from 1 gram mole of its monoacidic base.
\ m2g Platinum will be obtained from m1 g of platinum salt of monoacidic base.
m × 195
195 g platinum is obtained from 1 g salt = Molecular wt. of salt
22
Molar mass of chlomroplatinate salt of
m1 × 195
(i) monoacidic base [B2 (H 2 PtCl6 )] =
m2
m1 × 195
(ii) diacidic base [B2 (H 2 PtCl6 ) 2 ] = ×2
m2
m1 × 195
(iii) polyacidic base [B2 (H 2 PtCl6 ) n ] = ×n
m2
Molecular mass of the base B.
1
= [molar mass of chloroplatinate salt – molar mass of (H 2 PtCl6 )N]
2
1
= [molar mass of chloroplatinate salt – n × (410)]
2
Where 410 is the molar mass of H2PtCl6; n = Acidity of Base.
∆
B2 + H 2 PtCl6 → B2 H 2 PtCl6  → Pt
wt.of pt.salt 2B + 410
= (M. wt = B × Acidity of Base)
wt.of Pt 195
Illustrations
1. 0.70 g of an organic compound was Kjeldahlised and the liberated ammonia was absorbed in 100 mL of N/10
H2SO4. After absorption the left over acid required 10 mL of N/5 NaOH for complete neutralization. Calculate
the percentage of nitrogen in the given compound.
Ans. 10 mL N/5 NaOH ≡ 20 mL N/10 NaOH ≡ 20 mL N/10 H2SO4
Acid consumed = (100 – 20) mL of N/10 H2SO4
Ans. N = 16%
2. 0.4 g of an organic compound was Kjeldahlised and ammonia evolved was absorbed into 50 mL of seminormal
solution of sulphuric acid. The residual acid solution was diluted with distilled water and the volume was made
to 150 mL. 20 mL of this diluted solution required 31 mL of 0.05 N NaOH for complete neutralization. Calculate
the percentage of nitrogen in the compound.
Ans. 20 mL diluted acid solution ≡ 31 mL of 0.05 N NaOH
31
150 mL diluted acid solution ≡ × 150 mL 0.05 N NaOH
20
≡ 232.5 mL 0.05 N H2SO4
≡ 23.25 mL 0.5 N H2SO4
Ans. N = 46.81%
3. In Kjeldahl method the gas evolved from 1.325 g sample of a fertilizer is passed into 50 mL of 0.2030 N H2SO4.
25.32 mL of 0.1980 N NaOH are required for the titration of the unused acid. Calculate the percentage of nitrogen
in the fertilizer.
Ans. 25.32 mL 0.1980 N NaOH
≡ 25.32 mL 0.1980 N H2SO4
≡ 24.696 mL 0.2030 N H2SO4
≡ 24.7 mL 0.2030 N H2SO4
Ans. N = 5.43%
4. 1.5 g of an organic compound in a quantitative determination of phosphorus gave 2.5090 g of Mg2P2O7. Calculate
the percentage of phosphorus in the compound.
62 Mass of Mg 2 P2 O7
Ans. Percentage of P = × × 100
222 Mass of org. compound
Ans. P = 46.7%
5. A compound X gave the following results on combustion:

(i) 0.36 g gave 0.528 g CO2 and 0.324 g water.
(ii) In nitrogen estimation by Duma’s method, 0.295 g gave 56 mL of N2 at NTP.
(iii) X is a monoacid base. Its platinichloride contains 37.39% platinum.
Find the molecular formula of the compound.
Ans. Molecular mass of the compound (acidity = 1)
1  100 
= ×1×  × 195 − 410  = 56
2  37.39 
Ans. C3H9N
6. 0.21 g of an organic substance containing C, H, O and N gave on combustion 0.462 g carbon dioxide and
0.1215 g water. 0.104 g of it when distilled with NaOH evolved H2SO4. Calculate the empirical formula.
Ans. 15 mL 0.05 N H2SO4 ≡ 15 mL 0.05 N NH3 ≡ 15 mL

1.4 × 0.05 × 15
0.05 N N2 Percentage of N2 = = 10.09
0.104
Ans. C7H9NO2
7.An organic liquid on analysis yielded the following results:

(i) The compound consisted carbon, hydrogen, nitrogen and sulphur.
(ii) On combustion, carbon and hydrogen were found to be 41.37% and 5.75% respectively.
(iii) On Kjeldahlising, ammonia obtained from 2.02 g of the substance was neutralized completely by 23.2 mL
N HCl
(iv) In the Carius estmation of sulphur, 0.1033 g of the substance resulted in the precipitation of 0.2772 g of
BaSO4.
(v) 0.1015 g of the liquid when vaporized displaced 27.96 mL of dry air measured at 15°C and 750 mm pressure.
Find the formula of the substance.
273 750
Ans. Volume of air at NTP = 27.96 × × = 26.16 mL
288 760
22400 × 0.1015
The molecular mass of the substance = = 86.9
26.16
Ans. Molecular formula = C3H5NS
8. A substance on analysis gave the following data:

0.3112 g gave 0.4291 g of CO2 and 0.0585 g of water. 0.2293 g of the substance when heated with nitric acid and
silver nitrate gave 0.3969 g of bromide and chloride of silver. 0.2202 g of this mixture of halides was found to
contain 0.1435 g of silver. Find the empirical formula of the original substance.
Ans. Let x g of AgCl be present in the 0.2202 g of the mixture of AgBr and AgCl
108x 108 × (0.2202− x )

So, + = 0.1435
143.5 188
x = 0.0954 g
Determine the amounts of AgCl and AgBr in 0.3969 g of the mixture.
x
AgCl = × 0.3969 = 0.1720 g
0.2202
AgBr = (0.3969 – 0.1720) = 0.2249 g
35.5 0.1720
Thus, percentage of Cl = × × 100 = 18.55
143.5 0.2293
80 0.2249
and percentage of Br = × × 100 = 41.73
188 0.2293
Ans. C6H4ClBr
PRACTICAL ORGANIC CHEMISTRY (C) on reaction with PCl5 followed by Mg/Ether gives
(E). Action of (E) on (D) followed by hydrolysis gives
1. Compound A (C8H12Cl) exists as a racemic form. (F). Identify (A) to (F).
Compound A does not decolourise either Br2/CCl4 or Sol.
dilute aqueous KMnO4. When A is treated with Zn/ OH
CH3COOH, two fractions B and C both with molecular NH2
A= B=
formula C8H16 are obtained fraction B consists of a H3C
racemic form and can be resolved. Fraction C can’t be H3C CH3
resolved. Treating A with sodium ethoxide in ethanol O
converts A into D(C8H14). Hydrogenation of D using OH
platinum catalyst yields C. Ozonolysis of D, followed C= D=
by treatment with zinc and water yields. H3C
H3C CH3
O CH3
MgCl OH
CH3
H3C E= F=
H3C H3C CH3
O
4. In a reaction flask propanedial was reduced with
Assign structures to A, B, C and D.
excess LiAlH4 to give (A), which gave a red
Sol. colouration with cerric ammonium nitrate. Treatment
Cl CH3 of (A) with excess PBr3 converts (A) to (B). (B)
CH3
A= B= on reaction with excess of magnesium in dry ether
CH3 CH3 formed (C). In another reaction flask, 1, 4-pentadiene
was treated with excess of HCl in the presence of
&+ &+
benzoyl peroxide to give (D). (D) on treatment with
& ' excess of aqueous KOH gave (E). (E) was subjected
&+ &+ to oxidation with excess of CrO3 - pyridine to give (F)
having M.F. C5H8O2. The compound (F) was added
2. An organic compound (A), C5H9Br which readily dropwise to compound (C) in dry ether to isolate a
decolourises bromine water and KMnO4 solution gives salt which on acidification with dil. HCl gave (G),
(B), C5H11Br on treatment with Sn/HCl. The reaction having M.F. C8H16O2 as a major product. (G) was
of (A) with NaNH2 Produces (C) with evolution of difficult to oxidise by CrO3/H+. Identify (A) to (G).
ammonia. (C) neither reacts with sodium nor forms Representation of the above reactions should be given
any metal acetylide but reacts with Lindlar catalyst to clearly.
give (D) and on reaction with Na/liq. NH3 produces
Sol.
(E). Both the compounds (D) and (E) are isomeric.
Give structures of (A) to (E) with proper reasoning. H
Sol. O HO
Ex. LiAlH 4 Ex. PBr3
A = CH3—CH = CBrC2H5
B = CH3—CH2—CHBr — C2H5 (Reduction )
C = CH3—C ≡ C C2H5 O HO
D = CH3CH = CHC2H5 (cis) H (A)
E = CH3CH=CHC2H5 (trans)
Br BrMg
3. An organic compound (A) of m.f. C3H9N which gives Excess
a repulsive odour with CHCl3 and KOH, on treatment Mg
with aq. HNO2, gives two isomeric compounds (B) Br BrMg
and (C). (B) on treatment with H+/KMnO4 gives (D). (B) (C)
H2 C Cl OH
+&
H3 C H3C
Ex. HCl Ex. aq. KOHl A= % &+
(Markownikoff (Substitution) CH3
addition) H3 C SURSHQH
Cl propan-2-ol
H2 C (D)
2
OH O +&
H3 C H3 C +&
[O] CrO3 (C) & &+ '
&+
SURS\QH
H3 C H3 C DFHWRQH
(E) OH (F) O
6. Five isomeric para-disubstituted aromatic compounds
CH3 A to E with molecular formula C8H8O2 were given for
OH identification. Based on the following observations,
give structures of the compounds.
(i) Both A and B form a silver mirror with Tollen’s
CH3 reagent; also B gives a positive test with FeCl3
(G) OH solution.
(ii) C gives positive iodoform test.
5. An alcohol (A) on treatment with conc. H2SO↑4 gave (iii) D is readily extracted in aqueous NaHCO3 solu-
an alkene (B). The compound (B) on reacting with tion.
Br2 water and subsequent dehydrobromiantion with (iv) E on acid hydrolysis gives 1,4-dihydroxyben-
NaNH2 produced a compound (C). The compound zene.
(C) with dil. H2SO4 in presence of HgSO4 gave Sol.
a compound (D). The compound (D) can also be
CH2OH OCH3
obtained by oxidation of (A) by KMnO4 or from
distillation of Ca acetate. Name (A), (B), (C), D) and A= or
explain reactions. OHC OHC
Sol. i) (d) is also obtained by distillation of Ca acetate CH2CHO
as well as by oxidation of (A) by KMnO4. Thus, (D) is B=
acetone and (A) is propan-2-ol. HO
2(CH 3 COO) 2 Ca 
→ 2CaCO3 + 2CH 3 COCH 3 O
Calcium acetate (D)
CH 3 CHOHCH 3 
→ CH 3 COCH 3 C – CH3
(A) Propan -2-ol (D) Propanone C=
HO
ii) (A) on treatment with conc. H2SO4 gives (B)
CH 3 CHOHCH 3  → CH 3 − CH = CH 2 CO2H
(A) (B) Propene D=
iii) (b) reacts with Br2 water and subsequent dehydro- CH3
bromination by NaNH2 produces (C). O–H
CH 3 CH = CH 2 
Br2
→ CH 3 CHBr − CH 2 Br E=
1,2 − dibromopropane
CH 2 = CH – O
CH 3 CHBr − CH 2 Br → CH 3 C ≡ CH
NaNH 2
−2HBr
(C) Propyne 7. Compound (A), C6H12O, forms an oxime but gives
iv) (C) gives (D) on action of H2SO4 + HgSO4 a negative Fehling’s test. When (A) is reduced
with LiAlH4, compound (B), C6H14O is produced.
CH 3 C ≡ CH + 2H 2 O 
H 2 SO4
+ HgSO 4

→ Compound (B) on heating with conc. H2SO4 gives
O
|| (C), C6H12. (C) on ozonolysis gives (D) and (E). (D)
CH 3 − C − CH 3 + HgSO 4 gives a negative Tollen’s test but a positive iodoform
test. Compound (E) gives a positive Tollen’s test and C = H5 C 6 C CH3

a negative iodoform test. Identify (A) and (E) and
explain different reactions involved. HO N
Sol. D = H3 C C NH
CH3
O C 6 H5
A= H3C CH3 E = H5 C 6 C NH
O O CH3
CH3 F = H5C6 — NH2
O
B= H3C CH3
G= H5 C 6
OH
OH
CH3
Na in
C= (b) H3 C
CH liquid NH3
H3C CH3 but-1-yne
CH3 X
H3C
H3 C –NaX
D= O Na
H3C HgSO4
H3C H 2SO4
H3C
E= CH3
O pent-2-yne
8. a) Compound ‘A’ (C8H8O) on treatment with NH2OH. H3C O

