(Krishna's Text Book) Alok Bariyar, R.P Singh, Babita Agrawal, Babita Agrawal, Prashant Singh - Organic Chemistry-I-Krishna Prakashan Media (2015)

Krishna's
TEXT BOOK
ORGANIC
CHEMISTRY-I
B.Sc. First Year Second Paper
st
(For B.Sc. I year Students of all Colleges affiliated to Universities in Uttar Pradesh)
As per U.P. Unified Syllabus (w.e.f. 2011-12)
By
Alok Bariyar
Ph.D. (CSIR fellow), M.Sc.(IIT Delhi), GATE., NET
Ex. Scientist (Nuclear)

Bhabha Atomic Research Centre,
Mumbai (Maharashtra)
R.P. Singh Babita Agrawal

M.Sc., Ph.D. M.Sc., Ph.D.
Head, Dep’t of Chemistry Head, Dep’t of Chemistry
KNI of Physical Social Science, B.S.A. (P.G.) College,
Sultanpur (U.P.) Mathura (U.P.)
Ashish Dwivedi Prashant Singh

M.Sc., Ph.D. M.Sc., Ph.D.
Asst. Prof., Dep’t of Chemistry Asst. Prof., Dep’t of Chemistry
Ganpat Sahai P.G. College, KNIPSS, Sultanpur (U.P.)
Sultanpur (U.P.)
KRISHNA Prakashan Media (P) Ltd.

KRISHNA HOUSE, 11, Shivaji Road, Meerut-250 001 (U.P.), India
Jai Shri Radhey Shyam
Dedicated
to
Lord
Krishna
Authors & Publishers
P reface
W
e are happy to present this book entitled “Organic Chemistry-I”. It has been written
according to the latest U.P. Unified Syllabus to fulfil the requirement of B.Sc. Ist
year students of all Colleges & Universities in Uttar Pradesh.
The book is written with the following special features:

1. It is written in a simple language so that all the students may understand it easily.
2. It has an extensive and intensive coverage of all topics.
3. In each Chapter, Solved Examples are given based on different Topics.

4. The complete Syllabus has been divided into Seven Chapters under Four Units.
5. Sufficient Numerical Problems, Subjective Questions and Objective type questions with
Hints & Solutions given at the end of each chapter will enable students to understand the concept .
First of all we want to express our sincere gratitude to Purnima Sinha, Dr. S.B.P Sinha,
Prof. J.C. Ahluwalia, Prof. N.K. Jha for their invaluable guidance, immense interest and
constant encouragement for the successful completion of the work. We are also thankful to
Bandana Bariyar, Ashish Bariyar, Abhishek Bariyar, Archi Bariyar & Aradhyaa Bariyar for
their kind help at many occasions.
We are extremely grateful to our respected and beloved Parents whose incessant
inspiration guided us to accomplish this work. We also express gratitude to our respective
Families for their moral support.
We are immensely thankful to Mr. S.K. Rastogi (Managing Director), Mr. Sugam Rastogi
(Executive Director), Mrs. Kanupriya Rastogi (Director) and entire team of Krishna Prakashan
Media (P) Ltd., for taking keen interest in this project and outstanding Management in getting
the book published.
The originality of the ideas is not claimed and criticism and suggestions are invited from the
Students, Teaching community and other Readers.
July 2015 –Authors
(iv)
Syllabus
ORGANIC CHEMISTRY-I
B.Sc. Ist Year; IInd Paper
UGC Model Curriculum (w.e.f. 2001) & U.P. UNIFIED Syllabus (w.e.f. 2011-12)
M.M. 50
UNIT-I
1. Structure and Bonding: Hybridization, bond lengths and bond angles, bond energy, localized and
delocalized chemical bonding, Van der Waals interactions, inclusion compounds, clatherates, charge
transfer complexes, resonances, hyperconjugation, aromaticity, inductive and field effects, hydrogen
bonding.
2. Mechanism of Organic Reactions: Curved arrow notation, drawing electron movements with allows,
half-headed and double-headed arrows, homolytic and heterolytic bond fission, Types of reagents –
electrophiles and nucleophiles, Types of organic reactions, Energy considerations. Reactive
intermediates – Carbocations, carbanions, free radicals, carbenes, arynes and nitrenes (with examples).
Assigning formal charges on intermediates and other ionic species. Methods of determination of
reaction mechanism (product analysis, intermediates, isotope effects, kinetic and stereochemical
studies).
3. Alkanes and Cycloalkanes: IUPAC nomenclature of branched and unbranched alkanes, the alkyl
group, classification of carbon atom in alkanes, Isomerism in alkanes, sources methods of formation
(with special reference to Wurtz reaction, Kolbe reaction, Corey-House reaction and decarboxylation of
carboxylic acids), physical properties and chemical reactions of alkanes, Mechanism of free radical
halogenation of alkanes: orientation, reactivity and selectivity. Cycloalkanes – Nomenclature, methods
of formation, chemical reactions, Baeyer's strain theory and its limitations. Ring strain in small rings
(cyclopropane and cyclobutane), theory of strain less rings. The case of cyclopropane ring, banana
bonds.
UNIT-II
4. Stereochemistry of Organic Compounds: Concept of isomerism, Types of isomerism; Optical
isomerism – elements of symmetry, molecular chirality, enantiomers, stereogenic center, optical
activity, properties of enantiomers, chiral and achiral molecules with two stereogenic centers,
disasteromers, threo and erythro diastereomers, meso compounds, resolution of enantionmer,
inversion, retention and recemization. Relative and absolute configuration, sequence rules, D & L and R
& S systems of nomenclature. Geometric isomerism – determination of configuration of geometric
isomers, E & Z system of nomenclature, geometric isomerism in oximes and alicyclic compounds.
Conformational isomerism – conformational analysis of ethane and n-butane; conformations of
cyclohexane, axial and equatorial bonds, conformation of mono substituted cyclohexane derivatives,
Newman projection and Sawhorse formulae, Fischer and flying wedge formulae, Difference between
configuration and conformation.
UNIT-III
5. Alkenes, Cycloalkenes, Dienes and Alkynes: Nomenclature of alkenes, methods of formation,
mechanisms of dehydration of alcohols and dehydrohalogenation of alkyl halids, regioselectivity
(v)
in alcohol dehydration, The Saytzeff rule, Hoffmann elimination, physical properties and relative
stabilities of alkenes. Chemical reactions of alkenes – mechanism involved in hydrogenation,
electrophilic and free radical additions, Markownikoff's rule, hydroboration- oxidation,
oxymercuration-reduction. Epoxidation, ozonolysis, hydration, hydroxylation and oxidation with
KMnO4, Polymerization of alkenes, Substitution at the allylic and vinylic positions of alkenes,
Industrial applications of ethylene and propene. Methods of formation, conformation and chemical
reactions of cycloalkenes; Nomenclature and classification of dienes : isolated, conjugated and
cumulated dienes, Structure of allenes and butadiene, methods of formation, polymerization, chemical
reaction – 1, 2 and 1, 4 additions, Diels-Alder reaction. Nomenclature, structure and bonding in
alkynes, Methods of formation, Chemical reactions of alkynes, acidity of alkynes, Mechanism of
electrophilic and nucleophilic addition reactions, hydroboration-oxidation, metal-ammonia
reductions, oxidation and polymerization.
UNIT-IV
6. Arenes and Aromaticity: Nomenclature of benzene derivatives, The aryl group, Aromatic nucleus
and side chain, Structure of benzene; molecular formula and kekule structure, stability and carbon-
carbon bond lengths of benzene, resonance structure, MO picture. Aromaticity: The Huckle rule,
aromatic ions. Aromatic electrophilic substitution – general pattern of the mechanism, role of s and p
complexes, Mechanism of nitration, halogenation, sulphonation, mercuration and Friedel-Crafts
reaction. Energy profile diagrams. Activating and deactivating substituents, orientation and ortho/para
ratio, Side chain reactions of benzene derivatives, Birch reduction; Methods of formation and chemical
reactions of alkylbenzenes, alkynylbenzenes and biphenyl, naphthalene and Anthracene;
7. Alkyl and Aryl Halides: Nomenclature and classes of alkyl halides, methods of formation, chemical
reactions, Mechanisms of nucleophilic substitution reactions of alkyl halides, SN2 and SN1 reactions
with energy profile diagrams; Polyhalogen compounds : Chloroform, carbon tetrachloride; Methods
of formation of aryl halides, nuclear and side chain reactions; The addition-elimination and the
elimination-addition mechanisms of nucleophilc aromatic substitution reactions; Relative reactivities
of alkyl halides vs. allyl, vingl and aryl halides, Synthesis and uses of DDT and BHC.
(vi)
Detailed Contents
Unit - I
Chapter 1 Structure and Bonding O–01-62
1. Introduction 03
2. Localised and Delocalized Chemical Bonding 03
3. Characteristics of Covalent Bond 07
$ Solved Examples 10
4. Delocalized Chemical Bonding and Resonance 13
5. Hybridization 18
6. Electron Displacement Effect 29
7. Electromeric Effect 33
8. Strength of Acids and Bases 42
$ Exercise 55
$ Answers 61
$ Hints & Solutions 62
Chapter 2 Mechanism of Organic Reactions O–63-102

1. Fundamental Concepts of Organic Reaction 63
2. Various Reaction Intermediates 76
3. Methods of Determination of Reaction Mechanism 96
$ Exercise 99
$ Answers 102
Chapter 3 Alkanes & Cycloalkanes O–103-134

1. Alkanes 103
2. Cycloalkanes 116
3. Stability of Rings and Ring Strain 124
$ Exercise 130
$ Answers 133
Unit - II
Chapter 4 Stereochemistry of Organic Compounds O–135-200
1. Introduction 135
(vii)
2. Structural Isomerism 136
3. Stereoisomerism 140
4. Geometrical Isomerism 159
5. Conformational Isomerism 173
$ Exercise 186
$ Answers 194
Unit - III
Chapter 5 Alkenes, Cycloalkenes Dienes and Alkynes O–201-274
1. Alkenes 201
2. Cycloalkene (or Cycloolefin) 233
3. Dienes 238
4. Alkynes 245
$ Exercise 266
$ Answers 273
Unit - IV
Chapter 6 Arenes and Aromaticity O–275-344
1. Arenes 275
2. Structure of Benzene 278
3. Aromaticity and Huckel's Rule 283
4. Electrophilic Aromatic Substitution Reactions 287
5. Disubstitution in Benzene Ring and Theory of Substituent Effect 299
6. Fused or Condensed Aromatic Hydrocarbons 312
7. Anthracene 322
8. Biphenyls 329
$ Exercise 331
$ Answers 341
Chapter 7 Alkyl and Aryl Halide O–345-396

1. Introduction 345
2. Alkyl Halides 345
3. Aliphatic Nucleophilic Substitution 354
4. Polyhalogen Compounds 367
5. Aryl Halides 370
6. Synthesis and Uses of DDT 382
7. Synthesis and Uses of BHC 383
$ Exercise 391
$ Answers 395
❍❍❍
(viii)
Book-2
Organic C hemistry-I
Unit-I
Chapter 1 : Structure and Bonding
Chapter 2 : Mechanism of Organic Reactions
Chapter 3 : Alkanes and Cycloalkanes
Unit-II
Chapter 4 : Stereochemistry of Organic Compounds
Unit-III
Chapter 5 : Alkenes, Cycloalkenes, Dienes and Alkynes
Unit-IV
Chapter 6 : Arenes and Aromaticity

Chapter 7 : Alkyl and Aryl Halide
UnitO-3
-I
C HAPTER 1
Structure and Bonding
1. Introduction
Before starting any discussion on organic chemistry, first let us make it very clear that the fundamentals
involving bond cleavage, various intermediates and their reactivities, types of reagents, field effects etc form
the backbone of entire organic chemistry. These concepts will be useful in understanding the acidic or basic
behaviour of many organic compounds, types of various organic reactions, mechanism of various reactions
and their other aspects.
2. Localised and Delocalized Chemical Bonding

2.1 Types of Bond
As stated a chemical bond is an attraction between atoms. This attraction may be seen as the result of
different behaviors of the outermost electrons of atoms. Although all of these behaviors merge into each other
seamlessly in various bonding situations so that there is no clear line to be drawn between them, customarily
the chemical bonds are classified into different types.
One more point has to be reiterated before discussing the classification of chemical bond. Atom may attain a
stable electronic configuration in three different ways by losing electron, by gaining or by sharing electron.
Moreover, elements may be divided into following three types depending upon their electronegativity as:
1. Electropositive elements: Those elements whose atoms give up one or more electron fairly readily.
2. Electronegative elements: Which will accept electron.
3. Elements which have little tendency to lose or gain electrons.
Three different types of bond may be formed depending on the electropositive or electronegative character of
atom involved.
Electropositive element + Electropositive element → Metallic bond
Electropositive element + Electronegative element → Ionic bond
Electronegative element + Electronegative element → Covalent bond
O-4
2.2 Covalent Bond

In the simplest view of a so-called 'covalent' bond, one or more electrons (often a pair of electrons) are drawn
into the space between the two atomic nuclei. Here the negatively charged electrons are attracted to the
positive charges of both nuclei, instead of just their own. This overcomes the repulsion between the two
positively charged nuclei of the two atoms, and so this overwhelming attraction holds the two nuclei in a fixed
configuration of equilibrium, even though they will still vibrate at equilibrium position. Thus, covalent
bonding involves sharing of electrons in which the positively charged nuclei of two or more atoms
simultaneously attract the negatively charged electrons that are being shared between them. These bonds
exist between two particular same or different atoms, and have a direction in space, allowing them to be
shown as single connecting lines between atoms in drawings. For Example, Two chlorine atoms react to form
a Cl2 molecule
Cl + Cl Cl Cl
Each chlorine atom gives a share of one of its electrons to other atom. A pair of electrons is shared equally
between both atoms and each atom now has eight electrons in its outer shell (stable octet). In a similar way, a
molecule of tetra chloromethane CCl4 is made up of one carbon and four chlorine atoms.
Cl
C + 4C Cl C Cl
Cl
The carbon atom is short off four electrons so as to have noble gas structure. Consequently, it forms four
bonds with the chlorine atoms which themselves are short of one electron so they each form one bond by
sharing electrons. In this way, both carbon and all four chlorine atoms attain a noble gas structure.
N + 3[H ] H N H
H
A molecule of ammonia (NH3 ) is made up of one nitrogen and three hydrogen atoms. Other examples of
covalent bonds include water (with two covalent bonds) and hydrogen fluoride (one covalent bond and three
lone pairs).
H O , H F
H
In a polar covalent bond, one or more electrons are unequally shared between two nuclei. Covalent bonds
often result in the formation of small collections of better-connected atoms called molecules. These molecules
in solid and liquid state are bound to other molecules by intermolecular forces that are often much weaker
than the covalent bonds that hold the molecules internally together. Such weak intermolecular bonds give
organic molecular substances, such as waxes and oils, their soft character, and their low melting points. When
covalent bonds link long chains of atoms in large molecules, however (as in polymers such as nylon), or when
covalent bonds extend in networks through solids that are not composed of discrete molecules (such as
diamond or quartz or the silicate minerals in many types of rock) then the structures that result may be both
strong and tough, Also, the melting points of such covalent polymers and networks increase greatly.
O-5
2.3 Types of Covalent Bonds Sigma (σ) and Pi (π) Bonds

Depending upon the type of overlapping, the covalent bonds are mainly of two types.
1. Sigma (σ) bond: When a bond is formed between two atoms by the overlap of their atomic orbitals
along the internuclear axis the resulting bond is called sigma(σ) bond. Such type of overlap is also
known as end to end or head on overlap. It is a strong bond and cylindrically symmetrical. The
overlapping along the internuclear axis can take place in any of the following ways:
(i) s—s overlapping: This type of overlapping takes place between atoms having half filled
s–orbitals in their outer most energy shell. For example, in the formation of hydrogen molecule,
1s orbital of one hydrogen atom overlaps with 1s orbital of other hydrogen atom thus forming a
sigma bond.
+ + +
1s arbital of 1s arbital of s–s overlap

H–atom H–atom
Fig. 1: Overlap of s orbital
(ii) s— p overlapping: In this case, half filled s–orbital of one atom overlaps with the half filled
p–orbtial of another atom. A simple example of this type is the formation of hydrogen fluoride.
Here 1s orbitals of hydrogen overlaps with 2pz orbital of fluorine.
+ +
+
1-s orbital 2pz orbital s–p overlap

of H–atom of F–atom
Fig. 2: Overlap of s–p orbital
(iii) p—p overlapping: This type of overlapping occurs when p–orbital of one atom overlaps with
the p–orbital of the other as in case of fluorine molecule. The molecule of fluorine is produced by
the overlapping of 2pz orbitals of the two fluorine atoms.
+ +
+
2pz orbital p–p overlap

2pz orbital
of F–atom of F-atom
Fig. 3: Overlap of p–p orbital
2. Pi (π) bond: Pi (π)bond is formed by lateral or sidewise overlapping of p orbitals. Sideways overlap
means overlapping of p orbitals in a direction perpendicular to the internuclear axis. A π bond is not
formed between two bonded atoms unless the two are held together with a σ −bond. It is relatively a
weaker bond since the electrons are not strongly attracted by the nuclei of bonding atoms. For example,
O-6
(i) In case of oxygen molecule (each oxygen atom having electronic configuration,
1s2 2s2 2p2x 2p1y 2p1z ), the two atoms are held together by one σ-bond and one π-bond.
O2 molecule
Two Half–filled Two Half–filled
p–orbitals of p–orbitals of (O=O)
O–atom O–atom
Fig. 4: Formation of O2 molecule
(ii) In the molecule of nitrogen both nitrogen atoms are held together by one σ-bond and 2 π-bonds.
Nitrogen atom has an electronic configuration 1s2 2s2 2p1x 2p1y 2p1z .
N–atom N–atom N2 molecule

–
(N=N)
2
Fig. 5: Formation of nitrogen
It is important to remember that the 's' orbitals can only form σ-bonds, whereas the p, d & f
orbitals can form both σ and π-bonds.
2.4 Multiple Bonding

When two atoms share a single pair of electrons, the bond is referred to as a single bond. Atoms can also
share two or three pairs of electrons in the aptly named double and triple bonds. The first bond between two
atoms is called the σ (sigma) bond. All subsequent bonds are referred to as π (pi) bonds. In Lewis structures,
multiple bonds are depicted by two or three lines between the bonded atoms. The bond order of a covalent
interaction between two atoms is the number of electron pairs that are shared between them. Single bonds
have a bond order of 1, double bonds 2, and triple bonds 3. Bond order is directly related to bond strength
and bond length. Higher order bonds are stronger and shorter, while lower order bonds are weaker and
longer. The Lewis structures for some common molecules involving multiple covalent bonds can be found
below.
O-7
H H H H
C C C N C O
H H H H H
Ethylene Formaldimine Formaldehyde
(ethere)
– +
H C C H H C N C O
acetylene hydrogen carbon
cyanide monoxide
Fig. 6: Lewis structures of molecules with multiple bonds
2.5 Co–ordinate Bond

A covalent bond results from sharing of a pair of electrons between two atoms, where each atom contributes
one electron to the bond. It is also possible to have an electron pair bond where both the electrons come from
one of the two binding atoms and there is no contribution from the other atom. Such bonds are called
co–ordinate bonds or dative bonds. So, co–ordinate bond is a special type of covalent bond in which both the
bonded electrons come from one of the two binding atoms. One common example is formation of
ammonium ion. Even though the ammonia molecule has a stable electronic configuration it can react with a
hydrogen ion (H+) by donating a lone pair of electrons from N atom to H+ ion forming the ammonium ion
NH4+ .
H + H +
H
H N + [H+] H N H or H N H
H H H
Covalent bonds are usually shown as a straight line joining the two atoms, and co–ordinate bonds as arrows
indicating which atom is donating the electron. Similarly, ammonia donates its lone pair to boron trifluoride
and by this means the boron atom attains noble gas configuration.
H F H F
H N + B F H N B F
H F H F
In a similar way a molecule of BF3 can form a co–ordinate bond by accepting a lone pair from a F − ion.
– F –
F
F + B F F B F
F
F
3. Characteristics of Covalent Bond

Some important characteristics of covalent bonds like bond length, bond angle and bond energy are
discussed below:
O-8
3.1 Bond Length

In molecular geometry, bond length or bond distance is the average distance between nuclei of two
bonded atoms which may be same or different in a molecule.
It is a transferable property of a bond between atoms of fixed types, relatively independent of the rest of the
molecule. Bond length is related to bond order, when more electrons participate in bond formation the bond
will get shorter. Bond length is also inversely related to bond strength and the bond dissociation energy, as all
other things being equal a stronger bond will be shorter. In a bond between two identical atoms half the bond
distance is equal to the covalent radius. Bond lengths are measured in the solid phase by means of X-ray
diffraction, or approximated in the gas phase by microwave spectroscopy. A set of two atoms sharing a bond
is unique going from one molecule to the next. For example the carbon to hydrogen bond in methane is
different from that in methyl chloride. It is however possible to make generalizations when the general
structure is the same.
The actual bond length between two atoms in a molecule depends on such factors as the orbital hybridization
and the electronic and steric nature of the substituents. The carbon-carbon bond length in diamond is 154 pm
which is also the largest bond length that exists for ordinary carbon covalent bonds.
There are compounds in which shorter than average carbon–carbon bonds distances are also possible.
Alkenes and alkynes have bond lengths of respectively 133 and 120 pm due to increased s-character of the
sigma bond and presence of π bond.
153.5 pm 133.9 pm 120.3 pm
C2H6 C2H4 C2H2

Fig. 8: Bond length in different hydrocarbons
O-9
In benzene all C-C bonds have the same length, 139 pm, due to resonance.
Tabel 1: Bond lengths in organic compounds
C—H Length (pm) C—C Length(pm) Multiple–bonds Length (pm)
sp3—H 110 sp3—sp3 154 Benzene 140
sp2—H 109 sp3—sp2 150 Alkene 133.9
sp—H 108 sp2—sp2 147 Allene 120.3
sp3—sp 146
sp2—sp 143
sp—sp 137
3.2 Bond Angle

Molecular geometry is the three-dimensional arrangement of the atoms that constitute a molecule. It
determines several properties of a substance including its reactivity, polarity, phase of matter, color,
magnetism, and biological and physical activities as well. Molecular geometries can be specified in terms of
bond lengths, bond angles and torsional angles. A bond angle is the angle formed between three atoms
across at least two bonds. For four atoms bonded together in a chain, the torsional angle is the angle between
the plane formed by the first three atoms and the plane formed by the last three atoms. As a matter of fact, the
angles between bonds that an atom forms also depend on the rest of molecule, albeit weakly. Some of the
molecules alongwith bond angles are shown below,
109° 47
120°
180°
Linear Trigonal
planar Tetrahedral
90°
90° 120°
90°
Trigonal
Octahedral
bipyramidal
Fig. 9: Different molecular shapes along with bond angles
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Solved Examples
Example1: Predict all bond angles in the following molecules.
(i) CH3Cl (ii) CH3CN (iii) CH3COOH
Solution: (i) The Lewis structure of methyl chloride is:

H
H C Cl
In the Lewis structure of CH3Cl carbon is surrounded by four regions of high electron density, each of which
forms a single bond. Based on the VSEPR model, we predict a tetrahedral distribution of electron clouds
around carbon, H - C - H and H - C - Cl bond angles of 109.5°, and a tetrahedral shape for the molecule. Note
the use of doted lines to represent a bond projecting behind the plane of the paper and a solid wedge to
represent a bond projecting forward from the plane of the paper.
(ii) The Lewis structure of acetonitrile, CH3CN is:

H
H C C N
H
The methyl group, CH3-, is tetrahedral. The carbon of the -CN group is in the middle of a straight line
stretching from the carbon of the methyl group through the nitrogen.
109.5° H
H C C N
H 180°
(ii) The Lewis structure of acetic acid is:

H O
H C C O H
H
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Both the carbon bonded to three hydrogens and the oxygen bonded to carbon and hydrogen are centers of
tetrahedral structures. The central carbon will have 120° bond angles.
The geometry around the first carbon is tetrahedral, around the second carbon atom is trigonal planar, and
around the oxygen is bent.
3.3 Bond Energy

In chemistry, bond energy (E) is the measure of bond strength in a chemical bond. It is the energy required
to break one mole of molecules into their individual atoms. For example, the carbon-hydrogen bond energy
in methane E(C-H) is the enthalpy change involved with breaking up one molecule of methane into a carbon
atom and 4 hydrogen radicals divided by 4. Bond energy (E) must not be confused with bond-dissociation
energy. As such, bond energy is an average of different bond dissociation energies of the same type of bonds.
The same bond can appear in different molecules, but it will have a different bond energy in each molecule as
the other bonds in the molecule will affect the bond energy of the specific bond. So the bond energy of C-H in
methane is slightly different than the bond energy of C-H in ethane. One can calculate a more general bond
energy by finding the average of the bond energies of a specific bond in different molecules to get the average
bond energy.
Table 2: Average bond energies (kj/mol)
Single Bonds Multiple Bonds
H—H 432 N—H 391 I–I 149 C=C 614
H—F 565 N—N 160 I–Cl 208 C≡C 839
H—Cl 427 N—F 272 I–Br 175 O=O 495
H—Br 363 N—Cl 200 S–H 347 C = O* 745
H—I 295 N—Br 243 S–F 327 C≡O 1072
C—H 413 N—O 201 S–Cl 253 N=O 607
C—C 347 O—H 467 S–Br 218 N=N 418
C—N 305 O—O 146 S–S 266 N≡N 941
C—O 358 O—F 190 Si–Si 340 C≡N 891
C—F 485 O—Cl 203 Si–H 393 C≡N 615
C—Cl 339 O—I 234

O-12
C—Br 276 F—F 154 Si–C 360
C—I 240 F—Cl 253 Si–O 452
C—S 259 F—Br 237
Cl—Cl 239
Cl—Br 218
Br—Br 193
Some of the characteristics of bond energy values are:

1. Average bond energy values are not as accurate as a molecule specific bond-dissociation energies.
2. Double bonds are higher energy bonds in comparison to a single bond (but not necessarily 2-fold
higher).
3. Triple bonds are even higher energy bonds than double and single bonds (but not necessarily 3-fold
higher).
Example 2: (i) What is the definition of bond energy? When is energy released and absorbed?
(ii) If the bond energy for H-Cl is 431 kJ/mol. What is the overall bond energy of 2 moles of
HCl?
(iii) Using the bond energies given in the chart above, find the enthalpy change for: the
decomposition of water
2H2O(g)→2H2+O2(g)
Is the reaction written above exothermic or endothermic? Explain.

(iv) Which bond in list below has the highest and lowest bond energy? H-H, H-O, H-I, H-F.
Solutions (i) Bond energy is the energy required to break a bond that exists between two atoms. Energy is
given off when the bond is broken, but is absorbed when a new bond is created.
(ii) Simply multiply the average bond energy of H-Cl by 2. This leaves one with 862 kJ/mol (using the
table).
(iii) The enthalpy change deals with breaking two mole of O-H bonds and the formation of 1 mole of O-O
bonds and two moles of H-H bonds.The sum of the energies required to break the bonds on the
reactants side is 4×460 kJ/mol = 1840 kJ/mol.The sum of the energies released to form the bonds on
the products side is
2 moles of H-H bonds = 2 x 436.4 kJ/mol = 872.8 kJ/mol
1 moles of O–O bond – 1 x 498.7 kJ/mol = 498.7 kJ/mol
The released energy = 872.8 kJ/mol + 498.7 kJ/mol = 1371.5 kJ/mol. Total energy difference is 1840
kJ/mol - 1371.5 kJ/mol = 469 kJ/mol, which indicates that the reaction is endothermic and that 469 kJ
of heat is needed to be supplied to carry out this reaction.
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(iv) H-F has the highest bond energy since the difference in electronegativity is the greatest. However, the
H-I bond is the lowest bond energy (not due to the electronegativity difference, but due to the greater
size of the I atom).
3.4 The Shape of Molecules

The three dimensional shape or configuration of a molecule is an important characteristics. This shape is
dependent on the preferred spatial orientation of covalent bonds to atoms having two or more bonding
partners. Three dimensional configurations are best viewed with the aid of models. In order to represent such
configurations on a two-dimensional surface (paper, blackboard or screen), one can normally use
perspective drawings in which the direction of a bond is specified by the line connecting the bonded
atoms. In most cases the focus of configuration is a carbon atom, so the lines specifying bond directions will
originate there. As defined in the diagram, a simple straight line represents a bond lying approximately in the
surface plane. The two bonds to substituents A in the structure below are of this kind,
A normal bond
wedge bond
C D
A B
or
}hatched bond
dashed bond
A wedge shaped bond is directed in front of this plane (thick end toward the viewer), as shown by the bond to
substituent B; and a hatched bond is directed in back of the plane (away from the viewer), as shown by the
bond to substituent D. Some texts and other sources may use a dashed bond in the same manner as we have
defined the hatched bond, but this can be confusing because the dashed bond is often used to represent a
covalent bond that is partially formed or partially broken.
4. Delocalized Chemical Bonding and Resonance