HCl gives ‘B’ and ‘C’. ‘B’ and ‘C’ rearrange to give
‘D’ and ‘E’, respectively, on treatment with acid. ‘B’, CH3
‘C’, ‘D’ and ‘E’ are all isomers of molecular formula pentan-2-one
(C8H9NO). When ‘D’ is boiled with alcoholic KOH an
oil ‘F’ (C6H7N) separates out. ‘F’ reacts rapidly with 9. An unknown compound of carbon, hydrogen and
CH3COCl to give back ‘D’. On the other hand, È’ on oxygen contains 69.77% C and 11.63% H, and has
boiling with alkali followed by acidification gives a a molecular weight of 86. It does not reduce Fehling
white solid ‘G’ (C7H6O2). Identify ‘A’ to ‘G’. solution but forms a bisulphate addition compound
b) Carry out the following transformation in not more and gives a positive iodoform test.What are the
than three steps. possible structures?
Sol.
H3C O
H3C (i) For empirical formula
H Element % Relative no. Simplest
CH3
of atoms ratio
Sol. C 69.77 5.76 5
a) H 11.63 11.63 10
O O 19.20 1.2 1
A= CH3 \ Empirical formula of compound is C5H10O.

and Empirical formula wt. = 86
Also Molecular wt. = 86
H5C 6 C CH3 \ Molecular formula of compound is C5H10O.
B= (ii) Compound forms bisulphate addition compound
N OH and thus, has carbonyl gp. i.e., aldehyde or ketone.
(iii) It does not reduce Fehling solution and thus, it is O

not aldehyde but it is ketone.
(iv) It gives positive iodoform test and thus, it has
G= O
O
H3 C O
11. A compound A of the formula C7H5O2NCl2 is soluble
(v) Above facts reveals that compound is in alkali. The compound on reduction with Fe/HCl
H3 C followed by treatment with HNO2 gives a primary
CH3
alcohol B which contains no nitrogen. B on oxidation
CH 3 .CH 2 .CH 2 .C.CH 3 or gives an acid C, the equivalent mass of which is 191 g
mol–1. (C) on decarboxylation gives (D) which gives
H3 C O one monosubstituted product. Identify (A), (B), (C)
O
Pentan-2-one 3-methylbutan-2-one and (D).
Sol.
10. The compound C8H6Cl (A) on treatment with Cl Cl
KCN followed by hydrolysis gives C9H10O2 (B). NO2 OH
Ammonium salt of B on dry distillation yields C A= B=
which reacts with alkaline solution of bromine to
give C8H11N (D). Another compound (E) C8H10O2 is Cl Cl

obtained by the action of nitrous acid on (D) or by
Cl O Cl
the action of aqueous potash on (A). (E) on oxidation
gives (F) C8H8O4 which gives the inner anhydride (G) OH
on heating. Deduce the structures of (A) to (G) giving C= D=
the reactions involved.
Cl Cl
Sol.
12. An organic compound A (C9H11NO2) on nitration in
O
acetic acid gives only one mono nitro derivatives B.
Cl
On hydrolysis with dilute sulphuric acid B gives one
OH molecule of C and one molecule of acetic acid. C, on
CH3 B= CH3 diazotization and heating with hypophosphorus gives
A= D. The latter is oxidized with alkaline KMnO4 to an
acid E which on decarboxylation gives nitrobenzene.
Deduce the structures A to E giving relevant reactions.
Sol.
O
NH2 HO
A= NH
NH2 O
CH3
C= CH3 D= H3C
HO
NH
B= O
HC
OH O OH NO2 3
O
HO
CH3 NH2
E= F= OH C=
NO2
HO Sol.
NH2 OH NC CN COOH
D=
NO2
HO
E=
O CH3 CH3 CH3 CH3 COOH
NO2
(A) (B) (C) (D) (E)
13. An aromatic compound (A), having M.F C7H5NO2C12
15. A pungent smelling liquid (A) was analysed and found
on reduction with Sn/HCl gives (B), which on reac-
to contain carbon, hydrogen, chlorine and possibly
tion with NaNO2/CH1 gives (C). Compound (B) is
oxygen and upon reaction with aqueous ammonia a
unable to form a dye with β-naphthol. However, (C)
neutral compound (B) was formed. When this was
gives red colour with ceric ammonium nitrate and
treated with bromine and potassium hydroxide a base
on oxidation gives an acid (D), having equivalent
(C) resulted. In acidic solution substance C reacted
weight 191. Decarboxylation of (D) gives (e) which
with sodium nitrite, giving nitrogen and an alcohol (D).
forms a single mononitro derivative (F), on nitra-
Upon mild oxidation, the alcohol (D) was converted
tion. Give the structures of (A) to (F) with proper
into compound (E) of M.F. C2H4O which gave a
reasoning.
positive test with ammoniacal silver nitrate solution.
Sol. Describe the chemistry involved in these reactions and
identify the compounds (A) (B) (C) (D) and (E).
Cl Cl Cl
Sol.
CH2NO2 CH2NH2 CH2OH A = CH3CH2COCl B = CH3CH2CONH2;
C = CH3CH2NH2; D = CH3CH2OH;
E = CH3CHO
Cl Cl Cl 16. Reaction of a compound (A) (C11H14) with trioxygen

(A) (B) (C) and then water gave (B) (C8H8O) and (C) (C3H6O)
in equimolar amounts. (C) was unaffected by
Cl Cl Cl ammoniacal silver nitrate, but (B) reacted with this
COOH NO2 reagent to give (D) (C8H8O2). When (D) was treated
successively with sulphur dichloride oxide and
ammonia, (E) (C8H8NO) was formed. E reacted with
bromine and sodium hydroxide to give (F) (C7H9N),
Cl Cl Cl a much weaker base than methylamine. Identify the
compounds (A) to (F), as far as is possible and comment
(D) (E) (F)
on the reactions. Suggest further experiments (i) to
confirm the identification of (C) and (ii) to be carried
14. An organic compound (A) having M.F C7H9N on out on compound (D) to complete the identification of
treatment with NaNO2 and HCl at room temperature compounds (D) to (F).
forms another compound (B), C7H8O. When (A) or
Sol.
(B) is treated with bromine water, they form dibromo
A = CH3—C6H4—CH=C(CH3)2
derivatives, When (A) is reacted with chloroform
B = CH3C6H4—CHO
and alkali, it forms (C) having the molecular formula
C = CH3COCH↑3
C8h7N. Hydrolysis of (C) followed by reaction with
D = CH3—C6H4—CO2H
NaNO2 and HCl at low temperature and subsequent
E = CH3—C6H4CONH2
reaction with HCN in the presence of Cu(D), which
F = CH3—C6H4—NH2
is isomeric to (C). (D) on hydrolysis followed by
oxidation gives a dibasic acid, which on halogenation 17. An acidic compound (A), C4H8O3 loses its optical
forms only one monohalo derivative. Identify the activity on strong heating yielding (B), C4H6O2 which
compounds (A) to (E). reacts readily with KMnO4. (B) forms a derivative
(C) with SOCl2, which on reaction with (CH3)2NH COOH

gives (D). The compound (A) on oxidation with
E=
dilute chromic acid gives an unstable compound (E) OSO2C6H5
which decarboxylates readily to give (F), C3H6O. The
compound (F) gives a hydrocarbon (G) on treatment CO2H
with amalgamated Zn and HCl. Give structures of (A) F=
to (G) with proper reasoning. OSO2C6H5
Sol. CO2H
(A) CH3CHOHCH2COOH
(B) CH3CH=CHCOOH G=
(C) CH3CH = CHCOCl OH
(D) CH3—CH = HCON(CH3)2
19. An aqueous alcoholic solution of acetoacetic ester
(E) CH3COCH2COOH
imparts a blue colour with a solution of FeCl3. To
(F) CH3COCH3
this solution if bromine solution is added carefully,
(G) CH3CH2CH3
the initial colour disappears and the brown colour of
18. A solid organic compound (A), C9H6O2 is insoluble bromine appears, which fades soon and the solution
in dilute NaHCO3. It produces a dibromoderivative after remaining colourless for some time regains the
(B), C9H6O2Br2 on treatment with Br2/CS2. Prolonged blue violet colour. Explain.
boiling of (A) with concentrated KOH solution Sol.
followed by acidification gives a compound (C),
Acetoacetic ester shows tautomerism and the two
C9H8O3. The compound (C) gives effervescence with
aqueous NaHCO3. Treatment of (C) with equimolar forms are called as keto and enol forms.
amount of Me2SO4/NaOH gives (D), C10H10O3. O O OH O
The compound (D) is identical with the compound C2H5
C2H5
prepared from ortho-methoxy benzaldehyde by H3C O H3C O
condensation with acetic anhydride in the presence Keto form Enol form
of sodium acetate. Treatment of (C) with alkaline
OH
C6H5SO2Cl produces (E) which on vigorous oxidation |
with KMnO4 gives (F). Hydrolysis of (F) gives a The enol (H3C − C == CH−) gives blue-violet colour
steam volatile compound (G) having M.F. C7H6O3. with FeCl3 solution. When Br2 is added, it reacts at
Give the structures of (A) to (G) giving the proper
reaction sequences. once with of the enol form
Sol.
OH O
A=
C2H5 + Br2
O O H3C O
Br
Br
Br
B= HO
C 2H5
O O O
H3C
CO2H Br O
C=
OH As soon as enol form is consumed, its colouration with
CO2H FeCl3 disappears and excess of bromine gives brown
colour. As keto and enol forms are in equilibrium,
D= O when enol form is used, the equilibrium shifts to right
hand side to give more enol form which discharges
CH3
the colour of excess of Br2 and gives blue violet
colour with excess of FeCl3 present in the reaction Sol.

mixture. CH3 CH3
20. A hydrocarbon (A) which decolourises when treated
A = H3C
with Br2/CCl4 and gets reduced by 1 mole of H2 in
presence of Ni. When A is treated with dilute aqueous CH3
KMnO4 solutions gives B which on treatment with
Cl
phthalic acid gives a polymeric compound C which is
CH3
poly (ethylene glycol phthalate). Write the structures
of A, B and C. B= H C
3
Sol. CH3
A = H2C = CH2
CH3 Cl
B = HO – CH2 – CH2 – OH
HOOC C = H3C
O
C=
O CH3
O CH3
O O
OH CH3
O
D = H3C
O
|| CH3 Cl
C O O H
H
H2O CH3
Ph – C C – Ph C
|| || O
O O C C O E = H3C
CH3 CH2
Ph Ph CH3 CH3
21. An organic compound is optically active, but does F = H3C
not reduce Tollens reagent and Fehling solution.
Cl CH3
However, on heating with dilute mineral acids it gives
a mixture of one aldose and one ketose which reduced H3C CH3
Fehling’s and Tollens reagents. On reaction with acetic
anhydride and dimethyl sulphate in alkaline solution it G=
gives an octaacetate and octamethyl derivatives. It is CH3
H3C
not oxidized with Br2 – H2O but conc. HNO3 oxidises
it into oxalic acid. What is it?
23. Two isomeric alkyl bromides (A) and (B), C5H11Br
Sol. yield the following results in the laboratory. (A) on
This compound is a disaccharide sucrose. treatment with alcoholic KOH gives (C) and (D)
C5H10 (C) on ozonolysis gives HCHO and 2-methyl
22. An alkane (A) with M.F. C6H14 reacts with chlorine propanal. (B) on treatment with alcoholic KOH gives
in the presence of U.V light to yield three isomeric (D) and (E), C5H10. All compounds (C), (D) and (E)
monochloro derivatives (B), (C) and (D). Of these on catalytic hydrogenation give (F), C5H12. Deduce
only (C) and (D) undergo dehydrohalogenation with structures of (A) to (F).
sodium ethoxide in ethanol to produce an alkene. Sol.
Moreover (C) and (D) yields the same alkene (E)
(C6H12). Hydrogenation of (E) produces (A). Treating Br
(E) with HCl produces a compound (F) that is an CH3
isomer of (B), (C) and (D). Treating (F) with Zn and A=
H3C
acetic acid gives a compound (G), which is isomeric
with (A). Propose structures for (A) to (G). CH3
Br H3C
H3C CH3
F=
B= CH3
H3C
O
CH3
H3C CH2 H3C CH3 ≡
G=
C= O
H3C O
H3C CH3
H = H3C OH ≡ OH
D=
H3C CH3 O
CH3 25. A hydrocarbon (A) of molecular weight 54 reacts
with an excess of Br2 in CCl4 to give a compound (B)
E = H2C
whose molecular weight is 593% more than of (A).
CH3 However, on catalytic hydrogenation with excess of
H3C CH3 hydrogen, (A) forms (C) whose molecular weight
is only 7.4% more than that of (A). (A) reacts with
F= CH3CH2Br in the presence of NaNH2 to give another
H3C CH3 hydrocarbon (D) which on ozonolysis yields diketone
(E). (E) on oxidation gives propanoic acid. Give
24. An alkane (A), C5H12, on monochlorination at 300°C structures of (A) to (E) with reasons
gives a mixture of four monochlorinated derivatives Sol.
(B), (C), (D) and (E). Two of these derivatives give (i) Mol. wt. of (a) suggests is to be C4H6 i.e.,mol.
same stable alkene (F) on dehydrohalogenation. On wt. = 54
oxidation with hot alkaline KMnO4, followed by (ii) C4H8 has terminal triple bond as it reacts with
acidification (F) gives two products (G) and (H). Give CH3CH2Br in presence of NaNH2
structures of (A) to (H) with proper reasoning.
(iii) CH 3 CH 2 C ≡ CH 
Br2
→ CH 3 CH 2 CBr2 CHBr2
Sol. (A) (B)
CH3 Mol. wt. = 54 Mol. wt. = 374