In chemistry, resonance is a way of describing delocalized electrons within certain molecules or polyatomic
ions where the bonding cannot be expressed by one single Lewis formula. So, resonance is a bonding
behaviour in which a molecule or ion with such delocalized electrons is represented by several contributing
structures also known as resonating structures or canonical forms. Each contributing structure can be
represented by a Lewis structure, with only an integer number of covalent bonds between each pair of atoms
within the structure. Several Lewis structures are used collectively to describe the actual molecular structure.
However these individual contributors are not real structures. So, these cannot be observed in the actual
resonance-stabilized molecule; the molecule does not oscillate back and forth between the contributing
structures, as might be assumed from the word "resonance". The actual structure is an approximate
intermediate between the various canonical forms, but its overall energy is lower than each of the
contributors. This intermediate form between different contributing structures is called a resonance
hybrid.The point of importance is that the contributing structures differ only in the position of electrons, not
in the position of nuclei.
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4.1 Resonance Energy Concept along with Development

Resonance is a key of valence bond theory. Electron delocalization lowers the potential energy of the
substance and thus makes it more stable than any of the contributing structures. The difference between the
potential energy of the actual structure and that of the contributing structure with the lowest potential energy
is called the resonance energy or delocalization energy. Resonance is different from tautomerism and
conformational isomerism, which involve the formation of isomers, thus the rearrangement of the nuclear
positions.
4.2 Characteristics of Resonance

Molecules and ions with resonance have certain basic characteristics.
O O– –O
C C C
–O O –O O O O–
Fig. 10: Contributing structures of the carbonate ion
In diagrams, contributing structures are typically separated by double-headed arrows (←→ ). The arrow
should not be confused with the right and left pointing equilibrium arrow ( ).
[S=C=N S–C N]
Fig. 11: Contributing structures of the thiocyanate ion
All structures together may be enclosed in large square brackets, to indicate they picture one single molecule
or ion, not different species in a chemical equilibrium. Alternatively to the use of resonance structures in
diagrams, a hybrid diagram can be used. In a hybrid diagram, π bond that are involved in resonance are
usually pictured as curves or dashed lines, indicating that these are partial rather than normal complete π
bonds. In benzene and other aromatic rings, the delocalized π-electrons are sometimes pictured as a solid
circle. Some of the important characteristics are :
1. They can be represented by several Lewis formulas, called "contributing structures", "resonance
structures" or "canonical forms". However, the real structure is not a rapid interconversion of
contributing structures. To represent the intermediate, a resonance hybrid is used instead.
2. The contributing structures are not isomers. They differ only in the position of electrons, not in the
position of nuclei.
3. Each resonating form must have the same number of valence electrons and thus the same total charge,
and the same number of unpaired electrons, if any.
4. Bonds that have different bond orders in different contributing structures do not have typical bond
lengths. Measurements reveal intermediate bond lengths.
5. The real structure has a lower total potential energy than each of the contributing structures would have.
This means that it is more stable than each separate contributing structure would be.The gap of the
potential energies of the resonance hybrid and the most stable resonating structure is known as
resonance energy, as stated earlier.
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4.3 Resonance Hybrids

The actual structure of a molecule in the normal quantum state has the lowest possible value of total energy.
This structure is called the "resonance hybrid" of that molecule. The resonance hybrid is the approximate
intermediate of the contributing structures, but the overall energy is lower than each of the contributors, due
to the resonance energy. Any molecule or ion exists in only one form - the resonance hybrid. It does not jump
back and forth between its resonance contributors- looking like one this moment and like another the next
moment.
4.4 Stability of Resonating Forms

One contributing structure may resemble the actual molecule more than another in the sense of energy and
stability. Structures with a low value of potential energy are more stable than those with high values and
resemble the actual structure more. The most stable contributing structures are called major contributors, so
more is the stability of a canonical form, more is its contribution towards the resonance hybrid. Energetically
unfavourable and therefore less probable structures are minor contributors. The stability of a canonical form
depends upon the following factors,
1. The atoms of the structure must obey as much as possible the octet rule, so that 8 valence electrons must
be present around each atom rather than having deficiencies or surplus.
2. More is the number of covalent bonds, higher is the stability.
3. A major contributer is the one that carry a minimum of charged atoms. If unlike charges are present their
separation must be least while for like charges the separation must be maximum.
4. In case of presence of negative charge, if any, it must be present on the more electronegative atoms and
positive charge, if any, on the most electropositive. So, in the following case, structure II is more stable
than I because the negative charge is placed on more electronegative O atom. Similarly positive
charges, if present, are best occupied on atoms of low electronegativity.
CH2–C–CH3 CH2 C–CH3
O O
I II
5. The greater the number of contributing structures, the more stable the molecule. This is because the
more states at lower energy are available to the electrons in a particular molecule, the more stable the
electrons are. Also the more volume electrons can occupy, the more stable the molecule is. It can be
understood by borrowing a concept of physics, which states that charge dispersed is directly
proportional to stability. Here, electrons can be termed as charged bodies and the more volume they
occupy, more the charge gets dispersed ultimately leading to stability.
6. Equivalent contributors contribute equally to the actual structure; those with low potential energy (the major
contributors) contribute more to the resonance hybrid than the less stable minor contributors. Especially
when there is more than one major contributor, the resonance stabilization is high.
4.5 Van der Waals Interactions

In chemistry, the Van der Waals force or Van der Waals interaction is the sum of the attractive or repulsive
forces between molecules or between parts of the same molecule other than those due to covalent bonds, or
the electrostatic interaction of ions with one another, with neutral molecules, or with charged molecules.
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Van der Waals forces include attractions and repulsions between atoms, molecules, and surfaces, as well as
other intermolecular forces. As such, Van der Waals forces define many properties of organic compounds,
including their solubility in polar and non-polar solvents etc.For example,in low molecular weight alcohols,
the hydrogen-bonding properties of the polar hydroxyl group dominate the weaker Van der Waals
interactions. In higher molecular weight alcohols, the properties of the nonpolar hydrocarbon chain(s)
dominate and define the solubility. Van der Waals forces quickly vanish at longer distances between
interacting molecules.
Van der Waals forces are relatively weak compared to covalent bonds which is quite expected of them being
the intermolecular forces and not a type of chemical bond. However, these forces play a fundamental role in
chemistry and its different offshoots like supramolecular chemistry, polymer science, nanotechnology, and
surface science. All Van der Waals forces are anisotropic except those between two noble gas atoms. It
means that the magnitude of these forces depend on the relative orientation of the molecules. The induction
and dispersion interactions are always attractive, irrespective of orientation, but the electrostatic interaction
changes sign upon rotation of the molecules. That is, the electrostatic force can be attractive or repulsive,
depending on the mutual orientation of the molecules. The main characteristics are:
1. They are weaker than normal covalent or ionic bonds.
2. Van der Waals forces are additive and cannot be saturated.
3. They have no directional characteristics.
4. They are all short - range forces and hence only interactions between nearest need to be considered
instead of all the particles. The greater is the attraction if the molecules are closer due to Van der Waals
forces.
5. Van der Waals forces are independent of temperature except dipole - dipole interactions.
4.5.1 Types of Van Der Waals Forces

Van der Waals forces include a number of interactions. These are discussed below,
1. Dipole-dipole interaction: A force between two permanent dipoles is known as dipole-dipole
interaction or Keesom force. It can be diagrammatically shown below,
δ+ δ– δ+ δ–
attraction
Fig. 12: Dipole–dipole interaction
Dipole-Dipole interactions result when two polar molecules approach each other in space. When this occurs,
the partially negative portion of one of the polar molecules is attracted to the partially positive portion of the
second polar molecule. This type of interaction between molecules accounts for many physically and
biologically significant phenomena. An example is shown below:
–
δ+ δ– δ+ δ
H—Cl H—Cl
Fig. 13:Dipole–dipole interaction in HCl
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2. Dipole - induced dipole interaction: A force between a permanent dipole and a corresponding
induced dipole is also known as dipole - induced dipole or Debye force. This type of attractive
interaction also depends on the presence of a polar molecule. However, the second participating
molecule need not be polar as shown below:
+ +
H2O Xenon
Fig. 14: Example of dipole induced dipole interaction
In the dipole-induced-dipole interaction, the presence of the partial charges of the polar molecule causes a
polarization, or distortion, of the electron distribution of the other molecule. As a result of this distortion, the
second molecule acquires regions of partial positive and negative charge, and thus it becomes polar. The
partial charges so formed behave just like those of a permanently polar molecule and interact favourably with
their counterparts in the polar molecule that originally induced them. Hence, the two molecules attract as
shown below:
δ– δ+
+
Spherical atom with no dipole, Upon approach of a charged ion,

The dot indicates the location electrons in the atom respond and the
of the nucleus atom develops a dipole.
Fig. 15: Dipole–induced dipole interaction
This interaction also contributes to the intermolecular forces that are responsible for the condensation of
hydrogen chloride gas.
3. Induced dipole-induced dipole interaction : It is a force between two instantaneously induced
dipoles also known as London dispersion force. This type of interaction acts between all types of
molecule, polar or not. It is the principal force responsible for the existence of the condensed phases of
certain molecular substances, such as benzene, other hydrocarbons, bromine, and the solid elements
phosphorus (which consists of tetrahedral P4 molecules) and sulfur (which consists of crown-shaped S8
molecules). The interaction is called the dispersion interaction or, less commonly, the
induced-dipole-induced-dipole interaction. Two nonpolar molecules of argon are considered near each
other as shown below,
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Ar Ar
δ– δ+ δ– δ+
Fig. 16: Example of induced–dipole induced dipole interaction
Although there are no permanent partial charges on either molecule, the electron density can be thought of as
ceaselessly fluctuating. As a result of these fluctuations, regions of equal and opposite partial charge arise in
one of the molecules and give rise to a transient dipole. This transient dipole can induce a dipole in the
neighbouring molecule, which then interacts with the original transient dipole as shown here,
– + – +
Attract
– + + –
Repulse
Fig. 17: Induced dipole induced dipole interaction
Although the latter continuously flickers from one direction to another (with an average of zero dipole
overall), the induced dipole follows it, and the two correlated dipoles either attract or repel with one another.
5. Hybridization
109.5° 120°
180°
A
A A
In chemistry, hybridization is one of the landmark concept of chemical bonding explaining a number of
properties of covalent compounds. It refers to the concept of mixing atomic orbitals into new hybrid orbitals
with different energies, shapes, etc., than the component atomic orbitals suitable for the pairing of electrons
to form chemical bonds in valence bond theory. Hybrid orbitals are very useful in the explanation of
molecular geometry and atomic bonding properties. Although sometimes taught together with the valence
shell electron-pair repulsion (VSEPR) theory, valence bond and hybridization are in fact not related to the
VSEPR model. It is the process of intermixing of atomic orbitals of same atom, having almost similar energies,
followed by redistribution of energies to form new orbitals of identical energies and sizes. The new orbitals
formed are called hybrid orbitals. The number of hybrid orbitals formed is always equal to the number of pure
atomic orbitals employed for hybridization.
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It is not known whether hybridization actually takes place or not but it is a concept which is used to explain
certain observed properties of molecules. The following points are to be remembered about hybridization,
1. Orbitals belonging to the same atom or ion having almost similar energies get hybridized.
2. Number of hybrid orbitals is equal to the number of pure atomic orbitals taking part in hybridization.
3. The hybridization takes place to produce equivalent hybrid orbitals which are degenerate and which
give maximum symmetry.
4. Hybrid orbitals are always involved in head on overlap, so the type of bonding resulted is always sigma
(σ) bond.
5.1 Important Types of Hybridization

In organic chemistry the various types of hybridization encountered are - sp3, sp2 and sp. These are discussed
in detail.
Fig. 18: Shape of sp3 hybrid lobes
1. sp3 hybridization: In this type of hybridization, one 's' and three 'p' orbitals of the same value of n
(principle quantum number) mix up to form four sp3 hybridized orbitals. The mixing of orbitals is shown
below,
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The sp3 hybrid orbitals have 25% 's' character and 75% 'p' character. These orbitals orient themselves
towards the corners of a regular tetrahedron. The angle between the orbitals is 109°28'. The commonest
example is CH4 as shown below,
1s
H
H
sp3 σ
'
28
9°–
C C
10
sp3 σ
sp3
H H H H
sp3
σ
H
H
Fig. 20: Shape of methane
As such, in any organic compound if the atom is containing 4σ bonds or 3σ bonds plus one lone pair of
electrons or 2σ bonds plus 2 lone pairs of electrons, then the the type of hybridization undergone by the atom
is sp3.
Fig. 21: Lobes of sp2 hybrid orbitals
2. sp2 hybridization: This is a second type of hybridization involving pure one 's' and two 'p' atomic
orbitals of the same principle quantum number. These pure atomic orbitals mix together to form three
sp2 hybridized orbitals. The mixing of orbitals can be shown as,
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y
z
2s 2p 2py 2px
z
Unhybridised
sp2 hybridization unhybridised
p–orbitals
120°
Three sp2
hybrid orbitals
Three sp2
hybrid orbitals in one plane
Fig. 22: Formation of sp2 hybrid orbitals
The sp2 hybrid orbitals have 33.3% 's' character and 66.6% 'p' character. These F F
orbitals orient themselves towards the corners of an equilateral triangle, as B

shown above. It is important to remember that one p orbital perpendicular to
the molecular plane is unhybridised. An inorganic example is BF3,where the
central boron atom is sp2 hybridized.
In cases like ethene (C2H4), the bonding can be shown as, F
H H Fig. 23: Formation of BF3
π
C C
σ
H H
Fig. 24: Bond line notation of C 2H4
Upon exhaustive analysis , it is found that the two carbon atoms have one p–orbital each with an unpaired
electron.
p p
H H
sp2 sp2
C sp2 sp2 C 2
sp2 sp
H
p H
p
Fig. 25: Hybrid orbital arrangement of C2H4

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These two p-orbitals overlap in sideways manner to give rise to a double bond. Both and framework bonding
is shown. H1s H1s
2pz 2pz
z
2 H H
sp2 C C sp C C
H H
H1s H1s
(a)C2H4 σ–bonded framework (b)C2H4 π bonding
Fig. 26: σ and π bond arrangement of C2H4
It is always important to remember that when a bond is formed with head-to-head overlap, it is called a sigma
(σ) bond. Similarly,when a bond is formed with sideways overlap, it is called a pi (π) bond. As such, in any
organic compound if the atom is containing 3σ bonds or 2σ bonds plus one lone pair of electrons, then the
the type of hybridization undergone by the atom is sp2.
Fig. 27: Shape of sp hybrid lobes
3. sp hybridization: In this type, one 's' and one 'p' orbital of the same principle quantum number mix to
form two sp hybridized orbitals, for example in BeCl2, Be is sp hybridized. The mixing of s and p orbitals
can be shown as,
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They possess 50% 's' and 50% 'p' character. In cases like ethyne C2H2, the central carbon atom is sp
hybridized. Ethyne has the following Lewis structure.
H C C H
Hybridization wise, each carbon atom is sp hybridized having two perpendicular p orbitals with two unpaired
electrons present on each carbon atom. These overlap in sideways fashion and produce a triple bond. All the
overlaps are shown below,
pz- Orbital
py- Orbital
σ-bond
C C H
H
π-bond
π-bond
Fig. 29: Formation of ethyne
As such, in any organic compound if the atom is containing 2σ bonds or 1σ bonds plus one lone pair of
electrons, then the type of hybridization undergone by the atom is sp.
5.2 Inclusion Compounds