A= CH3 593 × 54
Thus, Mol. wt. of B = + 54
H3C 100
Cl = 320 + 54 = 374
B= H3C (iv) CH 3 CH 2 C ≡ CH 
H2
→ CH 3 CH 2 CH 2 CH 3
(C)
CH3 CH3
Mol. wt. = 58
CH3 7.4
Thus Mol. wt. of C = × 54 + 54 = 58
CH3 100
C= H3C
(v) CH 3 CH 2 C ≡ CH 
NaNH 2
CH3 CH 2 Br
→
Cl CH 3 CH 2 C ≡ CCH 2 CH 3
(D)
Cl CH3
D= (D) Ozonolysis [O]
CH3 CH3CH2–C–CCH2CH3
CH3 O O
E
E= CH3CH2COOH
H3C Cl F
STEP–I CHECK YOUR CONCEPT 10. In Lassaigne’s test for nitrogen the blue colour is due
to the formation of
1. Aniline, chloroform and alc. KOH on heating gives (a) Ferric-Ferro cyanide
(b) K4[Fe(CN)6]
(a) Phenyl isocyanide (b) Phenyl cyanide
(c) Na4[Fe(CN)6]
(c) Chlorobenzene (d) Phenol
(d) NaCN
2. Methyl ketones are usually characterized through
11. Nitrogen is estimated by
(a) Tollen’s test (b) Iodoform test
(a) Liebig method (b) Carius method
(c) Schiff test (d) Benedict’s test
(c) Duma’s method (d) None of these
3. ClCH2COOH is heated with fuming nitric acid in the
12. In Kjeldahl’s method, nitrogen element is estimated
presence of AgNO3 in a Carius tube. After filtration
as
and washing a white precipitate is obtained. The
precipitate is (a) N2 (b) NO
(c) NH3 (d) NO2
(a) AgNO3 (b) Ag2O
(c) AgCl (d) ClCH2COOAg 13. 0.10 g of an organic compound containing phosphorus
gave 0.222 g of Mg2P2O7. Then the percentage of
4. Which of the following is used for separating aniline
phosphorus in it is
from nitrobenzene?
(a) 62 (b) 6.2
(a) Na2CO3 (b) HCl
(c) 31 (d) 13
(c) NaHCO3 (d) NaCl
14. The Prussian blue colour obtained during the test of
5. The compound that does not give a blue colour in
nitrogen by Lassaigne’s test is due to the formation of
Lassaigne’s test is
(a) Fe4[Fe(CN)6]3
(a) Aniline (b) Glycine
(b) Na3[Fe(CN)6]
(c) Hydrazine (d) Urea
(c) Fe(CN)3
6. The Lassaigne’s extract is boiled with dil. HNO3 (d) Na4[Fe(CN)5NOS]
before testing for halogens because
15. A compound which does not give a positive test in
(a) Silver halides are soluble in HNO3 Lassaigne’s test for nitrogen is
(b) Na2S and NaCN are decomposed by HNO3
(a) Urea (b) Hydrazine
(c) Ag2S is soluble in HNO3
(c) Azobenzene (d) Phenyl hydrazine
(d) AgCN is soluble in HNO3
7. In which of the following compounds, nitrogen cannot
be tested by Lassaigne’s test?
(a) C6H5NH2 (b) NH2.NH2.H2O
1. Which of the following reagent is used for the
(c) CH3CONH2 (d) C6H↑5NO2
separation of acetaldehyde from acetophenone?
8. When a nitrogen containing organic compound is (a) NH2OH (b) NaOHI2
strongly heated with conc. H2SO4, the product is (c) NaHSO3 (d) C6H5NHNH2
(a) HNO3 (b) (NH4)2SO2
2. The ammonia evolved from the treatment of 0.30 g of
(c) NH3 (d) N2
an organic compound for the estimation of nitrogen
9. A mixture of o-nitrophenol and p-nitrophenol can be was passed in 100 mL of 0.1 M sulphuric acid. The
separated by excess of acid required 20 mL of 0.5 M sodium
(a) Sublimation hydroxide solution for complete neutralization. The
(b) Steam distillation organic compound is
(c) Fractional crystallization (a) Urea (b) Thiourea
(d) Distillation (c) Acetamide (d) Benzamide
3. Duma’s method involves the determination of When 0.24 g of the substance was Kjeldahlised and the
nitrogen content in the organic compound in the form N
ammonia formed was absorbed in 50 cm3 of H SO . The
of 4 2 4
N
(a) NH3 (b) N2 excess acid required 77 cm3 of NaOH for complete neu-
(c) NaCN (d) (NH4)2SO4 10
tralization. Molecular mass of the following elements?
4. How will you separate a solution (miscible) of Answer the following questions:
benzene + CHCl3? 11. The compound has maximum percentage composition
(a) Sublimation (b) Filtration of which of the following elements?
(c) Distillation (d) Crystallization (a) C (b) H
5. A compound containing only carbon, hydrogen and (c) N (d) O
oxygen, has a molecular weight of 44. On complete 12. What is the percentage composition of carbon in the
oxidation it is converted into a compound of molecular compound?
weight 60. The original compound is (a) 16% (b) 8%
(a) An aldehyde (b) An acid (c) 28% (d) 48%
(c) An alcohol (d) An ether
13. Percentage composition of nitrogen in the compound
6. An organic compound which produces a bluish green will be
coloured flame on heating in presence of copper is (a) 16 (b) 61
(a) Chlorobenzene (b) Benzaldehyde (c) 6 (d) 28
(c) Aniline (d) Benzoic acid 14. Which among the following is the empirical formula
7. Which of the following compounds may give blood of the compound?
red colouration while performing Lassaigne’s test for (a) C8H4NO2 (b) C4H8N2O
nitrogen? (c) C4H8NO (d) C8H4NO
(a) (NH2)2CO 15. Molecular formula of the compound will be
(b) (NH2)2C = S (a) C8H4NO2 (b) C4H8N2O
(c) p-NMH2C6H4SO3H (c) C4H8NO (d) C8H4NO
(d) C6H5SO3H
8. The desiccants used for absorbing water during STEP–III CHECK YOUR EXPERTISE
Liebig’s method for estimation of carbon and Confront the Conceptual Questions As Present JEE Pattern
hydrogen are
1. Sodium nitroprusside Na2[Fe(CN)5NO] is used
(a) Anhydrous CaCl2 (b) Anhydrous Na2SO4
as reagent for detection of ___________ and the
(c) MgSO4.7H2O (d) Mg(ClO4↑)2
compound formed is ___________.
9. Presence of halogen in a compound is tested by (a) Sulphur, Na4 [Fe(CN)5NOS]
(a) Iodoform test (b) Millon’s test (b) Nitrogen, Na4[Fe(CN)6]
(c) Silver nitrate test (d) Beilstein test (c) Sulphur, Na2[Fe(CN)4NOS]
(d) Sulphur, Na2[Fe(CN)5NOS]
10. Which of the organic compounds will give white
precipitate with AgNO3? 2. The Prussian blue colouration obtained in the test for
(a) C6 H 5 NH 3+ Cl− nitrogen in the organic compound is
(b) NaCl (a) K4[Fe(CN)6] (b) Fe4[Fe(CN)6]3
(c) C6H5Cl (c) Fe[Fe(CN)6] (d) Fe3[Fe(CN)6]2
(d) 2,6,6,-Trinitrochlorobenzene 3. If N and S both are present in an organic compound
Passage during Lussaigne’s test, both will change into
0.9 g of an organic compound gave on combustion: (a) Na2S and NaCN
(b) NaSCN
(i) 1.584 g CO2 (c) Na2SO3 and NaCN
(ii) 0.648 g H2O (d) Na2S and NaCNO
4. Which of the following will not give test for N in 11. In Kjeldahl’s method during digestion, the nitrogen of
sodium extract? the organic compound is converted into
(a) C6H5NHNH2 (b) NH2CONH2 (a) NH4Cl (b) (NH4)2SO4
NH2 (c) NH4NO3 (d) NH3
12. 0.46 g of an organic compound containing C, H,
(c) NH2NH2 (d) oxygen was heated strongly in stream of N2 gas.
The gaseous mixture thus obtained was passed over
heated coke at 1373 K and then passed through warm
SO3H solution of iodine pentoxide when 2.54 g of iodine.
The percentage of O2 in the compound is
5. Which of the following will give blood red colour
with FeCl3 in sodium extract (Lassaigne’s extract)? (a) 69.56 (b) 34.78
(c) 47.38 (d) 38.47
(a) NH2CONH2 (b) NH2CSNH2
(c) C6H5NHNH2 (d) CH3C ≡ N 13. In paper chromatography
6. A mixture of acetone and CCl4 can be separated by (a) moving phase is liquid and stationary phase is
(a) Azeotropic distillation solid
(b) Fractional distillation (b) both are liquid
(c) Steam distillation (c) both are solid
(d) Vacuum distillation (d) moving phase is solid and stationary phase is
liquid
7. Silver salt method is used to determine molecular
14. In Carius tube the compound ClCH2COOH was
weight of
heated with fuming HNO3 and AgNO3. After filtration
(a) organic acids and washing, a white ppt was formed due to
(b) organic bases
(a) AgCl (b) AgNO3
(c) both acids and bases
(c) Ag2SO4 (d) ClCH2COOAg
(d) none of these
15. Which of the following reagents can be used to
8. An organic compound is heated with HNO2 at 0oC and
separate a mixture of aniline and phenol?
then the resulting solution is added to a solution of b-
naphthol whereby a brilliant red dye is produced. The I H2O II NaOH
observations indicate that the compound possesses: (a) NaCN (b) NaOH
(c) NaHCO3 (d) HCl
(a) –NO2 group
(b) –CONH2 group 16. In sodium fusion test of organic compound, the
(c) aromatic NH2 group nitrogen of an organic compound is converted into [If
(d) aliphatic NH2 group only C, H, N are present]
(a) NaCN (b) NaNH2
9. An organic compound contains C, H, N, S and Cl.
(c) NaNO2 (d) Na3N
For the detection of chlorine, the sodium extract of
the compound is first heated with a few drops of 17. CH3C ≡ CCH3 and CH3CH = CHCH3 can be distin-
concentrated HNO3 and then AgNO3 is added to get guished by
a white ppt of AgCl. The digestion with HNO3 before (a) reacting with ammonical AgNO3
the addition of AgNO3 is (b) reacting with ozone followed by hydrolysis with
(a) to prevent the formation of NO2 Zn and then treatment with Tollen’s reagent
(b) to create a common ion effect (c) reacting with acidified KMnO4 and heating
(c) to convert CN– and S2– to volatite HCN and H2S, (d) reacting with bromine water
or else they will interfere with the test forming OEt
AgCN or Ag2S 18. Compound CH3 – CH and CH3-CH2-O-CH2-
(d) to prevent the hydrolysis of NaCN and Na2S OEt
(P) (Acetal)
10. Aniline can be separated from phenol using CH3 can be differentiated by:
(a) Na2CO3 (b) NaNO2 + HCl at 0oC (a) H3O⊕, Na (b) H3O⊕, Tollens test
(c) NaCl (d) acidified KMnO4 (c) H3O , Fehling test (d) All of these
⊕
OH Above compounds can be differentiated by which of

OH OCH3
the following chemical test? (used in decreasing order)
(a) NaOH, NaHCO3↑, HCI
19. (b) HCI, NaOH, NaHCO3
(c) NaHCO3, NaOH, HCI
(d) NaOH, HCI, NaHCO3
(p- ethyl phenol) (p- methyl anisole) (p- ethyl benzyl alcohol)
Above compound can be differentiated by using the
reagent 23. and can be differentiated by
(a) NaOH, Tollen’s reagent, FeC13
(b) CrO3, Tollen’s reagent, FeC13
which of the following chemical test?
(c) Tollen’s reagent, CrO3, FeC13
(a) hv or ∆ than Na
(d) Na, Tollen’s reagent, FeC13
(b) hv or ∆ then amm AgNO3
NH2 NH2 (c) ∆or hv, then Br2/H2O
(d) C12/hv then Br2/H2O
20. and can be differentiated by: ⊕
NH3Cl– NO2
(aniline) (cyclohexyl amine)
Cl
(a) Hinbers test 24. and
(b) Iso-cyanide test
(c) NaNO2, HCI, then β-Napthol (P) (Q)
(d) NaOH Above compounds (P) and (Q) can be differentiated
OH OH by:
CO2H CO2Et (a) amm, AgNO3 (b) NaOH-
21. (c) FeC13 (d) Both (a) & (b)
25. Which of following acid give positive tollen’s reagent
Salicyclic acid Ethyl salicylate
test.
O O
CO2H CO2H
O – C – CH3 O – C – CH3 (a) (CH2)2 (b) CH2
CO2Et CO2H CO2H CO2H
CO2H
Ethyl acetyl acetyl salicyclic acid (c) (d) HCO2H
Above compounds can be differentiated by the salicy- CO2H
late. Which of the following chemical
test? (used in decreasing order) 26. Which of following compounds give positive Tollen’s
(a) NaOH, FeCI3, NaHCO3 test?
(b) aq. NaHCO3, FeCI3, NaOH O OCH O
3
(c) NaOI, NaOH, NaHCO3 (a) (c)
(d) NaOH, Na, NaHCO3 OCH3
OH CO2H O OH O
(b) (d)
22.
OH
NO2 NO2
(m-nitrophenol) (m-nitro benzoicacid) 27. Give test to differentiate (Bromobenzene) Ph-Br and
NH2 NO2 benzyl bromide (PhCH2Br).
(a) (i) aq. KOH (ii) Na
(b) AgNO3
NO2 NO2 (c) KMnO4
(m-nitro aniline) (m-Dinitro benzene) (d) All the above
28. Test to differentiate between (CH 3 OH) and (Ph −OH)

O
is/are:
(methanol) (Phenol)
(a) (b) O
(a) Litmus test (b) FeC13
(c) Br2/H2O (d) All (c) O (d) O
29. Acetaldehyde and Benzaldehyde can be differentiated 37. The following two compounds I and II can be
by: distinguished by using reagent
(a) Fehling test
(b) Iodoform test OH HO
(c) Tollen's reagent
(d) Both (a) and (b)
COOH COOH
30. Ethylamine and diethylamine cannot be differentiated
by: (1) aq. NaHCO3
(a) Hinsberg test (b) Carbylamine test (2) Neutral FeCI3 (aq.) (FfeCI3 + NH4OH + H2O)
(c) Iodoform test (d) Both (a) and (b) (3) Blue litmus solution
(4) Na metal
31. Sodium nitroprusside when added to an alkaline (5) HCl (ZnCl2 anhydrous)
solution of sulphide ions produces a colouration (a) 1 or 3 (b) 2 or 5
which is: (c) 4 or 5 (d) 3 or 4
(a) red (b) blue
38. Tolien’s regent (AgNO3 + NH4OH) can be distin-
(c) brown (d) purple
guished between
32. In Kjeldhi’s method of estimation of nitrogen, K2SO4 (a) H–C–H and Ph–C–H
acts as:
(a) an oxidizing agent O O
(b) Catalytic agent O O O
(c) Hydrolysing agent O
(d) Boiling point elevator (b) H and H H
33. p-nirophenol and o-nitrophenol are separated by:
D O Me
(a) distillation C C=O
(b) steam distillation
(c) crystallization (c) and
(d) fractional crystallization
C=O
34. Which of the following reagent is used for the Me
separation of acetaldehyde fro acetophenone?
(d) Ph–C–Ph and Me–C–Me
(a) NH2OH (b) NaOI
(c) Tollens reagent (d) C6H5NHNH2 O O
35. The formula of gas is [CO]x. If its vapour density 39. Observe the following compound and select +Ve &
is 70, the value of x will be: –Ve tests respectively
(a) 2.5 (b) 3.0
(i) Na metal
(c) 5.0 (d) 6.0
HO C=CH (ii) NaHCO3
(i) Na metal
No H2 gas evolved COOH
OHC (iii) 2,4-DNP
(ii) Cl2/hv 3-monochloro
36 C4H10O (iv) Lucas reagent
products
(iii) Lucas reagent
–Ve test (a) + + + – (b) + + + +
Compound is (c) + – + – (d) + – – +
40. Consider following compounds and decide as to O–H O–CH3

which of the following statements are true ?
(c) (d)
CH3 CH3
CH2 = CH – C – COOH CH3 – C – OCH3 CH3
H CH3
43. Compound P(C6H10) does not have any geometrical
(I) (II)
isomer. ON ozonolysis, two products R(C3H4O) and
CH3 Q(C3H6O) are formed. R gives negative iodoform
test while Q responds positively towards I2/NaOH
CH3O – C = C – H CH3 – C – CH2OCH3 solution. S, another isomer of P is an unsymmetrical
OH alkene and on ozonolysis produces T(CSH10O2) which
also gives a yellow precipitate with I2/NaOH solution
(III) (IV)
and also gives positive test with Tollen’s reagent.
(a) (II) gives no reaction with Na metal, however, 1 Which of the following does not represent any of the
mole of (IV) on reaction with Na metal will be molecules amongst P, Q, R, S & T.
rate 22.4 litres of H2 gas at STP H OO H
(b) (I) will give brisk effervescence on addition of (a) O (b)
NaHCO3 but will not bring any change in the co-
lour of Br2 water H OO H
(c) (III) liberates H2 gas with Na metal, gives white (c) (d)
precipitate with Tolien’s reagent but does not
respond towards lucas reagent or 2, 4-DNP
test. 44. A set of reagents (1 to 8) are successively reacted with
(d) (IV) gives turbidity with anhydrous ZnCl2 the follow it compound
41. An aromatic compound ‘X’ (C5HSO3) turns blue litmus O

to red. It gives yellow precipitate with I2 NaOH and
forms Y (C8H6O4).Y forms three mononitro isomeric OH
products. Identify X.
OH
COCH3 COCH3
COOH
(a) (b) 1. NaHCO3 2. 2, 4, DNP
COOH 3. Na metal 4. AgNO3 + OH
5. Fehling’s solution 6. Cu2Cl2 + NH4OH
COCH3 7. Br2/H2O 8. NaNO2 + HCl
The reagents which give positive test with the given
(c) (d) None of these compound are:
(a) 1, 2, 3, 4, 5
COOH (b) 3, 4, 5, 6, 8
(c) 1, 2, 3, 4, 8
42. Compound Y1C7H8O is insoluble in water, dil HCl and (d) All reagents except 1 and 8
aqueous NaHCO3. It dissolves in dilute NaOH. When 45. Compounds (C8H8O) X will give following laboratory
Y is treated with bromine water it is converted rapidly tests.
into a compound of formula C7H5OBr3.ldentify the
structure of Y Isomers FeC13 AgNO3/ Na metal
OH OH NH4OH
CH3 X Coloured Negative ½ H2 ↑
(a) (b) solution
CH3 X can be:
OCH3 CH2OH followed by AgNO3 + NH4OH solution. The mixture

contains
(a) (b) O
(a) NH2
CH = O CHO CH3–(CH2)8–CHO and
H3C O
COOH COOH
OH O
(b) and
(c) (d)
NO2
CH = CH2 OH CHO
46. The compound A gives following reactions. (c) and
NO2
Na metal
H2 gas ↑ NH2
CHO CHO
2, 4-DNP
A(C6H8O2) yellow orange ppt (d) and
O3
B(C6H8O4)
MORE THAN ONE CORRECT ANSWERS
Its structure can be
(a) CH2=CH–(CH2)2–C–CH2OH 1. In Lassaigne’s test, the organic compound is first
fused with sodium metal. The sodium metal is used
O because
(b) OHC–(H2C2)2–HC – COOH (a) The melting point of sodium metal is low
OH (b) Sodium metal reacts with elements present in or-
(c) ganic compounds to form inorganic compounds
(c) All sodium salts are soluble in water.
O (d) All sodium salts are not soluble in water.
OH 2. Ethanol and ethanal are distinguished by
(d) (a) Fehling’s solution test
(b) Tollen’s reagent test
CHO (c) iodoform test
47. In compound A (C30H60O) following tests are observed (d) cerric ammonium nitrate
negatively, A can be: 3. Which of the following statements are correct?
Br2v/H2O
(a) An organic compound is pure if mixed melting
–Ve point is same
(b) Ethanol and water can be separated by azeotropic
2, 4–DNP distillation because it forms azeotrope
C30H60O –Ve
(c) Impure aniline is purified by steam distillation as
(A)
Na metal
–Ve it is steam volatile.
(d) Glycerol is purified by vaccum distillation be-
(a) an unsaturated ether cause it decomposes at its normal boiling point.
(b) an epoxide 4. Which of the following will respond to iodoform test?
(c) a cyclic ketone O OH
(d) a cycloaikanol
(a) CH3 – C – COOH (b) CH3 – CH – COOH
48. A mixture of two orgnaic compound gives red coloured
OH
precipitate with cuprous chloride (ammonical) and
silver mirror on heating with Zn dust and NH4Ci (c) CH3 – CH – CH3 (d) CH3CH2OH
5. Which of the following will not show iodoform 12. Kjeldhal’s method cannot be used for
test? (a) C6H5NO2
O O (b) C6H5NHCOC6H5
(a) CH3 – C – CH3 (b) CH3 – C – Cl (c) azobenzene
(d) pyridine
O
(c) CH3 – C – NH2 (d) CH3–COOH 13. Which of the following can be purified by steam
distillation?
6. HCOOH and CH3COOH can be distinguished by (a) Salicyladehyde
(b) Bromobenzene
(a) Tollen’s reagent (b) Fehling’s solution
(c) p-Hydroxybenzaldehyde
(c) KMnO4 (d) NaHCO3
(d) Nitrobenzene
7. An organic compound has the structure
14. Which of the following will give benzoic acid on
CHO
acidic hydrolysis?
(a) Phenyl cyanide (b) Benzoyl chloride
. It will give (c) Benzyl chloride (d) Methyl benzolate
OH
O O
CH3
CH2 – COOH
15. CH3 – C – C2H5 and CH3 – C – CH3
(a) cerric ammonium nitrate test CH3
(b) give brisk effervescence with sodium bicarbonate.
(c) it will give a characteristic colouration with cannot be distinguished by
neutral ferric chloride after decarboxylation and
(a) 2, 4-DNP (b) iodoform reaction
reduction by Clemmenson’s method.
(c) NaHSO3 (d) Na metal
(d) It will give Fehling’s test.
16. Compound X and Y both have the same molecular
8. Which of the following organic compounds will give
formula (C4H8O). They give following observation in
white precipitate with AgNO3?
some lab test.
(a) C6H5NH3+Cl–
(b) NaCl Test X Y
(c) 2, 4, 6-trinitrochlorobenzene Br2-water Positive negative
(d) Benzyl chloride Na-metal Positive negative
Lucas reagent turbidity after negative
9. A compound reacts with CHCl3 and KOH gives some time
offensive smelling compound A. ‘A’ can be Iodoform test negative negative
(a) Primary aliphatic amine The compound X and Y are
(b) Primary aromatic amine
(c) 2o amine
(a) OH
(d) Tertiary amine
10. HCOOH and HCHO may be distinguished by (b) OH