In host-guest chemistry, the definition of inclusion compounds is very broad, extending to channels formed
between molecules in a crystal lattice in which guest molecules can fit. As such, an inclusion compound is
a complex comprised of two chemical species, one chemical compound is the "host" which generally forms a
cavity. Another is the "guest" compound which are located in the cavities of the host. If the spaces in the host
lattice are enclosed on all sides so that the guest species is 'trapped' as in a cage, the compound is known as a
clathrate. In this type of molecular encapsulation a guest molecule is actually trapped inside another
molecule.
Fig. 30: Guest molecule is trapped inside the host

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5.3 Clathrate Compounds

A clathrate is a chemical substance consisting of a lattice that traps or contains molecules. The word
clathrate is derived from the Latin clatratus meaning with a lattice. Traditionally, clathrate compounds are
polymeric and completely envelop the guest molecule, but in modern usage clathrates also include
host-guest complexes and inclusion compounds. According to IUPAC convention, clathrates are
Inclusion compounds in which the guest molecule is in a cage formed by the host molecule or by a lattice of
host molecules.
Traditionally clathrate compounds refer to polymeric hosts containing molecular guests. More recently, the
term refers to many molecular hosts, including some inorganic polymers such as zeolites. Many clathrates are
derived from an organic hydrogen-bonded frameworks. These frameworks are prepared from molecules that
"self-associate" by multiple hydrogen-bonding interactions. The most famous clathrates are methane
clathrates where the hydrogen-bonded framework is contributed by water and the guest molecules are
methane. Large amounts of methane naturally frozen in this form exist both in permafrost formations and
under the ocean sea-bed. Other hydrogen-bonded networks are derived from hydroquinone, urea, and
thiourea. A much studied host molecule is Dianin's compound which is shown below,
Fig. 31: Dianin's compound
5.4 Charge Transfer Complexes

Charge-transfer complexes exist in many types of molecules, inorganic as well as organic, and in solids,
liquids, and solutions. A well-known example is the iodine starch complex formed by iodine when combined
with starch, which exhibits an intense blue charge-transfer band. A charge-transfer complex or CT complex
or electron-donor-acceptor complex is an association of two or more molecules, or of different parts of
one large molecule, in which a fraction of electronic charge is transferred between the molecular entities. The
resulting electrostatic attraction provides a stabilizing force for the molecular complex. The source molecule
from which the charge is transferred is called the electron donor and the receiving species is called the
electron acceptor. The nature of the attraction in a charge-transfer complex is not a stable chemical bond,
and is thus much weaker than covalent forces. Many such complexes can undergo an electronic transition
into an excited electronic state. The excitation energy of this transition occurs very frequently in the visible
region of the electro-magnetic spectrum, which produces the characteristics intense color for these
complexes. These optical absorption bands are often referred to as charge-transfer bands (CT bands). Optical
spectroscopy is a powerful technique to characterize charge-transfer bands.
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nitrogen atoms have a

higher electron density
than the carbonyl groups
acceptor
and lend it to the
acceptor
O O O O O O
N N N N N N
O O O O O O
donar
carbonyl groups suck
electron density away
from the acceptor unit
5.5 Hydrogen Bonding

Hydrogen bond is a weak force of attraction formed between an H atom and highly electronegative atom like
O, N or F either of the same molecule or of a different molecule but to which it is not directly attached.
Moreover the H atom itself should be attached to a highly electronegative atom like O, N or F. HF is
considered as an example. The hydrogen fluorine bond in hydrogen fluoride is polar covalent bond as
fluorine is a strongly electronegative element. As a result fluorine acquires a partial negative charge and
hydrogen acquires a partial positive charge.
δ+ δ−
H− F
The lone pair on the fluorine atom in another molecule of hydrogen fluoride will attract the positive charge on
hydrogen in a molecule of hydrogen fluoride electrostatically. This bond between hydrogen and fluorine of
different molecules is known as hydrogen bond. This type of linkage is represented by dotted lines.
δ+ δ – δ+ δ – δ+ δ –
H – F .......... H – F............ H – F
Hydrogen Bond
Here, it is important to remember that hydrogen bonding is not a type of chemical bond rather it is an
intermolecular force of attraction.
5.5.1 Conditions for Hydrogen Bonding

1. The molecule must contain a highly electronegative atom linked to hydrogen atom.
2. The size of electronegative atom should be small. These conditions are met only by F, O and N atoms.
Although Cl has the same electronegativity as nitrogen, it does not frequently form effective hydrogen bond. This
is because of its larger size than that of N with the result that its electrostatic attractions are weak.
5.5.2 Types of Hydrogen Bonding

Generally the hydrogen bonds are classified into two types -
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1. Intermolecular hydrogen bonding

2. Intramolecular hydrogen bonding
1. Intermolecular hydrogen bonding: In this type of hydrogen bonding, the two or more than two
molecules of same or different compounds combine together to give a polymeric aggregate. Some of
the examples are,
δ+ δ–
O – H..........O
(iii) H – C C–H
O..........H – O
δ– δ+
(iv)
Cl O – H......Cl O–H
2. Intramolecular hydrogen bonding: In this type, hydrogen bonding occurs within two atoms of the
same molecule. This type of hydrogen bonding results into ring formation commonly known as
chelation. Organic compounds frequently show this type of H bonding. Some of the examples are,
+ O–H
O – Hδ O
Cl δ–
N
O
o–chlorophenol o–nitrophenol
5.5.3 Effects of Hydrogen Bonding

1. Boiling point and melting point: The high boiling point of water can be explained on the basis of
hydrogen bonding.Water molecules associate through extensive network of hydrogen bonding and
thus require more energy to break the intermolecular forces. Similarly we can explain the higher boiling
point of alcohols, amines, amides etc. Moreover, H2O is a liquid but H2S is a gas because H2O can form
hydrogen bond but H2S cannot.
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Up till now those examples are considered where boiling point is increased due to hydrogen bonding.
Normally, this happens in the case of intermolecular hydrogen bonding. However, there are certain
cases where the boiling point is decreased due to hydrogen bonding. It happens in the case of
intramolecular hydrogen bonding. For example o–hydroxy, nitro, carbonyl, carboxylic or chloro
compounds have lower melting and boiling points than the respective meta or para isomers. The
explanation is intramolecular hydrogen bonding taking place between the two groups placed ortho to
each other. It prevents the association of the molecule with other neighbouring molecules. As a result,
the intermolecular forces of attraction decreases which eventually leads to decreased melting and
boiling points.
O O O
H H H
Intramolecular
Hydrogen bonding
O Cl O
N N
o–chlorophenol
O O–H
o–nitrophenol
o–hydroxy
benzoic acid
On the other hand, in case of meta– and para–isomers, intramoelcular hydrogen bonding is not possible
because of the bigger size of the ring formed. Rather, these molecules indulge into intermolecular
hydrogen bonding which causes association. This association of molecules eventually leads to higher
mp and bp for meta and para isomers.
2. Water solubility: A substance is said to be soluble in water if it is capable of forming hydrogen
bonding with water molecules. For example alcohols are soluble in water due to hydrogen bonding.
H – O ...........H – O .......... H – O .......... H – O
H R H R
It is important to note that when alkyl groups in alcohols are bulkier having four or more carbon atoms,
the alkyl group predominates over OH group. So, hydrogen bond forming ability is subdued with the
result that the solubility of such alcohols in water decreases. On the contrary side, when a compound
has a large ratio of –OH groups to hydrocarbon group, it will be highly water soluble. Thus sugar, certain
starches and polyvinyl alcohol are quite soluble in water. Solubility of other compounds (organic or
inorganic) having one or more than one –OH group can be explained on the basis of hydrogen
bonding. Detergents are also soluble in water due to solubilizing effect of hydroxyl groups.
It is important to note that while the intermolecular hydrogen bonding increases solubility of the
compound in water, the intramolecular hydrogen bonding decreases. This is due to fact that the
formation of intramolecular hydrogen bond prevents hydrogen bonding of the compound with water. It
eventually reduces solubility of the compound in water.
For Example: o–nitrophenol is less soluble in water then p–nitrophenol because due to intramolecular
hydrogen bonding –OH group is not available to form hydrogen bond with water.
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O–H
O δ– δ+
N O–H
O
H
Hydrogen bonding with H2O molecule is not
possible because – OH group of o–nitrophenol
o–Nitrophenol
is not available for intermolecular bonding.
3. Volatile nature: A compound having high boiling point is less volatile and vice versa. As
intermolecular hydrogen bonding increases the boiling point so it can be concluded that volatile nature
of a compound decreases if intermolecular hydrogen bonding is present. On the other side, the volatility
increases if intramolecular hydrogen bonding is present.
5.6 Aromaticity
In organic chemistry, aromaticity is formally used to describe an unusually stable nature of some planar or
flat rings of atoms such that the ring may be homonuclear as in case of benzene or hetronuclear as in case of
pyridine.
H H
H C H
C H C H
C
C C
C C
H H
C C C
H H
N
H
These structures contain a number of double bonds that interact with each other according to certain rules. As
a result of their being highly stable, such rings tend to form easily, and once formed, tend to be difficult to
break in chemical reactions. Since one of the most commonly-encountered aromatic system of compounds
in organic chemistry is based on derivatives of benzene which is commonly found in petroleum, the word
"aromatic" is occasionally used to refer informally to benzene derivatives, and this is how it was first defined.
Nevertheless, many non-benzene aromatic compounds do exist as well. In living organisms, for example, the
most common aromatic rings are the double-ringed bases in RNA and DNA, and interestingly benzene and
its derivatives are too rare in biology. Huckel's rule helps us to decide that a given compound would be
aromatic or not by observing its structure. According to this rule, for a compound to be aromatic, it must
satisfy the following conditions,
1. There must be cyclic delocalization in the compound.
2. The closed loop formed due to cyclic delocalization must have a total of (4n + 2)π electrons where n is
an integer having values 0, 1, 2, 3…… . The (4n + 2)π electrons is called Hukel number.
The first condition of cyclic delocalization takes into account the conditions required to show resonance so
that the compound must have conjugation and the compound must be planar or nearly planar. If both the
above conditions are fulfilled, then the compound would be aromatic and if any of the above condition fails,
then it is non-aromatic.
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First of all, let us take the simplest example of benzene. As it is evident from the structure that there is
conjugation in the ring leading to cyclic delocalization. Moreover,the closed loop thus formed
would have 6π electrons which corresponds to n=1 in the Huckel's rule. Thus, benzene is said to be
aromatic compound. The same would be true for phenol and nitrobenzene also.
OH NO2
The rule is discussed in details in chapter VI.
6. Electron Displacement Effect

In organic chemistry, there are some important mechanisms of electron displacement like field and inductive
effect, electromeric effect, mesomeric effect and hyperconjugation. These effects are discussed below one by
one.
6.1 Field and Inductive Effect

Inductive Effect is an experimentally observed effect of the transfer of charge - negative or positive, through a
chain of atoms in a molecule.
The permanent dipole induced in one bond by another is called inductive effect. The electron cloud in a
σ-bond between two unlike atoms is not uniform and is slightly displaced towards the more electronegative of
the two atoms. This causes a permanent state of bond polarization, where the more electronegative atom has
a slight negative charge (δ-) and the other atom has a slight positive charge (δ+). If the electronegative atom is
then joined to a chain of atoms, usually carbon, the positive charge is relayed to the other atoms in the chain.
This is the electron-withdrawing inductive effect, also known as the -I effect. Some groups, such as the alkyl
group, are less electron-withdrawing than hydrogen and are therefore considered as electron-releasing. This
is electron releasing character and is indicated by the +I effect. In short, alkyl groups tend to give electrons,
leading to induction effect.
Explanation
First let us look at the C–C bond in ethane. This C–C bond has no polarity because it connects two similar atoms.
However, the C–C bond in ethyl chloride is polarized by the presence of the electronegative chlorine atom. This
polarization is actually the sum of three effects. In the first of these, the Cl atom have been deprived of some of its
electron density by the higher electronegativity of Cl. Secondly, the electron deficiency of C1 is partially
compensated by drawing the C–C electrons closer to itself, resulting in polarization of this bond and a slight
positive charge on the C2 atom. Thirdly, the polarization of the C–C bond causes a (slight) polarization of the three
methyl C–H bonds. The effect of C1 on C2 is less than the effect of Cl on C1 atom.
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6.2 Field Effect

In addition to such inductive effect operating through the σ–bonds in a compound, an analogous effect can
also operate either through the space surrounding the molecule or in solution via the molecules of solvent
that surround it which is called field effect. A point of distinction between the two effects is that the inductive
effect depends only on the nature of bonds while the field effect depends on the geometry of the molecule.
However, in many cases, it is not possible to distinguish inductive effect with this field effect. But in general,
reference to an inductive effect is assumed to include any such field effect.
6.3 Characteristics of I Effect

Some important characteristics of inductive effect are;
1. It is a permanent electron displacement effect. It is because no attacking reagent (electrophile or

nucleophile)is required to cause the electron displacement.
2. It always causes partial charge separation as shown below,
3. It decreases with increases of distance
4. It does not involve delocalization of π-electrons. Rather,it involves displacement of σ-electrons only.
6.4 Types of Inductive Effect

The inductive effect is divided into two types depending on their strength of electron withdrawing or electron
releasing nature with respect to hydrogen.
1. Negative inductive effect (-I): The electron withdrawing nature of groups or atoms is called as
negative inductive effect. It is indicated by -I. Following are the examples of groups in the decreasing
order of their -I effect:
NH +3 > NO2 > CN > SO3H > CHO > CO > COOH > COCl > CONH2 > F > Cl > Br > I > OH > OR >
NH2 > C6H5 > H
2. Positive inductive effect (+I): It refers to the electron releasing nature of the groups or atoms and is
denoted by +I. Following are the examples of groups in the decreasing order of their +I effect.
C(CH3)3 > CH(CH3)2 > CH2CH3 > CH3 > H
For measurements of relative inductive effects, hydrogen is chosen as reference point in the molecule CR3 -
H. If the H atom in this molecule is replaced by X (an atom or group of atoms), the electron density in the CR3
part of the molecule is less than in CR3 - H, then X is said to have a -I effect or electron withdrawing or electron
attracting inductive effect. If the electron density in the CR3 part is greater than in CR3 - H, then X is said to
have a +I effect or electron releasing or electron repelling inductive effect. Deuterium is also electron
donating with respect to hydrogen. Generally speaking, all alkyl groups exhibit +I effect when they are
attached to an unsaturated or trivalent carbon or other atom. Keeping other things equal, atoms with sp
bonding generally have a greater electron withdrawing ability than those with sp2 bonding, which in turn
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have more electron-withdrawing power than with sp3 bonding. This reasonably accounts for the fact that
arylic, vinylic and alkynyl groups exhibit -I effect.
Example 3: Why alkyl groups are showing positive inductive effect?
Solution: Though the C-H bond is practically considered as non-polar, there is partial positive charge on
hydrogen atom and partial negative charge on carbon atom. Therefore each hydrogen atom acts as electron
donating group. This cumulative donation turns the alkyl moiety into an electron donating group.
6.5 Applications of Inductive Effect

Some of the prominent applications of inductive effect are discussed below.
1. Stability of carbonium ions: The stability of carbonium ions increases with increase in number of
alkyl groups due to their +I effect. The alkyl groups release electrons to carbon, bearing positive charge
and thus stabilize the ion. The order of stability of carbonium ions is:
R R H H
most stable R C+ > R C+ > R C+ > H C+ least stable
R H H H
a tertiary a secondary a primary methyl cartion
carbocation carbocation carbocation
2. Stability of free radicals: In the same way the stability of free radicals increases with increase in the
number of alkyl groups. Thus the stability of different free radicals is:
H CH3 CH3 CH3
C < C C< C <
H H H H H CH3 H3C CH3
Methyl radical Primary radical Secondary radical Tertiary radical
least stable most stable
3. Stability of carbanions: However the stability of carbanions decreases with increase in the number
of alkyl groups since the electron donating alkyl groups destabilize the carbanions by increasing the
electron density.Thus the order of stability of carbanions is:
H H
C
H
methyl > 1° > 2° > 3°
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4. Acidic strength of carboxylic acids and phenols: The electron withdrawing groups (-I) decrease
the negative charge on the carboxylate ion and thus by stabilizing it. Hence the acidic strength increases
when -I groups are present. However the +I groups decrease the acidic strength. For example,
(i) The acidic strength increases with increase in the number of electron withdrawing Fluorine
atoms as shown below.
CH3COOH < CH2FCOOH < CHF2COOH < CF3COOH

(ii) Formic acid is stronger acid than acetic acid since the -CH3 group destabilizes the carboxylate
ion. Generally in gaseous medium, the order of basic strength is,
(iii) On the same lines, the acidic strength of phenols increases when-I groups are present on the ring.
e.g. The p-nitrophenol is stronger acid than phenol since the -NO2 group is a -I group and
withdraws electron density. Whereas the para-cresol is weaker acid than phenol since the -CH3
group shows positive (+I) inductive effect.
5. Basic strength of amines: The electron donating groups like alkyl groups increase the basic strength
of amines whereas the electron withdrawing groups like aryl groups decrease the basic nature.
Therefore alkyl amines are stronger Lewis bases than ammonia, whereas aryl amines are weaker than
ammonia. Thus the order of basic strength of alkyl and aryl amines with respect to ammonia is :CH3NH2
> NH3 > C6H5NH2 . Generally in gaseous medium, the order of basic strength for primary, secondary
and tertiary amines with respect to ammonia is,
CH3 CH3
CH3 N > NH > CH3 NH2 > NH3
CH3 CH3
However, the same order changes in aq. medium depending upon the fact that ammonia is ethylated or
methylated.So, the order of basic strength are given below,
(CH3)2NH > CH3NH2 > (CH3)3N
2° 1° 3°
(C2H5)2NH > (C2H5)3N > C2H5NH2

2° 3° 1°
Basic character decreases
6. Reactivity of carbonyl compounds: The +I groups increase the electron density at carbonyl
carbon. Hence their reactivity towards nucleophiles decreases. Thus formaldehyde is more reactive
than acetaldehyde and acetone towards nucleophilic addition reactions.
Example 4: The inductive effect can be best described as:

(i) The conjugation of σ-bonding orbital with the adjacent π-orbital.
(ii) The ability of atom or group to cause bond polarization.
(iii) The transfer of lone pair of electrons from more electronegative atom to lesser
electronegative atom in a molecule.
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(iv) All of the above.
Solution. (iii)
Example 5: Which of the following statement is incorrect about the inductive effect ?
(i) It is a permanent effect.
(ii) It decreases with increases of distance.
(iii) It involves delocalization of π-electrons.
(iv) It involves displacement of σ-electrons.
Solution. (iii)
Example 6: Which of the following shows positive (+I) inductive effect?

(i) - NO2
(ii) -OCH3
(iii) -COOH
(iv) -CH3
Solution. (iv)
Example 7: Which of the following group shows negative (-I) inductive effect ?
(i) -CH2CH3
(ii) -C(CH3)3
(iii) -C6H5
(iv) -CH3
Solution. (iii)
7. Electromeric Effect
Electromeric effect is a molecular polarizability effect taking place by an intramolecular electron
displacement. It is characterized by the substitution of one electron pair for another within the same atomic
octet of electrons. So, the simplified version is that electromeric effect is the movement of electrons from one
atom to another as a reagent attacks a π–bond. This effect is shown by those compounds containing multiple
bonds. When a double bond or triple bond is exposed to an attack by a reagent, a pair of bonding electrons
involved in the π bond is transferred completely from one atom to another. This is referred as a temporary
electron displacement effect because this effect will remain as long as the attacking reagent is present. As soon
as the reagent is removed, the polarized molecule will come back to the original state as shown below,
In the presence
of reagent +
A=B A —B–
In absence
of reagent
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Since A has lost its shared pair of electrons, it acquires a positive charge while B has gained the electron pair,
thus it acquires a negative charge.
The most common example illustrating the electromeric effect is the reaction of an alkene with Br2 in CCl4.
R R R R Br
Br2 in + – –Br– – Br
C=C C—C C—C C—C
1 2 CCl4 1 2
+
– + Br Br
Br Br
cyclic bromonium ion vicinal dibromide
In this reaction, when the attacking reagent (bromine) approaches alkene, the temporary polarization
develops on the alkene with C2 atom gaining a negative charge and Cl atom acquiring positive charge as it
can be compensated by the +I effect of R group. The alkenes being electron rich compounds, due to the
presence of π electron cloud, are attacked by the electrophile (Br+) to give a cyclic bromonium ion. Here, the
formation of cyclic bromonium ion as intermediate is possible because bromine is of considerably large size
having lone pairs to be bonded to both the carbons simultaneously. The cyclic bromonium ion is then
attacked by Br − from the top (as lower side is already blocked) whereby the three membered ring is cleaved
by trans opening giving vicinal dibromide as the product.
7.1 Types of Electromeric Effect

Like inductive effect, electromeric effect is also of two types - +E and -E effect, as discussed below in details.
+E Effect: If the attacking species is an electrophile, the π electrons are transferred towards the positively
charged atom. This is the +E effect.
+ +
C = C +H C – C
H
+E effect
An example is the protonation of ethene. When the H+ comes near the double bond, the bond is polarized
towards the proton.
+ δ+ δ– + +
H2C=CH2 + H H2C–CH2 + H H2C–CH3
-E Effect: If the attacking reagent is a nucleophile, the electrons are transferred away from the attacking
reagent and into the π system. This is the -E effect and it is being shown below,
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Z
δ+ δ–
C O + Z C
–
Attacking O
species
An example is attack on a carbonyl carbon by cyanide ion which can be represented as,
7.2 Resonance Effect or Mesomerism

The mesomeric effect or resonance effect in chemistry is a property of compounds having a
characteristic set of substituents or functional groups present. The effect is used in a qualitative way and
describes the electron withdrawing or releasing properties of substituents based on relevant resonance
structures and is symbolized by the letter M or R. As such, it is another type of electron displacement effect
shown by various compounds. Definitionwise, it refers to the electron withdrawing or releasing effect
attributed to a substituent through delocalization of p or π electrons. It can be visualized by drawing various
canonical forms. It is important to know about the conditions necessary for a compound to show resonance
effect. The two essential conditions are,
1. There must be conjugation in the molecule. The conjugation is defined as the presence of alternate
double and single bonds in the compound like.
–C=C–C=C–
2. The part of the molecule having conjugation must be essentially planar or nearly planar.
The first condition of conjugation is not only confined to the presence of alternate double and single bonds as
mentioned above. There are some other ways available to achieve conjugation. These are
+
(i) – C = C – C – (ii) – C = C – C –
O
(iii) – C = C – C – (iv) – C = C – O – (v) – C = C – N
O
So, any molecule satisfying both the conditions will show resonance and hence resonance effect. For
example, phenol is considered to show mesomeric effect. The structure of phenol is
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O–H
By looking at the structure, it must be clear that the compound possess conjugation of the type
− C = C − C = C − as well as the category (iv) because the lone pairs on oxygen are in conjugation
| | | |
with unsaturated (sp2 hybridised) carbon of the ring. Since, oxygen atom is sp3 hybridised in phenol, the lone
pairs on oxygen are nearly planar with respect to the p z orbital of carbon linked to oxygen. Thus, both the
conditions are fulfilled by phenol. So the compound shows resonance and hence mesomeric effect is
operational. Its various resonating structures are represented as
O–H ⊕O –H ⊕O –H ⊕O –H O–H
This has to be borne in mind that resonance and henceforth the subsequent the electron displacement always
results in different distribution of electron density. It is a permanent effect because no attacking reagent is required
to carry out the displacement. Some more examples of electron displacement are shown below. In, 1,
3-Butadiene the different resonance structures and the electron displacement therein is shown.
⊕ ⊕
CH2 CH—CH CH2 CH2 —CH CH —CH2 CH2—CH CH—CH2
Similarly, electron displacement can be shown in vinyl chloride,
⊕
CH2 CH—Cl CH2 —CH Cl
7.3 Types of Resonance Effect

Resonance (mesomeric) effect is of two types
1. If the atom or group of atom is electron releasing through resonance, it is called +R or +M effect. For
example,
Other groups that show +M effect are –NHR, –NR2, –OH, –OR, –NHCOR, –Cl, –Br, –I etc.
2. If the atom or group of atom is withdrawing electrons through resonance, it is called –R or –M effect.
For example,
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Other groups showing M effect are –CN, –CHO, –COR, –CO2H, –CO2R, –CONH2, –SO3H, –COCl etc.
In general, if any atom (of the group) attached to the carbon of benzene ring bears atleast one lone pair,
then the group shows +M effect while if the atom (of the group) linked to the benzene carbon bears
either a partial or full positive charge, then the group exhibits –M effect.
7.4 Illustrations & Applications of Resonance Effect or Mesomeric Effect

1. The negative resonance effect (–R or –M) of carbonyl group is shown below. It withdraws electrons by
delocalization of π electrons and reduces the electron density particularly at ortho and para positions.
H3C H3C – H3C –
O O Oδ
C C C
+ δ+ δ+
etc.
δ+
2. The nitro group, -NO2, in nitrobenzene shows -M effect due to delocalization of conjugated π electrons
as shown below. Note that the electron density on benzene ring is decreased especially on ortho and
para positions.
This is the reason for why nitro group deactivates the benzene ring towards electrophilic substitution
reaction.
3. The -NH2 group in aniline also exhibits +R effect. It releases electrons towards benzene ring through
delocalization. As a result, the electron density on benzene ring increases particularly at ortho and para
positions. Thus aniline activates the ring towards electrophilic substitution.
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It is also worth mentioning that the electron density on nitrogen in aniline decreases due to
delocalization which is the reason for its less basic strength when compared to ammonia and alkyl
amines.
4. The positive resonance effect (+R or +M) of methoxy group is shown in the compound below
7.5 Inductive Effect vs. Resonance Effect

In most of the cases, resonance effect is stronger and outweighs inductive effect. For example, the -OH and
-NH2 groups withdraw electrons by inductive effect (-I). However they also release electrons by delocalization
of lone pairs (+R effect). Since the resonance effect is stronger than inductive effect the net result is electron
releasing to rest of the molecule. This is clearly observed in phenol and aniline, which are more reacting than
benzene towards electrophilic substitution reactions.
However,the inductive effect is stronger than the resonance effect in case of halogen atoms attached to
benzene ring. Halogens are electronegative and hence exhibit -I effect. However, at the same time they also
release electrons due to delocalization (+R effect) of lone pair. This is evident in case of reactivity of
halobenzenes, which are less reactive than benzene towards electrophilic substitution due to -I effect of
halogens. But it interesting to note that the substitution is directed at ortho and para positions rather than
meta position. It can be ascribed to the fact that the electron density is increased at ortho and para positions
due to +R effect of halogens as shown below,
Cl Cl Cl+ Cl+ Cl+
– –
–
I II III V
IV
7.6 Hyperconjugation (Baker Nathan effect)
As it has been observed that the general inductive effect of alkyl groups is R3C > R2CH > RCH2 > CH3. This
inductive order has been used satisfactorily to explain many phenomenon like the dipole moments in the gas
phase of PhCH3, PhC2H5, PhCH(CH3)2 and PhC(CH3)3 are 0.37, 0.58, 0.65 and 0.70 D respectively.
However, in some reactions, this order is reversed. For example, the rate of reaction of p-substituted benzyl
bromide with pyridine in acetone (follows SN2 pathway) is just opposite than that expected from the electron
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release by the inductive effect. That is, the methyl substituted compound reacted fastest and the t-butyl
substituted compound reacted slowest. The rate order for the R groups was Me > Et > iso Pr > t-Bu.
Br
+
R CH2 N R CH2 N
Thus, the order of electron release is exactly the reverse of inductive effect of alkyl groups. Therefore, alkyl
groups must also possess some other mechanism of electron release in which the order is Me > Et > isoPr >
t- Bu.
This mechanism of electron release is termed as hyperconjugation effect or Baker Nathan effect after its
discoverer. Thus, when the C—H bond is attached to an unsaturated carbon atom, the σ electrons of the
C—H bond becomes less localized by entering into partial conjugation with the attached unsaturated system
i.e., σ, π- conjugation.
This type of conjugation between the σ–electrons of single bond and π–electrons of multiple bond is known as
hyperconjugation. The molecular picture of the σ, π- hyperconjugation is shown below,
π bond H
C C σ bond
H H
Fig. 32: σ – π hyperconjugation
Definitionwise, hyperconjugation is the interaction of the electrons in a σ bond (usually C–H) with an
adjacent empty (or partially filled) non-bonding p-orbital, antibonding ( ∏ ) orbital, or filled ( ∏ ) orbital, to give
an extended molecular orbital that increases the stability of the system.
It is a permanent effect which stabilizes the molecule. When CH 3 group is attached to an unsaturated atom or
one with an unshared orbital, the canonical forms are drawn as
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H H⊕ H H
H – C – CH = CR2 H – C = CH – CR2 H ⊕ C = CH – CR2 H – C = CH – CR2
H H H H⊕
I II III IV
In such canonical forms there is no bond at all between the carbon and hydrogen but the hydrogen is not free
as H+ because it will then contradict the condition of resonance, in which the relative position of the atoms in
the molecule should not change. Thus, hyperconjugable hydrogens are not acidic in nature. It is due to this
fact, hyperconjugation is also referred as no bond resonance. The effect of II, III and IV on the actual molecule
is that the electrons in the C–H bond are closer to the carbon than they would be if II, III and IV did not
contribute at all. For the other alkyl groups sequence -C2H5, -CH(CH3)2, -C(CH3)3, the hyperconjugation is
further diminished because the number of C–H bonds decreases. Hence with respect to hyperconjugation
effect, methyl is the strongest electron donor and t-butyl the weakest.
Hyperconjugation is also operational in case of carbcations and free radicals. In these cases, electrons in
bonds that are β to the positively charged carbon can stabilize a carbocation or even a free radical by
hyperconjugation. The molecular orbital view is shown below,
H
Hyperconjugation Empty 2p
orbital of C
sp3–(–C–H)
σ bond H
+
C C
H
H
H
Fig. 33: Hyperconjugation in case of carbocation stability
7.7 Applications of Hyperconjugation