(a) Tollen’s test (b) sodium bicarbonate test
(c) OH
(c) 2, 4-DNP test (d) Benedict’s test
CHO (d) O
11. and CH3CHO can be distinguished by 17. Compound ‘P’ (C10H12O) evolves H2 gas with Na
metal. It reacts with Br2/CCI4 to give ‘Q’ (C10H,2Br2O).
(a) Tollen’s test (b) Benedict’s test With I2/NaOH it forms iodoform and an acid ‘R’
(c) Iodoform test (d) 2, 4-DNP test (C9H8O2). ‘P’ has geometrical and optical isomers.
The structure of ‘P and R’ should be 4. A: Secondary amines and phenols undergo Lieber-
COOH mann nitroso reaction.
(a) R: Secondary amines are more basic than primary
amines.
CH=CH2 5. A: Only one Aldehyde ‘X’ responds positively with all
the tests of carbonyl compounds like Tollen’s test,
(b) PH – CH = CH – COOH
Fehling test, 2, 4-DNP test, as well as iodoform test.
CH = CH – CH – CH3 R: All aldehydes respond all the four tests given in
(c) assertion.
OH
OH 6. A: A mixture is p-methylbenzoic acid and picric acid
CH = CH – CH3 is separated by NaHCO3 solution
(d) R: p-Methylbenzoic acid is soluble in NaHCO3
because it give effervescence of CO2
18. Which is/are the correct method for separating a
mixture of benzoic acid, p-methylaniline and phenol. COMPREHENSION TYPE
(a) 
aq. NaHCO3
→ 
aq. NaOH
→
(b) 
aq. HCI
→ 
aq. NaHCO3
→ Passage 1
(c) 
aq.NaOH
→ 
aq.NaHCO3
→ Steam distillation is used to purify a compound which is
steam volatile and insoluble in water. The impurities should
(d) 
aq.NaOH
→ 
aq.HCI
→ not be steam volatile. It is based on the principle that
liquid will boil when partial vapour pressure of liquid and
partial vapour pressure of steam both become equal to
ASSERTION AND REASON
atmospheric pressure. P = P1 + P2. It reduces the boiling
point of liquid.
INSTRUCTIONS: In the following questions an Assertion
(A) is given followed by a Reason (R). Mark your responses Weight of water distilled
from the following options. =
Wt. of substance distilled
(a) Both Assertion and Reason are true and Reason is the M. Wt of water × V.P. of steam
correct explanation of ‘Assertion’
M. Wt of substance × V.P. of substance
(b) Both Assertion and Reason are true and Reason is not
the correct explanation of ‘Assertion’
1. Which of the following is steam volatile?
(c) Assertion is true but Reason is false
(d) Assertion is false but Reason is true (a) o-nitrophenol
(b) p-nitrophenol
1. A: 1o, 2o, 3o Amine’s can be distinguished by diethyl (c) p-hydroxybenzaldehyde
oxalate.
(d) Ethanol
R: 1o amines form N-alkyl oxamide solid product, 2o
amine form oxamic ester which is liquid, 3o amine 2. Calculate weight of aniline distilled if weight of water
do not react. distilled is 100 g when Porganic compound = 100 mm Hg and
PH2O = 200 mm Hg.
2. A: Victor-Meyer’s Test is used to distinguish between
1o, 2o, 3o alcohols as well as nitro compounds. (a) 250 g (b) 258 g
R: Victor-Meyer’s method is used to determine mo- (c) 100 g (d) 25.8 g
lecular weight of volatile organic compounds.
3. Which of the following cannot be separated by steam
3. A: Acetaldehyde reacts with alkaline solution of distillation?
sodium nitroprusside to give red colouration (a) Nitrobenzene (b) Essential oil
R: Acetaldehyde is good reducing agent. (c) Aniline (d) Glycerol
Passage II 1. The compound P can be

Given are the isomers of C8H8O2. &+ &+±&+
O %U
C – O – Et CHO CO2H (a)
&+ &+±&+
%U
OCH3 CH3 (b)

(a) (b) (c)
O &+ &+±&+
O–H C – CH3 CH2 – CHO %U
(c)
&+ &+±&+
O – CH = CH2 O–H OH
(d) (e) (f) (d)
1. Which isomer gives positive iodoform test?
(a) a (b) b
%U
(c) d (d) e
2. What could be the structure of Q?
2. Which isomer gives +ive Tollen’s test, also reacts &22+
with FeCl3? &+2
(a) b (b) f
(c) c (d) d (a) (b)
3. Which isomer reacts with NaHCO3? %U &+
(a) c (b) d &+2 &+2
(c) e (d) f
%U
4. Which isomer on hydrolysis gives 1, 4-di hydroxy- (c) (d)
benzene?
(a) a (b) d
(c) e (d) f &+
Passage 3
3. Identify the structure of R
Observe the following sequence of reactions (a) HCOOH (b) CH3CHO
O3 / Zn, H2O (c) BrCH2 - CHO (d)
P(C9H9Br) R+Q
reductive
Passage-4
(i) Tollen’s Reagent
(ii) H+ An aromatic compound T (C10H10O2) give 2 moles of CHI3
and compound U (C3H4O4Na2) On treatment with I2 and
(S) + Ag ↓ NaOH. After acidification U gives two mononitro products
P shows geometrical isomersm. Q gives positive Tolen’s on nitration.
test and the oxidation product of Tollen’s test followed by 1. Compound (T) can aoso be obtained by ozonolysis
acidification is the strongest acid among its all position of V, in this ozonolysis one mole of OHC – CHO is
isomers. R gives positive lab tests with 2,4-DNP, Fehling obtained alongwith (T). Possible structure for Com-
solution and I2/NaOH reagents. pound V could be
&+ &221D &221D

&+
(a) (c) (d)
&221D
&221D
&+ MATRIX MATCH TYPE
1. Column-I
(b) Reaction
(a) Na2[Fe(CN)5NO] + Na2S →
(b) NaSCN + FeCl3 →
&+ (c) Na4[Fe(CN)6] + Fe3+ →
(d) Na3PO4 + (NH4)2MoO4  →
HNO3
&+
Column-II
(c) Product/colour
(p) Yellow ppt. of (NH4)3 PO4 . 12 MoO3
&+ (q) Blue colouration due to Fe4 [Fe(CN)6]3
(r) Blood red colour due to Fe(SCN)3
&+ (s) Violet colour due to Na4[Fe(CN)5NOS]
2. Column-I Reaction
(d) (a) Ammonical AgNO3
(b) I2/NaOH
(c) NaHCO↑3
&+ (d) Ozonolysis
Column-II Product/colour
2. Which of the following statement is true? (p) Detect or confirm the position of double bonds
2 2 (q) Presence of strongly acidic groups
&+ (r) Presence of acetylinic group or –CHO group
& & (s) Presence of – CH – CH3
&+
(a) T is Cl
3. X(C8H14) by ozonolysis forms Y[C8H14O2]. Y on
(b) Compound (V) decolourises pink colour of dilut- reaction with NaOI followed by acidification gives
ed solution of KMnO4. CHI3 and compound Z on strong heating forms W.
(c) All isomers (only acidic) of U after acidification
Column-I Column-II
gives one mole of CO2 with NaHCO3
(a) Compound X (p) Bayer’s Test
(d) After acidification of (U), it is most acidic in its all
(b) Compound Y (q) NaHCO3
other isomers.
(c) Compound Z (r) 2, 4-DNP
3. Compound U is (d) Compound W (s) Iodoform Test
&221D &221D (t) Na Metal
&221D 4. Match the following: (More than one option in column
(a) (b) - II may match with single option in column-I)
Column-I
(a) Sodium metal
2 + (b) Sodium bicarbonate
&
(c) 2,4-Dinitrophenlhydrazine
2 (d) Lucas reagent
Column-II C ≡ CH
C=C–H
(Z)
(X) COOH
OHC
CH = CH2
O
(W)
CH3 H3CO
C OH
C – CH3
O
(Y)
OH
ANSWER KEYS
STEP–I
1. (a) 2. (b) 3. (c) 4. (b) 5. (c) 6. (b) 7. (b) 8. (a) 9. (b) 10. (a)
11. (c) 12. (c) 13. (a) 14. (a) 15. (b)
STEP–II
1. (c) 2. (a) 3. (b) 4. (c) 5. (a) 6. (a) 7. (b, c) 8. (a, d) 9. (c, d) 10 (a,d)
11. (a) 12. (d) 13. (d) 14. (b) 15. (b)
SOLUTIONS
STEP–III (b) is correct because CCl4 and acetone differ in their
boiling point.
1. (A) Na2[Fe(CN)5NO] + Na2S → Na4[Fe(CN)5NOS]
(c) is used only in case of steam volatile substance. It
violet colour, sulphur is confirmed. is not correct.
2. (b) 4Fe3+ + 3Na4[Fe(CN)6] → Fe4[Fe(CN)6]3 + 12Na+ (d) Vaccum distillation is used in liquids which de-
(Prussian blue)
compose at their boiling point.
3. (B) Na + S + C + N → NaSCN 7. (A) (a) is correct because acids will react with AgNO3
to form silver salt whereas bases do not react. \ (b),
(a) is not correct because S and N will react with Na (c) and (d) are not possible.
metal to form NaSCN simultaneously.
(b) is not correct because Na2SO3 cannot be formed 8. (C)
(c) is not correct because NaCNO is not formed.
NH2
4. (C) The correct answer is (c) because hydrazine is not
an organic compound and cannot form CN– whereas 0ºC
+ HNO2
(a), (b), (d) are organic compounds.
5. (B) (b) is correct answer because it contains N and S,
therefore it will form NaSCN which reacts with FeCl3 N ≡ NX N=N
to give ferric thiocyanate, which is blood red in colour.
OH OH
(a), (c) and (d) are not possible because they do not +
contain sulphur.
Red Dye
6. (B) (a) is used only to separate azeotropes, i.e.,
constant boiling mixture. Hence choice (c) is correct.
(a) is incorrect. 13. (b) Paper chromatography is liquid-liquid partition

Aliphatic p- and s-NO2 groups react with HNO2 but chromatography in which water adsorbed to cellulose
not with b-naphthol. of paper acts as stationary phase while mobile phase I
– C – NH2 group reacts with HNO2 and produces N2 mixture of solutes dissolved in solvent.
−
O 14. (A) Cl– + AgNO3 → AgCl + NO 3
gas and does not react with b-naphthol. 15. (d) is correct because NaOH reacts with phenol but
Hence choice (b) is incorrect does not react with aniline. HCl reacts with aniline
An aliphatic amine reacts with HNO2 and produces al- but does not react with phenol. (a), (b) and (c) are not
cohol. Here first an aliphatic diazonium salt is formed possible.
which being unstable immediately reacts with H2O 16. (A) Na + C N → NaCN
to form alcohol. Which aromatic amines when they
(b), (c) and (d) are ruled out.
form diazonium salts are highly stable and hence can
be used to take part in diazonium coupling reactions. 17. (b) is correct as
Hence choice (d) is incorrect. O O
(1) O3
|| ||
9. (C) Na + C + N ∆ CH3 – C≡C – CH3 CH 3 − C − C − CH3
NaCN
( 2 ) Zn / H2O
∆
The resulting product will not give Tollen’s test
Both NACN and Na2S will react with AgNO3 to While CH3–CH=CH–CH3  (1) O3
(2) Zn / H 2 O
→ 2CH3CHO;
form AgCN (white ppt. ) and Ag2S (black ppt.) They
must be removed before performing AgNO3 test for CH3CHO formed will give Tollen’s test Hence (b) is
halogens correct.
Thus, on adding HNO3, NaCN and Na2S (a) is wrong as none of the compound will react with
ammonical AgNO3.
NaCN + HNO3  → NaNO3 + HCN
(b) With acidified KMnO4 and heat both will give
Na2S + 2HNO3  → 2NaNO3 + H2S CH3COOH and hence cannot be distinguished.
Hence, CN– and S2– are removed as HCN and H2S by (d) Both will decolourize bromine-water and hence
adding HNO3. cannot be distinguished
Hence, choice (c) is correct while (a), (b) and (d) are
18. (d) 19. (b) 20. (c) 21. (b) 22. (c)
incorrect.
23. (c) 24. (d) 25. (d) 26. (c) 27. (d)
10. Aniline and phenol can be separated by adding NaNO2
28. (d) 29. (d) 30. (c) 31. (b) 32. (d)
(B) + HCl as aniline forms diazonium salt anilinium
chloride, while phenol does not 33. (a) 34. (c) 35. (c) 36. (b) 37. (b)
Hence, choice (b) is correct. 38. (c) 39. (a)
Choice (a) is incorrect because Na2CO3 neither reacts 40. (c)
with aniline nor with phenol.
Choice (c) is incorrect because NaCl does not react Na
with aniline and phenol.
Choice (d) is incorrect because KMnO4 oxidises both Tollens
aniline and phenol. reagent
CH3 – O – C ≡ C – H
11. (b) is correct. (II)
Lucas
2 NH3 + H2SO4 ( NH4)2 SO4 reagent
Ammonia Sulphuric acid Ammonium sulphate
32 wt. of I 2 formed
12. (A)% of oxygen = × × 2, 4-DNP
254 wt. of organic compound –ve test No.
– C – group
32 2.54 32
100 = × × 100 = = 69.56% O
254 0.46 0.46
(B), (C) and (D) are not possible. 41. (a)
OH OH (b) is correct, it is the usual method.