The significance of this effect is to explain certain facts like
1. o,p-directing influence of CH3 group: In toluene, as CH3 is linked to an sp2 hybridized carbon, it does
show hyperconjugation.
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H H H H
⊕ ⊕ ⊕
H—C—H H—C H H—C H H—C H
As it is evident from the hyperconjugable structures that the electron density will be high at ortho and para
positions, so electrophile attack is favoured at these two positions in preference to meta attack. Thus, the
directive influence of CH3 group is ortho & para.
2. m-directing influence of -CCl3 group:

Cl Cl Cl Cl
Cl — C — Cl Cl — C Cl Cl — C Cl Cl — C Cl
⊕ ⊕
From these structures it is evident that the electron density being greater at meta position than at ortho and
para, the electrophilic attack will be favoured at meta position. Thus, the directive influence of -CCl3 group is
meta.
3. Relative stability of alkenes: The stability of alkenes can be decided by looking at the structure of
alkenes. The alkene which has more hyperconjugable hydrogens will be more stable than the other with
lesser hyperconjugable hydrogens. For example,
In 1-butene, the hyperconjugable structures possible are only 2 while with 2 butene, it will be 6. Thus,
2-butene is more stable than 1-butene. In a chemical reaction leading to the formation of both these alkenes,
the 2-butene will be the major product while 1-butene will be the minor product. This is also decided by
Saytzeff's rule which is a result of the hyperconjugation only. Saytzeff rule states that the more substituted
alkene will be the major product in a reaction which can give two or more alkenes. Thus, 2 butene being
disubstituted would be the major product while 1 butene would be the minor product as it is
monosubstituted.
7.8 Application of Inductive and Resonance Effect

The inductive and resonance effect can be effectively employed to explain the stability of carbocations, free
radicals and carbanions and the acidic and basic strengths of various organic compounds. Let us take them
separately.
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8. Strength of Acids and Bases

There are various theories regarding acids & bases.
1. Arrhenius theory: According to Arrhenius theory, substances producing H + ions in solution are acids
and those producing OH − ions in solution are bases. Therefore, substances like H2O, HCl, H2SO4,
CH3COOH etc. are acids and the ones like NH4OH, NaOH, KOH, H2O etc. are bases.
2. Bronsted Lowry theory: In 1923, Bronsted and Lowry independently defined acids as proton
donors, and bases as proton acceptors. For aqueous solutions the definition does not vary much for
acids from the Arrhenius theory but it widens the scope of bases. In this, the bases need not contain
OH − ions and simply have to accept protons. So ions like Cl − , CH 3 COO– , Br − etc. which do not
contain OH − ions can be considered as bases under this definition.
3. Levelling solvents: Whenever an acid is dissolved in water, it acts as an acid only if the solvent acts as
a base. That is, if we dissolve acids like HCl, HNO3 etc in water, their acidic strength is almost the same
since water acts as a base for both these acids. In fact, it is known that all strong acids show equal acidic
strength when dissolved in water. This is because, water acts as a base to all these acids and thus forces
them to donate almost the same amount of protons irrespective of their chemical nature. Since water
levels the acidic strength of strong acids, it is referred to as a levelling solvent. In order to measure the
strength of strong acids, they are dissolved in glacial acetic acid and the amount of protons is measured
by conductometry. It is found that the strength of acids varies as:
HClO4 > HBr > H2SO4 > HCl > HNO3

4. Lewis theory: Lewis developed a definition of acids and bases that did not depend on the presence of
protons nor involve reactions with the solvent. He defined acids as materials which accept electron
pairs, and bases as substances which donate electron pairs. Thus a proton is Lewis acid and ammonia is
Lewis base since, the lone pair of electrons on the nitrogen atom can be donated to a proton:
H+ + :NH3 → [H←:NH3]+
Ag + + 2 NH3 → [H3N: → Ag ← :NH3]+
Lewis acid → Lewis base → Acid-base adduct
Conditions to be a Lewis Acid:

(i) Compounds whose central atoms have an incomplete octet e.g. BF3, AlCl3, GaCl3 etc.
(ii) Compounds in which the central atom have empty d-orbitals and may acquire more than an octet of
valence electrons.e.g.
SiF4 + 2F − → SiF62–
Other examples are : PF3, SF4, SeF4, TeCl4.
(iii) All simple cations : Na+, Ag+, Cu2+, Al3+, Fe3+ , Mg2+, Ca2+ etc.
Conditions to be a Lewis Base:

− −
(a) All simple negative ions e.g. Cl , F , O −2 , SO4–2 etc.
(b) Molecules with unshared pair of electrons: H2O, NH3 etc.
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(c) Multiple bonded compounds which form co-ordination compounds with transition-metals,e.g., CO,
NO, ethylene, acetylene etc.
5. Amphiprotic species: Water can either gain or lose a proton and thus can behave as an acid as well
as a base. Such species are called amphiprotic species. Similarly many other molecules and ions can
either gain or lose a proton.
Examples:
Acid Base Acid Base
–
HS– + OH– H2O + S2
HBr + HS– H2S + Br–
HSO4– + OH– H2O + SO42–

HClO4 + HSO4– H2SO4 + ClO4–
The oxides and hydroxides of metals near the boundary between metals and non-metals are amphiprotic
and can react either as acids or as bases.
8.1 Hard and Soft Acids and Bases (HSAB Principle)

Hardness is measured as the property of retaining valence electrons very strongly. Lewis acids and bases can
be classified as hard and soft acids and bases.Hard Acid is that in which the atom, which is accepting
electrons, is smaller in size and has a high positive charge. Soft acid is that in which the atom, which is
accepting electrons, is bigger in size, has low positive charge and the electrons in it can be easily
polarised.Hard Base is that in which the electron donating atom is small and has high electronegativity e.g.
F-, NH3, H2O, OH − etc. Soft Base is that in which the electron donating atom is bigger and has low
electronegativity e.g. I − , PH3, (CH3)3P etc. A hard acid prefer to bind to hard bases to form ionic bond and the
soft acids prefer to bind to soft bases to form mainly covalent bonds.
8.2 Factors Responsible for Influencing the Acidic and Basic Strength
The factors responsible for influencing the acidity of an organic compound, H–X are:
1. The strength of the H–X bond
2. The electronegativity of X
3. Factors stabilizing X– as compared to HX.
4. The nature of the solvent.
The most important factors among all is (3). These factors are used in tandem to predict the order of acidic
strength for organic acids.
(i) Hydrocarbons: Among hydrocarbons, acidic strength increases with increase in the % 's' character.
This is because, higher the 's' character, higher is the effective electro negativity of carbon atom. As a
result, electrons are closer to the nucleus of carbon and moved farther away from H. So H can be easily
removed as H+.Therefore, the order of acidic strength is CH3 - CH3 < CH2 = CH2 < CH ≡ CH.
(ii) Alcohols: Alcohols are more acidic than CH4 because oxygen is more electronegative than carbon
and consequently O–H bond easily give H+ than C–H bond. Therefore, the order of acidic strength is
H3C – H < CH3, O, H.If one has to predict the order of acidic strength of ethanol, isopropanol and
tertiary butanol, one can proceed as
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Me Me
δ– 2δ– 3δ–
Me CH2 O H CH O H C O H
Me Me
Me
As alkyl groups (methyl group) have a +I effect, the electron density at the oxygen atom will increase. More
the number of alkyl groups, more will be the intensity of negative charge on oxygen. The greater the negative
charge on the oxygen atom, the closer is the electron pair in the O–H bond driven to the hydrogen atom and
consequently separation of a proton becomes increasingly difficult. Thus, the acidic strength of given alcohols
will be in the order
Ethanol > isopropanol > t–butanol
Example 8: Out of ethanol and trifluoro ethanol, which is more acidic?

Solution : As the methyl group is weakly +I while the –CF3 group is strongly –I. Thus, due to –I effect of
–CF3 group, the electron pair in O–H bond will be drawn in towards the oxygen atom, thereby facilitating the
release of the hydrogen as a proton.
(iii) Phenols and substituted phenols: Phenols are stronger acid than alcohols. This is attributed to the
fact that in phenoxide (anion obtained by the loss of proton from phenol), there is possibility of the
delocalization of its negative charge through interaction with the π orbitals of the aromatic nucleus while
alkoxide cannot be stabilized by such effect. Thus pentoxide is a weaker base than alkoxide.
Consequently, the phenol would be stronger acid than alcohol.
PhOH PhO– + H+
phenoxide
O O O O O
phenoxide
ion
Delocalization also occurs in the undissociated phenol but as it involves charge separation, it is less effective
than in the phenoxide. Thus, phenoxide shows some reluctance to take up proton and the equilibrium lies to
the right, indicating greater stabilization of phenoxide and more acidity of phenols with respect to alcohols.
Phenols are less acidic than carboxylic acids due to the fact that delocalozation of the negative charge in the
carboxylate anion involves structures of identical energy content (as the negative charge resides on more
electronegative atom, oxygen) while in pentoxide, the negative charge also resides on the less
electronegative atom (carbon) making these structures of high energy content with respect to those structures
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in which the negative charge is on oxygen. Thus, the relative stabilization of the carboxylate with respect to
the undissociated carboxylic acid is more effective than the relative stabilization of phenoxide w.r.t. to
undissociated phenol. Thus, carboxylate is a weaker base than phenoxide, making the corresponding
carboxylic acid, a stronger acid than phenol.
R–CO2H RCO2–+H+
carboxylate ion
The presence of electron– with drawing groups in phenol increases its acidity while the presence of electron
releasing groups decreases the acidity of phenol.
Now, let us compare the acidic strength of o– , m– and p– nitrophenols. The corresponding phenoxide ions
obtained from the three nitrophenols would be stabilized by delocalization as
O– O O O O O
NO2 NO2 N N
O O
o–nitrophenoxide
O O– O– O
N N
O O
O– O O O O–
NO2 NO2 NO2 NO2 NO2
m–nitrophenoxide
O– O O O O O–
NO2 NO2 N N N N
p–nitrophenoxide O O O O O O O O
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From the structures of phenoxide ions, it is evident that o– and p– nitrophenoxides are more extensively
stabilized with respect to m–nitro phenoxide (as additional contributing structure is obtained by the dispersal
of negative charge over oxygen atom of NO2 group also in o– and p–nitrophenoxide but not in
m–nitrophenoxide). Thus corresponding o– and p–nitrophenols are much stronger acids than
m–nitrophenol. Out of o– and p–nitrophenols, p–nitrophenol is slightly stronger than o–isomer as o–isomer is
bit stabilized by intramolecular hydrogen bonding, thus having a decreased tendency to release proton.
O O
N H
The order of acidic strength of the nitrophenols is
p–nitrophenol > o–nitrophenol > m–nitrophenol
(iv) Aliphatic carboxylic acids: The aliphatic carboxylic acids are much stronger acids than alcohols and
even phenols. This is due to the fact that the carboxylate ion which is obtained by the loss of proton from
carboxylic acid is relatively more stabilized by delocalization than the penoxide and alkoxide ions with
respect to the their undissociated molecules.
R – C – OH R – C– O– +H+
O O
The presence of electron with drawing substituents in simple aliphatic acids increases their acidity while the
electron releasing substituents have reverse effect. For instance, let us compare the acidic strength of
fluoroacetic acid and acetic acid.
CH3 – C – OH CH3 – C – O– +H+
O O
F – CH2 – C – OH F CH2 C – O– +H+
O O
The fluoro acetate ion is stabilized more due to strong –I effect of fluorine, with respect to acetate ion. Hence,
fluro acetate ion is less basic than acetate ion, thereby making fluoroacetic acid stronger than acetic acid.
If there is a doubly bonded carbon atom adjacent to the carboxyl group, the acid strength is increased. This
will be evident if we compare the acid strength of propanoic acid and propenoic (acrylic) acid.
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O
α
CH2 = CH – CO 2H CH2 = CH – C +H+
O–
O
α
CH3 = CH2 – CO2H CH3 – CH2 – C +H+
O–
As we know that unsaturated α −carbon atom in propionate ion is sp2 hybridized, which means that electrons
are drawn closer to the carbon nucleus than in a saturated, sp3 hybridized α −carbon atom, due to greater s
contribution in the sp2 hybrid orbital. The result is that sp2 hybridized carbon atoms are less electron donating
than saturated sp3 hybridized ones. Thus, propionate ion will be comparatively less stabilized than prepe
noate ion, thereby making propanoic acid stronger than propenoic acid (but propenoic will still be weaker
than mechanic acid).
If there is a triple bonded carbon atom adjacent to carboxyl group, the acid strength is more with respect to
the presence of a doubly bonded carbon atom adjacent to –CO2H group. This is attributed to the fact that sp
hybridized carbon atoms are less electron– releasing than sp2 hybridized carbon atoms.
We can explain very strong acidic character of maleic acid than fumaric acid. If one proton is removed from each
of the acids, the corresponding ions are formed. The maleate ion can be stabilized by chelation because hydrogen
and oxygen are very near to each other, on the other hand fumarate ion can not be stabilized by chelation
because hydrogen and oxygen are on the opposite sides, hence the formation of fumarate ion does not take
place. This explains why maleic acid is a stronger acid than its isomer fumaric acid.
O
H COOH H C O–
C C
H
C C
O
H COOH H C
O
(Meleic acid) (Maleate ion)
(Chelation possible)
H COOH H COO–
C C
C C
COOH H HOOC H
(Fumaric acid) Fumarate ion (Chelation not possible)
Example 9: Compare the acidic strength of the following

(i) CH3COOH, CH3CH2COOH
(ii) CH3CH2COOH, CH2 = CHCOOH, HC ≡ C–COOH.
(iii) CH3 COOH, I–CH2 COOH, Br–CH2–COOH, F–CH2–COOH.
(iv) Cl2CHCOOH, CCl3COOH
(v) CH3(CH2)2CO2H,ClCH2(CH2)2CO2H,CH3CH(Cl)CH2CO2H,CH3CH2CH(Cl)CO2H
(vi) CH3COOH, C6H5COOH
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Solution : (i) In simple aliphatic acids, more the number of CH3 added, less is the acidic strength. This is due
to the +I (inductive) effect of CH3. This effect of adding CH3 decreases with increase in distance between CH3
added to the substituent, which releases H + .
Therefore the order of acidic strength is CH3–COOH > CH3–CH2–COOH
(ii) Increase in 's' character increases acidic strength of carboxylic acids.
Therefore the order of acidic strength is
CH3CH2COOH < CH2 = CHCOOH < HC ≡ C–COOH.
(iii) As the –I effect of the group increases, acidic strength increases
CH3 COOH < I–CH2 COOH < Br–CH2–COOH < F–CH2–COOH.
(iv) Increase in number of electron withdrawing substituents into simple aliphatic acids increases acidic
strength.
Therefore the order of acidic strength is Cl2CHCOOH < CCl3COOH
(v) If Cl is placed nearer to COOH group, more is acidic strength.
CH3(CH2)2CO2H < ClCH2(CH2)2CO2H < CH3CH(Cl)CH2CO2H < CH3CH2CH(Cl)CO2H
(vi) Benzoic acid is more acidic than acetic acid because benzoate anion shows/has more resonance.
Therefore the order of acidic strength is CH3COOH < C6H5COOH.
(v) Aromatic carboxylic acids: Benzoic acid is a stronger acid than its saturated analogue cyclohexane
carboxylic acid. This is due to the fact that phenyl group is less electron–donating (like a double bond)
as compared to saturated carbon atom towards the carboxyl group, as the carbon atom to which
–CO2H group is attached is sp2 hybridized in benzoic acid.
O O
H–C H–C
O–H O–H
⊕
⊕
O O– O–
C C ⊕ C
O–H OH OH
As it is evident from the above structures that the lone pair on O atom of the OH group in formic acid
undergoes delocalization with the CO group, thereby generating a positive charge center on O atom
which destabilize the O–H bond by withdrawing electron density from it. This consequently result in
easy release of proton. While in benzoic acid, due to +R effect of phenyl group, the lone pair in O atom
of the O–H group is prevented from entering into resonance with CO group to a large extent. This result
in a smaller (partial) positive charge on the O atom of the O–H group in benzoic acid with respect to
formic acid (the O atom of O–H group has full fledge positive charge), so the release of proton becomes
difficult in benzoic acid than formic acid.
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Now let us consider substituted benzoic acids. At this point, we will consider the effect of substituents from m –
and p – position only. First let us take methyl substituted benzoic acids. As the methyl group has +I effect, so
the net result will be to increase the +R effect in the m– or p– tolyl group. Since, the inductive effect decreases
with distance, so the +I effect of CH3 from para position would be less than the +I effect of CH3 group from
meta position. Thus, the electron density in the O–H bond of m–methyl benzoic acid would be greater than
that in p–methyl benzoic acid. Accordingly, the p–isomer should be more acidic than the m–isomer. But in
real practice, the order is reverse. Actually, we have ignored the hyperconjugation effect of CH3 group. Due
to hyper conjugation effect of CH3 in p isomer, the electron density in the O–H bond would be increased
greatly with respect to that in m isomer.
O O–H O O–H O O–H
C C C
H H+ H+ etc.
C–H C–H C–H
H H H
C C C
etc.
H–C–H H–C–H H – C – H+
H H H
Thus, the release of proton facilitated easily in m–isomer than in p–isomer.
Secondly, let us take intro substituted benzoic acids. As the –NO2 group exerts –I and –R effect (both
reinforming each other), the electron–density from the O–H bond would be withdrawn, thus destabilizing the
O–H bond and making m– and p–nitro benzoic acids stronger than benzoic acid.
As it is clear that –NO2 group exerts its electron withdrawing resonance effect from the p–position and not
from m–position, thus withdrawal of electron density from the O–H bond is greater in p–intro benzoic acid
than m–intro benzoic acid. Thus, p–isomer is stronger acid than m intro benzoic acid.
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Thirdly, we compare the acid strength of m– and p–methoxy benzoic acid. OMe group exerts –I and +R effects.
The electron–releasing resonance effect (+R) is operative in p– methoxy benzoic acid and not in m–methoxy
benzoic acid while –I effect is operative in both the isomers. Thus, the electron density is greatly increased in the
O–H bond in p– isomer than in m– isomer, thereby making m–isomer stronger acid than p–isomer.
O O–H
OMe
C C C
etc.
⊕ ⊕
OMe OMe OMe
There is a special effect shown by o–substituents called ortho–effect. It has been observed that irrespective of the
nature of the group present at ortho position in benzoic acid, nearly all o–substituted benzoic acids are stronger
than benzoic acid. As we have seen benzoic acid is a resonance hybrid and so the carboxyl group is coplanar with
the ring. Introduction of any o–substituent tends to prevent this coplanarity. Thus, resonance is diminished (or
prevented) and so the oxygen atom of the O–H group has a greater positive charge, resulting in increased acid
strength. Thus, it follows that greater the steric inhibition of resonance, the stronger is the acid.
o–hydroxy benzoic acid (salicylic acid) is far stronger than the corresponding m– and p– isomers. Steric
inhibition of resonance can not explain this very large increase, since the corresponding methoxy benzoic
acids all have similar strengths. The explanation here is the presence of intra molecular hydrogen bonding.
Hydrogen of the –OH group can form a hydrogen bond with the carboxyl group whereas the Me of OMe
cannot. Thus the carboxylate ion of o–hydroxy benzoic acid is stabilized by intramolecular hydrogen bonding
while that of m– and p–isomer is not, making o–hydroxy benzoic acid stronger than the corresponding
m–and p–isomers.
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8.3 Basic Strength of Organic Bases

Strength of bases is related to the ease of accepting a proton which inturn depends on the availability of
electron pair on the nitrogen atom (or some other basic atom). More is the availability of electron pair, more
easily the proton will be accepted and more will be the basic strength.
8.4 Aliphatic Bases

As increasing strength in nitrogenous bases is related to the readiness with which they take up protons and
which inturn depends on the availability of the unshared electron pair on nitrogen, we expect an increase in
basic strength on going from NH3→RNH2 →R2NH→R3N, due to the increasing inductive effect of successive
alkyl groups making the nitrogen atom more electron rich. But in actual practice the order of basic strength of
amines is
NH3 < Me3N < MeNH2 < Me2NH
pKa's 9.25 9.80 10.64 10.77
NH3 < EtNH2 < Et3N < Et2NH
and 9.25 10.67 10.88 10.93
It can 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. However, the introduction of
a third alkyl group to yield a tertiary amine, actually decreases the basic strength. 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 the 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 extensive solvation via hydrogen bonding between protonated amines and water.
H2O......H H2O......H H2O......H
⊕ ⊕ ⊕
R – N – H......OH2 > R–N –R> R–N –R
H2O......H H2O......H H2O......R

Decreasing stabilization by solving
Thus on going along the series, NH3 →RNH2→R2NH→R3N, the inductive effect will tend to increase the
basicity but progressively less stabilization of the cation by hydration will tend to decrease the basicity. The
net 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 assumed to be the right
explanation, no such changeover should be observed if measurements of basicity are made in a solvent in
which hydrogen bonding cannot take place. This is indeed found to be true. In chlorobenzene, the order of
basicity of the butylamines is BuNH2 < Bu2NH < Bu3N while their basic strength in water follows the order
Bu3N < BuNH2 < Bu2NH.
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Tetraalkylammonium salts, e.g. R4N⊕I − on treatment with moist silver oxide (AgOH) to yield basic solutions
comparable in strength with the mineral alkalis. This is readily understandable as R4N⊕ –OH formed is
completely ionized to give R4N+ and free OH − . The effect of introducing electron withdrawing groups, e.g. Cl,
NO2, close to a basic center decreases the basicity, due to their electron withdrawing inductive effect. Thus
the amine tris (triflora methyl) amine is found to be virtually non basic due to the presence of three powerfully
electron withdrawing CF3 groups. F3C
F3C N
F3C
The amides are also found to be only very weakly basic in water [pKa for ethanamide(acetamide) is ≈0.5],
because of the –I and –R effect of RCO group which makes the electron pair very slightly available on
nitrogen atom. O O–
⊕
R – C –– NH2 R – C = NH2
If two C = O groups are present the resultant imides often become sufficiently acidic to form alkali metal salts.
For example, benzene –1,2– dicarboximide is not basic but is acidic in nature because of the presence of two
electron-withdrawing CO groups.
O Oδ–
H OH– δ–
N N
δ–
O O
8.5 Aromatic Bases

Aniline is a weaker base than ammonia or cyclohexylamine. It is because of the fact that the electron pair on
nitrogen is involved in delocalization, making it less available for donation.
NH2
NH3
cycloheyxylamine ammonia
⊕ ⊕ ⊕
NH2 NH2 NH2 NH2 NH2
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If aniline accepts a proton, the anilinium cation formed cannot be stabilized by delocalization as the electron
pair on nitrogen is no longer available. Thus, it is 'energitically unprofitable' for aniline to take up a proton.
Thus it functions as a base with utmost reluctance.
⊕
NH3
Diphenylamine is even a weaker base than aniline due to the presence of another phenyl group
NH
and triphenylamine (Ph3N) is not basic at all by ordinary standards. Introduction of alkyl group (like Me) on
the nitrogen atom of aniline results in small increase in the basic strength.
C6H5NH2 < C6H5NHMe < C6H5NMe2
Unlike such introduction in aliphatic amines, this small increase in basic strength is progressive, indicating that
cation stabilization through hydrogen–bonded solvation, here has less influence on the overall effect. Let us
compare the basic strengths of o–, m– and p–nitroanilines. The electron withdrawing NO2 group exerts its –R
effect from o– and p–positions while its –I effect from all p–positions while its –I effect from all positions.
⊕ ⊕
O NH2 O NH2 O NH2
O=N O=N –O = N
so on
⊕ ⊕ ⊕
NH2 NH2 NH2 NH2
so on
N N N N
O O O O O O O– O
Since, the electron pair on nitrogen in o– and p–nitroanilines is delocalized extensively by –I and –R effect
combindly, so they are less basic than m–nitroaniline in which only –I effect operates. Out of o– and p–
isomers, ortho is less basic than para because –I effect of NO2 from ortho position is stronger than from para
position. Thus the basic strength of nitro anilines follow the order
m–nitroaniline > p–nitroaniline > o–nitroaniline
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Now if we take o–, m– and p–methoxy anilines. The OMe group exerts –I and +R effects (only from ortho
and para position).
As OMe group exerts +R from ortho and para position, so o– and p– methoxy anilines are stronger base than
m methoxy aniline, in which OMe exerts only –I effect.
NH2 NH2 NH2 NH2