Br Br (c) is correct as it is the usual method.
Br2/ H2O (d) is correct as vacuum distillation is done for com-
42. (b)
CH3 CH3 pounds which decompose below the boiling point.
Br 4. (ABCD) All respond to iodoform test.
CH3 O3 (a) respond to iodoform test due to presence of
43 (b) (P) C (Q)
CH3 O
||
CH3 – C – CH3 + (R) O CH3– C – group (b), (c) and (d) responds
because they gety oxidized to compounds having
O O
O3 H OO ||
(S) (T) CH3 – C – group.
44. (d) There is no COOH group or NH2 group. 5. (BCD)

\ Regents 1 and 8 will fall to give test. Choice (a) is incorrect
CH3–COCH3 + I2 CHl3↓ + CH3COOK
45. (c) Iodoform
OH O
||
46. (c) The compound gives positive test Choice (b) is correct CH3– C – Cl does not give iodo-
o form test due to presence of Cl group.
with Na Metal, 2, 4-DNP and it gives single product The H-atoms on C*atoms will not show acidic behav-
with O3 iour.
6. (ABC)
47. (b) The compound C30H60 O has one degree of
unsaturation since it gives –Ve negative test with (a) HCOOH gives silver mirror with Tollen’s reagent,
Br2/H2O, 2, 4 DNP and Na metal it must be an epoxide. acetic acid does not.
(b) HCOOH forms red ppt with Fehling’s solution,
48. –NO2 group gives +ve test with Zn/NH4Cl followed acetic acid does not.
by AgNO3 + NH4OH solution. (c) HCOOH decolourises KMnO4 but acetic acid
does not.
MORE THAN ONE CORRECT ANSWERS (d) Both react with NaHCO3 \ (d) is not correct.
7. (BC) The organic compound has –CHO group
1. (ABC) are true because sodium has weak metallic (aldehydic group) which will give Tollen’s test,
bond due to larger size, as well as low ionization Fehling’s test but in the structure, –CHO being
energy. Sodium salts are soluble in water because benzaldehyde type, will give only Tollen’s test and
hydration energy dominates over lattice energy. It not Fehling’s nor Benedict’s test.
follows that (d) is incorrect.
The organic compound contains an –OH group which
2. (ABD) is phenolic and not alcoholic and hence will not give
(a) Ethanal gives brick red ppt with Fehling’s solu- cerric ammonium nitrate test. Being a phenolic OH
tion whereas ethanol does not react. group it will give characteristic colour with neutral
(b) Ethanol gives silver mirror with Tollen’s reagent ferric chloride if all the functional groups apart
but ethanol does not from pehnolic OH are reduced or removed then the
(c) lodoform test cannot be used because both re- characteristic test with neutral ferric hlloride will
spond to iodoform test confirm such a phenolic Oh group. The organic
(d) Ethanol gives wine red colouration with cerric compound contains –COOH group and hence it will
ammonium nitrate whereas ethanal does not. give brisk effervescence with NaHCO3.
Hence choice (b) is correct (test for COOH group).
3. (ABCD) All are correct statements. Choice (c) is correct (test for phenolic –OH grop).
(a) is correct because impurities lower the melting Choice (a) is incorrect (because –OH group is not
point alcoholic).
Choice (d) is incorrect (because benzaldehydic –CHO CHO

will not give Fehling’s test).
8. (ABC) All those substances which can give Cl– ions 11. (BC) gives Tollen’s test, 2, 4-DNP
will give white ppt. with AgNO3.
Choice (a) is correct CH3CHO
+ + test, Benedict’s test, iodoform test and does not give
NH3Cl– NH3 Fehling’s test.
+ Cl–
CH3CHO gives Tollen’s test, 2, 4-DNP test, Fehling’s
AgNO3 + Cl– AgCl ↓ NO3– test, Benedict’s test, iodoform test.
Hence choices (b) and (c) are correct while (a), (d)
Choice (b) is correct
are incorrect.
NaCl + AgNO3 AgCl ↓ + NaNO3
12. (ACD) are correct because they cannot give NH3 on
heating with conc. H2SO4. (b) is not correct because it
Choice (c) is correct gives NH3
Cl O– 13. (ABD) are steam volatile and immiscible with water,
O 2N NO2 O2N NO2 therefore, can be purified by steam distillation. (c)
NaOH
+ Cl– p-Hydroxybenzaldehyde is not steam volatile.
14. (ABD) are correct
NO2 NO2
15. (ABD) (a) is correct as both will give characteristic
Cl– + AgNO3 AgCl↓ + NO3 colour with 2, 4-DNP
(b) is correct as both will give iodoform test
Choice (d) is also correct (d) is correct as both will not react with Na metal
O
||
(c) is incorrect as only CH 3– C − C2H5 will form
CH3
bisulphate while CH3 – C − C − CH3 will not due to
||
O CH3

9. (AB) RNH2 + CHCl3 + 3KOH → R–N = C + 3KCl + steric hindrance.
3H2O [Where R is alkyl or phenyl] 16. (c, d)
(c) in incorrect because 2o amines do not give carbyl-
amine reaction. 17. (b, c)
(d) is incorrect because 3o amines do not give carbyl- *
CH = CH – CH – CH3
amine reaction.
OH
10. (BC) HCOOH gives brisk effervescence with Na metal
NaHCO3 due to evolution of CO2 Ph – CH = CH – CH – CH3 + H3 ↑
(1)
HCOOH gives Tollen’s test, Fehling’s test, Benedict’s ONa
test and does not give 2, 4-dintrophenylhydrazine test OH
(2, 4-DNP) Br2 / CCl4
Ph – CH – CH – CH – CH3
HCHO gives Tollen’s test, Benedict’s test, Fehling’s (2)
Br Br
test, 2, 4-DNP test and does not give brisk efferves- (Q)
cence with NaHCO3 I2 / NaOH
Ph – CH = CH – COOH + CHI2
Hence choices (b) and (c) are correct, while choices (3) (R)
(a) and (d) are incorrect. ‘P’ has optical and geometrical isomers.
18. (a, b) 2. (B)

P/I2 AgNO2
COOH OH CH3CH2OH CH3CH2I
NH2
HNO2
+ + CH3CH2NO2 CH3CHNO2
CH3 NO
A B C
(A)
CH3 – CH – NO2 CH3 – C – NO2 + NaOH
NaHCO3
NO NOH
Nitrolic acid
COO Na NH2 OH
CH3 – C – NO2
+ +
NO–Na+
Soluble CH3 ppt Red colour
aq. NaOH P/I2 AgNO2

CH3 – CHCH3 CH3 – CHCH3
OH I
NO2
COOH NH2 OH HNO2
CH3CHCH3 CH3 – C – CH3
+ +
NO2 NO2
CH3
(B) Pseudonitrole
NaOH
aq. HCl Blue colour
⊕ 3 alcohols and 3 nitro compounds do not give this

o o
NH3Cl COOH OH test.

+ + Victor Meyer’s method is used to determine the
CH3 ppt molecular weight of volatile organic compounds.
Soluble The basic principle is that vapours of organic
NaHCO3 compound displace equal volume of air which can
be measured at room temperature and pressure and
⊕ can be converted at STP and by using mole concept,
COO Na OH molecular weight of organic compound can be
determined.
+
3. (b) Both A and R are correct but R is not correct
Soluble ppt
explanation of A.
4. (b) Both A and R are correct but R is not correct

ASSERTION AND REASON explanation of A.
1. (A) R R
NH + HNO2 N – N = O + H2O
R R
CO OC2H5 H NHR CONHR
OH OH
+ + 2C2H5OH
CO OC2H5 H NHR CONHR
N, N– Dialkyl oxamide (solid) + HNO2
COOC2H5 CONR2
+ HNR2
COOC2H5 COOC2H5 N=O
Oxamic ester (liquid)
Also s-amines are more basic than p-amines.
3o amines do not react. Hence both give Liebermann nitroso reaction.
5. (c) A: True, CH3CHO gives positive test with tollens 2. (d)

reagent, fehling solution, 2, 4-D.N.P. as well as 3. (b)
iodoform test.
R: False, all aldehydes do not give iodoform test. Passage 4
6. D Picric acid gives CO2 gas with NaHCO3 due to 1. (b)

stronger acidic nature of picric acid. 2. (d)
COMPREHENSION TYPE 3. (b)
Passage 1 CH3 CH3
1. (A) o-Nitrophenol is steam volatile i.e., vapourised by O3 CHO

O+ I2/NaOH
steam whereas others are not. V= O
CHO
2. (B) CH3 (T) CH2
WH2 O M H2 O p O
= × Steam [because p ∞ n]
WAniline M Aniline p Aniline
C – ONa
p H2 O n H2 O
= C – ONa
p Aniline n Aniline
(U)
100 18 200 O
= ×
WAniline 93 100
50 × 93 4650 MATRIX MATCH TYPE
Wt. of aniline = = = 258 g.
18 18
1. Na2 [Fe(CN)5NO] + Na2S Na4 [Fe(CN)5NOS]
3. (D) a, b and c are steam volatile, therefore, can be (Violet colouration)
separated by steam distillation and they are insoluble (B) → (R);
in water. Glycerol decomposes at its boiling point as
FeCl3+ 3NaSCN Fe(SCN)3+ NaCl
well as it is soluble in water. \ It cannot be separated
(Blood red colour)
by steam distillation, rather it is purified by distillation
under reduced pressure. (C) → (Q);
3Na4[Fe(CN)6] + 4Fe3+ Fe4[Fe(CN)6]3 + 12Na+
Passage 2
(Blue colouration)
1. (d) 2. (b) 3. (a) 4. (b) (D) → (P)
HNO3
Passage 3 Na3PO4 + (NH4)2 MoO4 (NH4)3 PO4. 12MoO3
(Yellow ppt.)
1. (b)
2. An ammonical AgNO3 solution can be used to
CH2 = CH – CH3 CHO identify the presence of acetylenic H atom as a white
Br Br precipitate will be formed due to the formation of
O2/Zn,H2O
+ CH3CHO silver acetylides
(reductive)
R − C ≡ CH + AgNO3 →
NH 4 OH
RC ≡ CAg
white ppt.
(i) Tollen’s Reagents
(ii) H+ Ammonical AgNO3 will also give silver mirror if
heated with compounds containing – CHO group.
COOH (B) → (S) ; All compounds containing
Br – CH – CH3 , – CH – CH3 or – C – CH3
+ Ag↓
OH X O
will give yellow ppt. when treated with I2/NaOH due O

to the formation of CHI3. CH3 Me
O3 (i) I2/OH
(C) → (Q); Any compound which has a strong acidic
(ii) Acidification
group will give brisk effervescence with NaHCO3. CH3 Me
O
Eg., –SO3H + NaHCO3 → –SO3Na + H2CO3 → H2O
(X) (Y)
+ CO2↑
O
(D) → (P); The ozonolysis method helps in the OH
determination of position of C = C e.g., in buten ∆
O
i.e., But-1-en will give CH3CH2CHO + HCHO on OH –CO2
–hv
ozonolysis. O
While CH3CH = CHCH3 will give onlyCH3CHO on (Z) (W)
ozonolysis.
4. (A – X, Y, Z, W); (B – Z) ;
3. (A – p) (B – r, s)
(C – X, Z) ; (D – Y)
(C – q, t) (D – r) a protic acid gives positive test with Na metal.
C8H14; DU = 2 a carboxylic functional group gives positive test with
Ozonolysis product Y[C8H14O2] has 8 C atoms indi- NaHCO3.
cates (X) is cyclic compound with one double bond. a carbonyl group gives yellow ppt. with 2, 4-DNP en
Thus A is symmetrical cyclohexene. alcohol gives positive test with Lucas Reagent.
SUBJECTIVE QUESTIONS ON IDENTIFICATION
1. The alkyl halide C4H9Br (A) reacts with alcoholic KOH 4. An organic compound (A) of molecular formula
and gives an alkene (B), which reacts with bromine to C4H9Cl on treatment with alcoholic KOH solution
give dibromide (C). (C) is transformed with sodamide gives 3 isomeric alkenes. The stable alkene among the
to a gas (D) which forms a precipitate when passed three (B), was treated with aqueous Br2 solution which
through an ammonical silver nitrate solution. Give the resulted in (C). (C) on treatment with NaOH liberated
structural formulae of the compounds (A), (B), (C) a gas with the formation of (D). (D) on treatment with
and (D) and explain reactions involved. CH3MgCl followed by hydrolysis gives (E). (E) on
treatment with H+/HBr gave (F) and (F) on treatment
2. An organic compound A, C6H10O, on reaction with alcoholic solution of NaOH gave (G). If (G) can’t
with CH3MgBr followed by acid treatment gives show geometrical isomerism identify the structures of
compound B. The compound B on ozonolysis gives (A) to (G).
compound C, which in presence of a base gives 1-ace-
tyl cyclopentene D. The compound B on reaction with 5. An organic compound (A) contains 40% C, and 6.7%
HBr gives compound E. Write the structures of A,B,C H. Its vapour density is 15. On reacting with a 50%
and E. Show how D is formed from C. concentrated solution of KOH, it gives two compounds
(B) and (C). When (B) is oxidised, original compound
3. A white precipitate was formed slowly when AgNO3 (A) is obtained. When (C) is treated with conc. HCl
was added to a compound (A) with molecular it gives a compound (D) which reduce Fehling’s
formula C6H13Cl. compound (A) on treatment with solution and Ammon. AgNO3 solution and also gives
hot alcoholic KOH gave a mixture of two isomeric effervescence with NaHCO3 solution. Write structure
alkenes (B) and (C) having formula C6H12. The of A,B,C, and D and explain reaction.
mixture of (B) and (C) on ozonolysis furnished four
compounds. 6. An open chain compound (A), C5H8O, is optically
(i) CH3CHO; (ii) C2H5CHO; active. When (A) is hydrogenated is presence of
palladium as catalyst, it absorbs two moles of
(iii) CH3COCH3; (iv) (CH3)2CH.CHO.
hydrogen per mole of (A) to produce compound
What are (A), (B) and (C)? (B), C5H12O, which is optically inactive. However
when (A) is warmed with dilute H2SO4 in presence structures of (A), (B), (C) and (E). show how (D) is
of HgSO4 it gives compound (C), C5H10O2 which is formed from (C).
still optically active. (C) responds to the iodoform
test. On oxidation with HNO3 (C) gives acetic acid 12. When bromobenzene is monochlorinated, two isomeric
and propanoic acid. Write the structures of (A), (B) compounds A and B are obtained. Monobromination
and (C) and explain the above reactions. of A gives several isomeric products of molecular
formula C6H3ClBr2 while monobromination of B
7. A hydrocarbon (A) (molecular formula C5H10) yields yields only two isomers C and D. Compound C is
2-methyl butane on catalytic hydrogenation (A) adds identical with one of the compounds obtained from
HBr (in accordance with Markownikofs rule) to the bromination of A, however D is totally different
form a compound (B) which on reaction with silver from any of the isomeric compounds obtained
hydroxide forms an alcohol (C), C5H12O. Alcohol (C) from the bromination of A. Give the structures of
on oxidation gives a ketone (D). Deduce the structure A, B, C and D and also structures of four isomeric
of (A), (B), (C) and (D) and show the reactions monobrominated product of A. Support your answer
involved. with reasoning.
8. A compound A C6H12O reacts with NH2OH but does 13. An organic compound A (C7H8O) is insoluble
not reduce Fehling’s solution. On reduction with in aqueous NaHCO3 but soluble in NaOH. The
H2 | Pt, A gives an alcohol which on dehydration is compound A on treatment with bromine water rapidly
converted into an alkene. The alkene on ozonolysis forms compound B (C7H5OBr3). Give structures for
gives a liquid product which reduces Tollen’s reagent A and B. What will be A if it does not dissolved in
but does not give yellow precpitate with I2 with NaOH but shows reactions given above? Give your
NaOH and (b) a liquid product which gives an yellow answer with proper reasoning?
precipitate with I2 and NaOH but does not reduce
Tollen’s reagent. Deduce the structure of A. 14. Compound A having empirical formula C6H6O is
soluble in sodium hydroxide but insoluble in NaHCO3.
9. Two isomeric gem dihalides of molecular formula A when treated with chloroform and sodium hydroxide
C5H10Br2 on hydrolysis give two isomeric compound forms B. Oxidation of B gives another compound C
C5H↑10O. Both form oxime with hydroxylamine which reacts with acetic anhydride in presence of
and do not react with Tollen’s reagent. One of these small amount of H2SO4 to give D (C9H8O4). Deduce
undergoes iodoform reaction while the other not. On structures of A, B, C and D.
strong oxidation with K2Cr2O7 and dil. H2SO4 both
give a mixture of propionic acid and acetic acid. What 15. An aromatic compound (a) having molecular formula
are the gem dihalides and the carbonyl compounds? C7H7NO2 dissolves in NaHCO3 to evolve CO2 and
when reacted with NaNO2/HCI forms (b), C7H6O3.
10. An organic compound (A) on treatment with acetic (B) dissolves in NaHCO3 and gives colour reaction
acid in the presence of sulphuric acid produces an with FeC13 and can be prepared by the action of
ester (B), (A) on mild oxidation gives (C), (C) with CC14 and NaOH on phenol. When (B) is reacted with
50% potassium hydroxide followed by acidification excess HNO3, it forms (C), C6H3N3O7. (C) undergoes
with dilute hydrochloric acid generates (A) and (D), acetylation and decomposes NaHCO3 to evolve
(D) with 50% potassium hydroxide followed by CO2. On reaction with PC15. (C) is converted to (D),
acidification with dilute hydrochloric acid generates C6H5N3O6C1 which when reacted with water gives
(A) and (D), (D) with phosphorus pentachloride back (C). Identify compounds (A) to (D).
followed by reaction with ammonia gives (E), (E) on
dehydration produces hydrocyanic acid. Identify the 16. An organic compound (A) of molecular weight
compounds A, B, C, D and E. 135, on boiling with NaOH evolves a gas which
gives white denso fumes on bringing a rod dipped
11. An organic compound (A), C6H10O, on reaction in Hcl near it. The alkaline solution thus obtained
with CH3MgBr followed by acid treatment gives on acidification gives the precipitate of a compound
compound (B). The compound (B) on ozonolysis (B) having molecular weight 136. Treatment of (A)
gives compound (C), which in presence of a base with HNO2 also yields (B), whereas it treatment with
give 1-acetyl cyclopentene (D). the compound (B) Br2/KOH gives (C). Compound (C) reacts with cold
on reaction with HBr gives compound (E). Write the HNO2 to gives (D), which give red colour with ceric
ammonium nitrate. On the other hand, (E) an isomer activity on strong heating yielding (B), C6H10O which
of (A) on boiling with dilute HCl gives an acid (F), readily reacts with dilute KMnO4. (A) on oxidation
having molecular weight 136. On oxidation followed with KMnO4 gives (C) having M.F C6H10O3 which
by heating, (F) gives an anhydride (G), which decarboxylates readily on heating to 3-pentanone.
condenses with benzene in the presence of anhydrous The compound (A) can be synthesized from a
A1C13 to give anthraquinone. Give the structures of carbonyl compound having M.F. C3H6O on treatment
(A) to (G) with proper reasoning. with dilute NaOH. Oxidation of (B) with ammonical
silver nitrate followed by acidification gives (D). (D)
17. An organic compound (A) (C4H11N) on reacting with forms a derivative (E) with SOCl2 which on reaction
HNO2 gave a compound (B) (C4H10O). Compound (B) with H3CNHCH2CH3 yields (F). Identify (A) to (F)
on mild oxidation gave (C) (C4H8O). Compound (C) giving proper reaction sequences. What is the name
on drastic oxidation gave (D) (C2H4O2). Compound of the reaction involved in the conversion of C3H6O
(D) on treatment with PCl5 followed by NH3 gave to (A)? Give the IUPAC nomenclature of compounds
(C2H5NO) which on treatment with Br2/NaOH gave (A) to (F).
(F) (CH5N). Deduce the structures of (A) (B) (C) (D)
(E) & (F) with reasoning. Write down the reactions 21. An organic compound A on treatment with ethyl
involved. alcohol gives a carboxylic acid B and compound
C. Hydrolysis of C under acidic conditions gives B
18. A pleasant smelling optically active ester (F) has M.W. and D. Oxidation of D with KMnO4 also gives B.
= 186. It does not react with Br2 in CCl4. Hydrolysis of The compound B on heating with Ca(OH)2 gives E
(F) gives two optically active compounds, (G) soluble (molecular formula C3H6O). E does not give Tollen’s
in NaOH and (H). (H) gives a positive iodoform test and does not reduce Fehling’s solution but forms
test and on warming with conc. H2SO4 gives (I) a 2, 4-dinitrophenylhydrazone. Identify A, B, C, D
(Saytzeff-product) with no geometrical isomers. (H) and E.
on treatment with benzene sulfonyl chloride gives
(J), which on treatment with NaBr gives optically 22. 1,4-pentadiene reacts with excess of HCl in the
active (K). When the Ag+ salt of (G) is treated with presence of benzoyl peroxide to give compound
Br2 racemic (K) is formed. Give structures of (F) to (X) which upon reaction with excess of Mg in
(K) and explain your choices. dry ether forms (Y). Compound (Y) on treatment
with ethyl acetate followed by dilute acid yields
19. An optically active organic compound C8H10O (A) on (Z). Identify the structures of compounds (X), (Y)
mild oxidation with chromic acid gave an optically and (Z).
inactive compound (B). C8H8O which forms an
oxime. Compound (B) on further oxidation with 23. A hydrocarbon (A) of the formula C8H10, on ozonolysis
alkaline KMnO4 gave a compound (C) C7H6O2 which gives compound (B) (C4H6O2) only. The compound
on treatment with PCl3 afforded a compound (D) (B) can also be obtained from the alkyl bromide (C)
C7H5ClO. Compound (D) on treatment with ammonia (C3H5Br) upon treatment with magnesium in dry
furnished compound (E), C7H7NO, which with Br2 ether, followed by carbon dioxide and acidification.
and alkali gave compound (F), C6H7N. Compound (F) Identify (A), (B) and (C) and also give equations for
on treatment with NaNO2/HCl and then with CuCN the reactions.
gave a compund (G), C7H5N which on treatment with
70% H2SO4 gave back (C). What are A, B, C, D, E, F, 24. When gas (A) is passed through dry KOH at low
G ? Explain the reactions involved in each step. temperature, a deep red coloured compound, (B) and
a gas (C) are obtained. The gas (A), on reaction with
20. Compound (A), M.F C6H12O2 reduces ammoniacal but-2-ene, followed by treatment with Zn/H2O yields
silver nitrate to metallic silver and loses its optical acetaldehyde. Identify (A), (B) and (C).
SOLUTIONS
1. (A) CH3CH2CH2CH2Br (C) CH3CH2CHBrCH2Br

(B) CH3CH2 – CH = CH2 (D) CH3CH2C ≡ CH
OMgBr Reactions:
O
CH 3MgBr
CH3 CH 3
2.
(alc.) KOH
CH − CH.CH 2 .CH 3
CH 3
(A)
CH3 Cl
3–chloro, 2–methylpentane
HOH
(A)
[H+]
CH 3
(B) CH − CH = CH.CH 3
O
CH 3 4–methylpent–2–ene
CH3
CH3 (B)
ozonolysis OC
CH 3
(B) + C = CH.CH 2 .CH 3
O 2–methylpent–2–ene
CH 3 (C)
OH– CH3
Intramolecular 4.
aldol condensation
(D) Cl
CH3 A = CH3
H3C
Br
CH3
B = H3 C
(E)
OH
3. i) (A) on treating with alcoholic KOH gives a
mixture of two isomeric alkenes (B) and (C). CH3
C = H3C
C6 H13 Cl 
alc. KOH
− HCl
→ C6 H12 + C6 H12 isomers
(B) (C)
Br
ii) Mixture of (B) and (C) on ozonolysis gives
four products (i) CH3CHO (ii) C2H5CHO (iii) O
CH3COCH3 (iv) (CH3)2CH.CHO
iii) Since (B) and (C) are of six carbon atoms each and D = H3C CH3
thus, product formed on ozonolysis for each al-
kene must contain in all six carbon atoms. That is CH3
why one alkene gives CH3CHO + (CH3)2CHCHO
and other alkene gives C2H5CHO and CH3COCH3. CH3
Thus, alkenes are E = H3C
CH3
OH
(CH 3 ) 2 CH.CH = CH.CH 3 ; C2 H5 .CH = C
(B) CH3 Br
(C) H3C
iv) Since (B) and (C) are formed from halide (A), F = CH3
thus, halide should be H3C
CH 3
H3C
CH − CH − CH 2 CH3 CH3
CH 3 G =
Cl
(A) CH3
5. i) CH3
Element % Rel.No. of atoms Simplest
CH2
ratio
B = H3C
C 40 3.33 1
H 6.7 6.70 2 Br
O 53.3 3.33 1 CH3
\ Empirical formula of (A) is CH2O; CH3

Empirical formula wt. = 30 C = H3C
∵ molecular wt = 2 × 15 = 30.;
\ molecular formula of A = CH2O OH
reacts with KOH(aq.) to give (B) and (C) i.e.,
CH3
(Cannizaro reaction) and thus, molecular formula of
(A) suggests it to be H – C – H.
CH3
O D = H3C
Reaction: HCHO 
KOH
→ CH 3 OH + HCOOK
(A) (B) (C) OH
CH 3 OH 
[O]
→ HCHO CH3
(B) (A)
HCO 2 K + HOH →

HCl
HCOOH
(C) (D)
8. A = H3C CO CH3
HCOOH + Ag 2 O → H2O + CO2 + 2Ag (silver
(D)
Br
mirror) 9. H3C Br
HCOOH + 2CuO → H2O + CO2 + Cu2O (Red. ppt.) CH3
H3C Br CH3
HCOOH + NaHCO3 → HCOONa + H2O + CO2↑ Br
H3C
O
6. A = H CH H3C CH3 H3C CH3

O
OH
H 10. A = CH3OH B = CH3COOCH3
C = HCHO D = HCOOH
B =
E = H.CONH2
H3C OH CH3
O
H O 11. A =
C = CH3
H3C OH CH3 B =
CH3 O
H
CH2 C = H3C
7. A = H3C O
COCH3 OH
D =
CH3
14. A =
E = Br
OH
12. Bromine is ortho- and para- directing. Hence,
monochlorination of bromobenzene yields.
O
B =
Br Br Br
Cl
Cl 2
+ OH OH
FeCl3
Cl O
(I) (II) C =
The monobromination of compound I will give four
products whereas that of compound II will give only O
two products as shown in the following.
Br Br Br O CH3
Br Cl Cl
Br2
+ + OH
FeBr3
Br O
Br D =
(I) (III) (IV)
Br Br COOH COOH
Cl Br Cl NH2 OH
+ 15.
Br (A) (B)
(V) (VI) Anthranilic acid salicylic acid
Br Br Br OH Cl
Br O2N NO2 O2N NO2
Br2
+
FeBr3
Br
NO2 NO2
Cl Cl Cl (C) (D)
(B) (VII) (VIII) picric acid Picryl chloride
The structure (V) and (VIII) are identical. Hence, the CH2CONH2 CH2COOH CH2NH2 CH2OH
structure (III) represents the compound C. Whereas
the structure (VII) represents the compound D. 16.
13. (A) (B) (C) (D)
OH OH
O
Br Br CONH2 COOH C
A = B =
O
CH3 CH3 CH3 C
CH3
(E) (F) (G)
m-cresol Br O
17. A = CH3CH(NH↑2)CH↑2CH↑3 NH2

B = CH3CH(OH)CH2CH3 CO2H COCl OC
C = CH3COCH2CH3
D = CH3CO2H
NH3 Br2/OH −
E = CH↑3CONH2 SOCl 2
F = CH3↑NH2
(C) (D) (E)
18. Is a saturated monoester with M.W = 186
NH2 CN
CH3 O CH3 NaNO2 /HCl
CuCN
CH3
F = H 3C O (F) (G)
CO2 H
CH3 CH3
H3O+
CH3 O
H (H)
G = H 3C O CH3
CH3 O
CH3 20. A = H3C
CH3 OH
H = H 3C CH3
CH3 O
B = H3C
CH3
CH3
I = H 3C
O
CH3 C = H3C H
OSO2 C6 H5
O O
CH3 CH3
J = H3C
O
CH3 D = H3C H
Br O
CH3
CH3
K = H3C Cl
E = H3C
CH3
O
OH O CH3 CH3
CH3 CH3 N
19. mild oxidation KMnO4 F = H3C
(A) (B) O CH3

21. The given reactions are as follows. Since B and D are obtained by acid hydrolysis of
C2H5OH C, the compound C must be an ester CH3COOC2H↑5
A B + C
(Carboxylic acid) (ethyl acetate).
H+ Since the compounds B (acetic acid) and C (ethyl
C B + D
acetate) are obtained by treating A with ethanol, the
compound A must be an anhydride (CH3CO)↑2O
KMnO4
(acetic anhydride).
B C3H6O The given reactions are
∆
(E) C 2 H5 OH
(CH3CO)2O `CH3COOH + CH3COOC2H5
The compound E must be ketonic compound acetic anhydride acetic acid ethyl acetate
as it does not give Tollens test and does not reduce (A) (B) (C)
Fehling’s solution but forms a 2, 4-dinitrophenyl-
hydrazone. Therefore, its structure would be H+
CH3COCH3 (acetone). Ca(OH) 2
Since E is obtained by heating B with Ca(OH)2,
the compound B must be CH3COOH (acetic acid). CH3COCH3 CH3COOH + C2H5OH
acetone acetic acid ethanol
Since B is obtained by oxidation of D with
(E) (B) (D)
KMnO4, the compound D must be an alcohol with
molecular formula CH3CH2OH (ethanol). KMnO4
22. HCl
CH 2 = CHCH2CH = CH2 CH3 — CH — CH 2 — CH — CH3
Mg/ether
Cl Cl
CH 3 — CH — CH2 — CH — CH3
MgCl MgCl (Y)

OMgCl H3C C OC2H5
H3C C O MgCl H3C C OC 2H5 O
H3C CH CH2 CH CH3 H3C CH CH2 CH CH3
MgCl
(Intermediate)
OMgCl OH
HOH
H3C C CH CH3 H3C C CH CH3
H3C C CH2 H3C CH CH2 (Z)

O
(Z) can also be H3C C CH (CH3)CH2 CH2 CH2CH3
23. The formula and reactions suggest that:

2 COOH Br + Mg
(B)
ozonolysis (cyclopropyl bromide)
C ≡C
(A) (dicyclopropyl ethyne)
MgBr + O = C = O HOH COOH
24. (A) is ozone as it reacts with butene-2 to show 3. How many CHI3 will be released from the given
ozonolysis. compound
CH3CH = CHCH2 + O3 O O l / NaOH 2
Zn/H2O
CH3 – CH – O – CH – CH3 2CH3CHO
O O 4. How many molecule of phenylhydrazine is used to
form osazone from glucose
The deep red coloured compound is KO3 and gas is O3
5O3 + 2KOH 
→ 2KO3 + H 2 O 2 + 5O 2 N – NH
(A) (B) (C) CHO
H OH N – NH
SHORT SUBJECTIVE QUESTIONS
HO H 3Ph–NH – NH2 HO H
1. A water insoluble organic mixture contained following H OH H OH
compounds
H OH H OH
(1) = Benzoic acid
(2) = salicyialdehyde CH2OH CH2OH
(3) = p-Hydroxybenzaldehyde + Ph – NH2 + NH3
(4) = a-Naphthylamine
(5) = Naphthalene
The following sequence of reagents are used to sepa- 5. How many CHI3 will be released from given
rate this mixture compound
O O
1+2+3+4+5
[Step-X] aq. HCl
H2N OCH3
[Insoluble] [Soluble]*
O
[Step-Y] aq. NaHCO3
O
[Insoluble] [Soluble]*
[Step-Y] aq. NaOH SHORT SUBJECTIVE ANSWER
[Insoluble]* [Soluble] 1.
[Step-W] Steam distillation X Y Z W
4 1 5 2
[distilled]* [left behind]
X = 4: a- Naphthylamine is soluble in aqueous HCI
Fill up the serial number of starred compound on- solution.
tained in the steps X, Y, Z and W respectively. Y = 1: Benzoic acid is soluble in aqueous NaHCO3
XY ZW solution.
Z = 5: Naphthalene insoluble in aqueous HCl, NaOH
2. How many acidic H is present in given compound of NaHCO3 solution.
W = 2: Salicylaldehyde has lower b.p. than p-hydroxy
O OH
benzaldehyde
O 2. 3
3. Zero
4. 3
OH 5. Zero, (None)
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VOLUME I

00 Prelims Volume I.indd 1 4/7/2015 1:07:09 PM

Editor—Acquisitions: Jitendra Gaur

Compositor: Mukesh Technologies Pvt. Ltd.

Chapter 1 IUPAC NOMENCLATURE 1.1–1.82

Chapter 2 GENERAL ORGANIC CHEMISTRY 2.1–2.278

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Reactions with Benzyne as the intermediate by Elimination-Addition Mechanism 4.77

Chapter 5 ANALYSIS OF ORGANIC COMPOUNDS 5.1–5.65

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00 Prelims Volume I.indd 8 4/7/2015 1:07:10 PM

DRAWING ORGANIC MOLECULES

&O & &O + & &O

catch hold of the top

One structure is, in reality, a simple rotation of the other one.

The commonest way to draw structural formulae

All of the next three structures represent butane.

&+ &+ &+

&+ &+ &+ &+

bond going back into

bond coming out of paper towards you

&+&+&O&+&+ &+ &+

&+&+ &+ &+&+ &+ &+

&+ 1&+&+ 1 &+ 1

Bond-line formulae are often used for cyclic compounds:

&+ + & &+

Muliple bonds are also indicated in bond-line formulae. For example:

& &+ &+ &+&+2+

CLASSIFICATION OF CARBON AND HYDROGEN OF ORGANIC COMPOUND

SULPDU\K\GURJHQ WHUWLDU\K\GURJHQ VHFRQGDU\K\GURJHQ &+

&+&+&+&+2+ &+&+&+2+ &+&+&+2+ &+&2+

&+ &+ &+

SULPDU\K\GURJHQ WHUWLDU\K\GURJHQ VHFRQGDU\K\GURJHQ

EXW\ODOFRKRO LVREXW\ODOFRKRO VHFEXW\ODOFRKRO WHUWEXW\ODOFRKRO

(b) Classification ‘B’–With Respect to the Functional Group

(c) Alkyl Groups

+& &+ &+

&+ &+ VHFRQGDU\SHQW\ORU

(d) Unsaturated Alkyl Group

CH­3 – CH = CH – CH2 – Crotyl

NOMENCLATURE OF ORGANIC COMPOUNDS

 Wood alcohol from wood

Compound Common name

(B) IUPAC (International Union of Pure and Applied Chemistry) Nomenclature

Nomenclature of Organic Compounds

Table 1.2 Some Prefixes

Number of carbons Prefix

Table 1.3 Some Primary Suffixes

Nature of Carbon Chain Primary Suffix

Table 1.4 Some Organic families and Secondary Suffixes

–CH3 – CH2 – CH2 – CH2 – OH Word root but

So, its name is But + ane + ol = Butanol or Butan – 1– ol.

Table 1.5 Some Alkyl Groups along with their Prefixes

Alkane Alkyl Group Abbreviation Prefix

Table 1.6 Functional groups which are always represented by prefixes

Functional Group Prefix Family IUPAC Name

Table 1.7 Some Characteristic Groups with their Prefixes

Characteristic group Prefix

Table 1.8 Prefixes for functional groups in polyfunctional compounds

Functional Group Prefix Functional Group Prefix

RULES FOR NOMENCLATURE (ALKANES)

Chapter 5 ANALYSIS OF ORGANIC COMPOUNDS 5.1–5.65

DRAWING ORGANIC MOLECULES

&+ &+ &+

&+ &+ &+ &+

&+&+&O&+&+ &+ &+

&+&+ &+ &+&+ &+ &+

&+ 1&+&+ 1 &+ 1

&+ + & &+

& &+ &+ &+&+2+

CLASSIFICATION OF CARBON AND HYDROGEN OF ORGANIC COMPOUND

SULPDU\K\GURJHQ WHUWLDU\K\GURJHQ VHFRQGDU\K\GURJHQ &+

&+&+&+&+2+ &+&+&+2+ &+&+&+2+ &+&2+

&+ &+ &+

EXW\ODOFRKRO LVREXW\ODOFRKRO VHFEXW\ODOFRKRO WHUWEXW\ODOFRKRO

+& &+ &+

&+ &+ VHFRQGDU\SHQW\ORU

CH3 – CH = CH – CH2 – Crotyl

NOMENCLATURE OF ORGANIC COMPOUNDS

RULES FOR NOMENCLATURE (ALKANES)

7ULPHWK\OKH[DQHDQGQRW &+ &+ &+

&+ &+ &+

&+&O &+ &+

RULES FOR NAMING COMPOUNDS CONTAINING DOUBLE AND TRIPLE BONDS

&+ & &+ &+ & &+

&+ &+ &+ &+

NOMENCLATURE OF COMPOUNDS CONTAINING FUNCTIONAL GROUPS

±&Ł1 QLWULOHVRUF\DQLGH ±1& LVRF\DQLGH

Root name: cyclohexane, therefore the name is PHWK\OF\FORKH[DQFDUER[\ODWH

&+ &+ &+ &+ &+ &+

&+ &+ &+ &+ &+ &+ &+2

&+ &2 Ethanoic propanoic anhydride

NOMENCLATURE OF COMPOUNDS WITH MORE THAN ONE

(vii) &+ &&O (viii) C6H5–CH = CH – COOH

(xvii) +1 12

&+ &+ &+ &+ 0RUHEUDQFKHG

WRITING THE STRUCTURE OF THE COMPOUND WHOSE NAME IS GIVEN