⊕ ⊕ ⊕
OMe OMe OMe OMe
etc.
NH2
OMe
NH2 NH2 NH2 NH2
etc.
OMe ⊕ OMe ⊕ OMe ⊕ OMe
–I effect of OMe from ortho position is stronger than from para position, thus decreasing the electron density
on nitrogen in o–methoxy aniline than in p–methoxy aniline. Thus, the order of basic strength would be
p–methoxyaniline > o–methoxyaniline > m–methoxyaniline
Example 10 : Arrange the following compounds in the inceasing order of basicity?
N N N N
H H H
(I) (II) (III) (IV)
Solution : In II, III and IV the lone pair is present in sp3 orbital but in II, the electron pair on nitrogen is
involved in delocalization making it least basic of all. In I, the unshared electron pair is present in sp2 orbital
which makes it less basic than III and IV and IV is less basic than III due to –I effect of oxygen atom. Thus, the
increasing order of basic strength would be
II < I < IV < III.
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Exercise
4. Explain the following order of acid strength -
Long Answer Type Questions Cl3C.COOH > Cl2CHCOOH >
1. What do you understand by the term "hybrid Cl CH2COOH > CH3COOH [Meerut 2008]
orbital"? Give geometry of the following:
5. What do you understand by the terms resonance
(i) sp3 (ii) sp2 and resonance energy?
(iii) sp [Bund. 2008; Kanpur 2011] OR
2. On the basis of orbital theory, explain the structure
What do you mean by hydrogen bonding? Discuss
of the following:
intermolecular and intramolecular hydrogen
(i) Ethane (ii) Ethylene bonding. [Agra 2008]
(iii) Ethyne (Acetylene) [Bund. 2009] 6. An organic compound contains C, H and O its
3. Write short notes on the following : vapour density is 30.0.30 gm of this compounds on
(i) Hydrogen bonding combustion yielded 0.44 gm of CO2 and 0.18 gm of
H2O. Find out the molecular formula of the
(ii) Hyperconjugation
compound. [Kanpur 2009]
(iii) Resonance energy
7. An organic compound A contains C = 37.2%, H =
(iv) Inductive effect [Hazaribagh 2010] 7.7% and Cl = 55.03%. This on treatment with
4. (i) In terms of hybridization of carbon atom KCN gives B. A on treatment with alcoholic
discuss briefly the shapes of methane, ammonia under pressure forms C, D, E and F. What
ethane and ethyne. are A, B, C, D, E and F? Give structure.
[Kanpur 2010]
(ii) Write short notes on any two of the following :
8. Write short note on hyperconjugation.
(a) Inclusion compounds [Avadh 2008]
(b) Clathrates 9. How resonance reduces the besicity and increases
(c) Picrates. [Hazaribagh 2011] the acidity of the molecule? Explain with suitable
5. Discuss the rules for deciding the relative stabilities example. [Kashi 2010]
of various canonical forms. 10. What is hyperconjugation? How is it used to
determine stability of carbocations and alkenes?
Short Answer Type Questions [Kashi 2011; Hazaribagh 2008]
1. Explain hyperconjugation and on its basis stability 11. What is a charge transfer complex? Give an
of alkenes. example. [Lko. 2011]
[Bund. 2010; Meerut 2010,11,12; Kanpur 2011] 12. Define aromaticity. [Lko. 2011]
2. Write short note on the following 13. Explain that inductive effect leads to the
(i) Hybridisation development of partial charges while the
(ii) δ bonds π [Meerut 2008]
electromeric effect causes full positive and negative
charges. [Rohd. 2009,10]
3. Write the short note of the following :
14. Explain inter - and intramolecular hydrogen
(i) Inductive effect
bonds. [Rohd. 2011]
(ii) Resonance
[Meerut 2008,09,10; Agra 2008; Lko. 2008] 15. Describe bond length and bond energy.
[Rohd. 2012]
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16. Butanol-1 has higher boiling point than diethyl 16. Explain the following :
ether, although both have same molecular formula. (i) Chloroacetic acid is stronger acid than acetic
Explain why? [D.D.U. 2008] acid
17. Why -OH group of carboxylic acid is more acidic (ii) Dimethyl amine is stronger base than
than the -OH group of an alcohol? [D.D.U. 2010] trimethyl amine. [Kanpur 2008]
18. The boiling point of butanol-1 is higher than that of 17. Write structural formulae of the following :
ethoxyethane, although both have same molecular
(i) Iso–octane
weight. Why? [D.D.U. 2010]
(ii) Dimethyl acetylene
19. Why chloroacetic acid is stronger acid than acetic
(iii) Trimethyl carbinol
acid? [D.D.U, 2011]
(iv) Ethylmethanonate [Kanpur 2008]
20. Explain the acidic nature of hydrogen in acetylene.
[D.D.U. 2011; Hazaribagh 2008,11] 18. Write short notes on the following :
(i) Hyperconjugation
Very Short Answer Type Questions (ii) Resonance [Kanpur 2008]
1. Explain why formic acid is more acidic than acetic 19. Explain mesomeric effect. [Kanpur 2009]
acid. [Bund. 2008; Kashi 2010]
20. Which is more basic and why?
2. Write short notes on inductive effect.
CH3NH2 and (CH3)2NH [Kanpur 2010]
[Bund 2008; Meerut 2009, 11, Kanpur 2010,11]
21. Write short notes on the following :
3. Explain why chloroacetic acid is more acidic than
acetic acid. [Bund. 2009] (i) sp3 hybridization
4. Explain why methyl amine is more basic than (ii) sp hybridization [Kanpur 2010]
ammonia? [Bund. 2010] 22. Why monochloro acetic acid is stronger than acetic
5. Explain why ethyl alcohol is readily soluble in acid? [Avadh 2010]
water? [Bund. 2010] 23. Boiling point of 1-Butanol is greater than diethyl
6. Explain charge transfer complexes. [Bund. 2010] ether although both have same molecular
formula.Why? [Avadh 2010]
7. Explain H-bond and its types.
[Bund. 2010; Meerut 2010,11] 24. Write short note on hyperconjugation.
8. Define bond energy. [Kashi 2008]
[Meerut 2009]
25. Draw all the resonating structures of nitro benzene.
9. What is steric effect ? [Meerut 2009]
[Kashi 2010]
10. Why acetic acid is a stronger acid than propionic
26. Why o-nitrophenol is less soluble in water than in
acid? [Meerut 2010]
p-nitrophenol? [Kashi 2010]
11. Why ethyl alcohol (mol wt.46) has higher boiling
27. Write hybridization state of each carbon atom of
point than diethyl ether (mol.wt.74). [Meerut 2010]
following molecule,
12. What is resonance?
CH3– CH = C = CH2 [Kashi 2011]
[Meerut 2011; Kanpur 2009,10,11]
28. Define quinol clathrates. [Lko. 2008]
13. What is sp hybridization? [Agra 2008]
29. What are charge transfer complexes ? [Lko. 2008]
14. Give an example of intermolecular and
intramolecular hydrogen bonding. [Kanpur 2008] 30. Draw the orbital picture of ethane. [Lko. 2008]
15. HF and HI have higher boiling point than HCl, 31. sp hybridized carbon is highly electronegative than
explain why? [Kanpur 2008] sp 2 and sp 3 . Why? [Lko. 2009]
32. Explain inclusion compounds. [Lko. 2010]
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33. Why boiling point of p-nitrophenol is more than 5. When the hybridization state of carbon atom
ortho-nitrophenol? [Lko. 2010] changes from sp3 to sp2 and finally to sp, the angle
34. Chloroacetic acid is stronger as compared to acetic between the hybridized orbitals
acid. Give reason. [Rohd. 2009,10] (a) Decreases gradually
35. Delocalisation leads stability. Explain with suitable (b) Increases progressively
example. [Rohd. 2013] (c) Is not affected
36. Write short notes on the bond dissociation energy (d) None of these
and bond energy. [Rohd. 2013] 6. The Cl–C–Cl angle in 1,1,2,2–tetrachloromethane
37. Formic acid is stronger than acetic acid. Explain and tetrachloromethane respectively will be about:
why? [D.D.U. 2008] (a) 120° and 109.5°
38. Giving reason, arrange (b) 90° and 109.5°
NH3 , CH3 − NH2 (CH3 )2 NH and (CH3 )2 N
(c) 109.5° and 90°
into their decreasing order of basicties. [D.D.U. 2008]
(d) 109.5° and 120°
39. Identify the compounds from the following which
7. Number of π −electrons in naphthalene is:
has sp hybrid orbital.
(a) 10 (b) 5
HC = CH, C2H6, C6H6 [Hazaribagh 2008]
(c) 3 (d) 6
40. Identify the compounds from the following which
has sp 3 hybrid orbital : 8. Number of tertiary carbon atoms in:
CH3 H CH3 H
CH3 − CH3 ≡ CH,CH2 = CH2
[Hazaribagh 2009]
H – C — C — C — C – CH3
Objective Type Questions CH3 CH3 CH3 CH3
(a) 4 (b) 3
Multiple Choice Questions
(c) 2 (d) 1
1. Molecule in which the distance between two
adjacent carbon atoms is longest is: 9. In which of the following organic compounds all the
carbon atoms do not lie in one plane:
(a) Ethane (b) Ethene
(a) Toluene (b) 2-butene
(c) Ethyne (d) Benzene
(c) Neopentane (d) Propene
2. Number of π − bonds in the following compound:
CH3C ≡ C–CN 10. The ratio of σ and π bonds in benzene is:
(a) 1 (b) 2 (a) 2 (b) 3
(c) 3 (d) 4 (c) 4 (d) 1

3. The bond between carbon atoms 1 and 2 in 11. Consider the following compound:
1 2 CH2=CH–CH=CH2
N ≡ C − CH = CH2 involves the hybridized carbons: 1 2 3 4
(a) sp2 and sp2 (b) sp3 and sp carbon-carbon bond length between C2 and C3 will
(c) sp and sp2 (d) sp and sp3 be:
4. The compound in which all carbons use only sp3 (a) 1.54Å
hybrid orbitals for bond formation:
(b) 1.3 Å
(a) HCOOH (b) (H2N)2CO
(c) Less than 1.54Å and greater than 1.33Å
(c) (CH3)3COH (d) (CH3)3C–CHO
(d) 1.21 Å
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12. Consider the following three halides: 15. Which one of the following is most basic:
(1) CH3-CH2-Cl NH2 NH2
(2) CH2=CH-Cl
(3) C6H5-Cl CH3
(a) (b)
Arrange C-Cl bond length of these compounds in
decreasing order:
(a) 1>2>3 (b) 1 > 3 > 2 NH2
NH2
(c) 3>2>1 (d) 2 > 3 > 1
CH3
13. Consider the following compounds:
CH3 (d)
NH2 NH2 NH2 NH2 (c)
CH3 CH3
16. Among the following the compound having the

most acidic alpha - hydrogen is :
NO2 CN CH3 (a) CH3CHO
(1) (2) (3) (4) (b) CH3COCH3
(c) CH3 − C − CH2CHO
Arrange these compounds in decreasing order of
||
their basicity:
O
(a) 1>2>3>4
(d) CH3–CO–CH2–CO2CH3
(b) 2>3>1>4
17. Allyl isocyanide has:
(c) 4>1>3>2
(a) 9 σ bonds and 4 π-bonds
(d) 4>1>2>3
(b) 9 σ bonds, 3 π-bonds and 2-non-bonding
14. Consider the following compounds: electrons
O
(c) 8 σ bonds and 5 π-bonds
(d) 8 σ bonds, 3 π-bonds and 4– non-bonding
electrons
N N N N
18. What is the correct increasing order of bond lengths
H H H of the bonds indicated as I, II, III and IV in following
(1) (2) (3) (4) compound:
II III IV
Order of basicity of these compounds in decreasing
order is: I
(a) 4>1>2>3
(b) 1>3>4>2
(c) 2>3>4>1 (a) I < II < III < IV
(d) 1>3>2>4 (b) I < III < IV < I

(c) IV < II < III < I
(d) IV < I < II < III
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19. In which of the following structures the pair of (c) δ– δ+

starred carbon atoms do not lie in the same plane CH2 =CH − CH = O
(d) δ– δ+
(a) * CH2 =CH − CH = O
H3C CH3
C C 24. The compound which has one isopropyl group is :
CH3—H2*C H (a) 2,2,3,3 -tetramethyl pentane
(b) * (b) 2,2 - dimethyl pentane

CH 3
(c) 2,2,3 - trimethyl pentane
(d) 2-methyl pentane
25. No bond resonance is:
* (a) Inductive effect
(c) H
CH *
C (b) Mesomeric effect
H (c) Steric effect
(d) Hyperconjugation [Bund. 2008]
*
26. Which do you expect has higher boiling point?
(d) H3C *
CH2–CH (a) HF(B) (b) HCl
3
C C (c) HBr (d) HI [Bund. 2008]
H3C H 27. Which of the following is more acidic?

* (a) CH3COOH
20. Which one of the following has the smallest heat of
hydrogenation per mole ? (b) ClCH2COOH
(c) CH2CHCOOH
(a) 1– butene
(d) Cl3CCOOH [Bund. 2008]
(b) trans 2– butene
28. In benzene, C atom exhibits the hybridization:
(c) cis –2– butene
(a) sp (b) sp2
(d) 1, 3– butadiene
(c) sp 3 (d) sp3d [Bund. 2008]
21. Which is the strongest carboxylic acid among the
following ? 29. In which of the following compounds
carbon-carbon bond is shortest in length?
(a) Cl3CCO2H
(a) HC = CH
(b) Br3CCO2H
(b) H2C = CH2
(c) F3CCO2H
(c) H3C - C ≡ CH
(d) Cl2CHCO2H
(d) H3C - C = CH2 [Bund. 2008]
22. The hybridization of carbon atoms in C–C single
bond of vinyl acetylene: 30. Which of the following is more basic
(a) NH3 (b) CH3NH2
(CH2 = CH – C ≡ CH) is :
(c) (CH3)2NH (d) (CH3)3N [Kanpur 2009]
(a) sp3-sp3 (b) sp2-sp
31. The + I effect is shown by
(c) sp-sp2 (d) sp3-sp
(a) –CH3 (b) –OH
23. Polarization of electrons in acrolein may be written as:
(c) –F (d) –C6H5 [Rohd. 2009,10]
(a) δ– δ+
CH2 = CH − CH = O 32. In a free radical the carbon atom carrying unpaired
(b) δ –
δ+ electron is
CH2 = CH − CH = O (a) sp hybridized
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(b) sp2 hybridized 11. In allenes the central carbon atom is ………
(c) sp hybridized
3 hybridized.
(d) dsp2 hybridized [Rohd. 2010]

True/False
33. In which of the following compounds delocalised
1. 3–cyclopentadiene is highly acidic in character.
bonding is not possible ?
2. Melting point of symmetrical molecule is more than
(a) 1, 4 – pentadiene
the unsymmetrical molecule.
(b) 1,3 – butadiene
3. Chloroacetic acid is more acidic than bromoacetic
(c) 1,3,5 – hexatriene acid.
(d) Benzene [Rohd. 2010] 4. Tricyanomethane is as strong acid as a mineral acid.
34. The +I effect is shown by
(a) –C2H5 (b) –OH 5. Delocalisation of lone pair of electrons decreases
(c) F (d) –C6H5 basicity of the compound.
35. Indicate the type of hybridization of the asterisked 6. n-hexanol does not dissolve in water whereas
carbon : ethanol dissolves.
7. All the carbon atoms in 2-butene lie in one plane.
H2C = C* = CH2
8. Tropylium cation maintains its aromatic character
(a) sp (b) sp2
in all of its resonating structures where as benzyl
(c) sp3 (d) no hybridisation
carbocation loses its aromatic character in some of
[Rohd. 2012]
the canonical forms.
36. The no. of σ and π bonds in 1-Pentene-3-yne are
9. Propene is more acidic than propyne.
(a) 10σ & 2π (b) 10σ & 3π
10. The chlorine atom in vinyl chloride is less reactive
(c) 8σ & 3π (d) 12σ & 3π due to +R effect.
[Rohd. 2012]
11. No bond resonance is termed as inductive effect.
Fill in the Blank

1. Aliphatic secondary amine is ………basic than
tertiary amine in solution.
2. Melting point of fumaric acid is ……… than the
maleic acid.
3. Tropylium cation is ……… stable than benzyl
carbocation.
4. Cyclopentadiene ……… is aromatic.
5. Amides are ……… basic than primary amines.
6. –I group present in a carboxylic acid ……… acidity
of the compound.
7. Pyridine is……… basic than pyrrole.
8. The boiling point of alcohols is ……… than those of
hydrocarbons of comparable molecular masses.
9. All the carbon atoms in 1,3-butadiene are………
hybridized.
10. Dipole moment of vinyl chloride is ……… than the
ethyl chloride.
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Answers
Objective Type Questions

1. (a) 2. (d) 3. (c) 4. (c) 5. (b)
6. (a) 7. (a) 8. (b) 9. (c) 10. (c)
11. (c) 12. (a) 13. (c) 14. (d) 15. (c)
16. (c) 17. (b) 18. (d) 19 (d) 20. (d)
21. (c) 22. (b) 23. (d) 24. (d) 25. (d)
26. (a) 27. (d) 28. (b) 29. (a) 30. (d)
31. (a) 32. (c) 33. (a) 34. (a) 35. (a)
36. (b)
Fill in the Blank

1. more 2. more 3. more
4. anion 5. less 6. decreases
7. more 8. higher 9. sp2
10. less 11. sp
True/False
1. True 2. True 3. True
7. True 8. True 9. False
10. True 11. False

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Hints and Solutions

Long Answer Type Questions
5. Hints: In drawing the canonical forms and deciding about their relative stabilities, following rules are
given for your guidance.
(i) All the canonical forms must be bonafide Lewis structures. For example, none of them may have
a carbon with five bonds.
(ii) All atoms taking part in the resonance must lie in a plane or nearly so. The reason for planarity is
to have maximum overlap of the p-orbitals.
(iii) All canonical forms must have the same number of unpaired electrons. Thus,
CH2 − CH ≡ CH − CH2 is not a valid canonical form for 1,3 butadiene.
(iv) The energy of the hybrid (actual) molecule is lower than that of any canonical form. Obviously
then, delocalization is a stabilizing phenomenon. The difference in energy between the hybrid
and the most stable canonical structure is called resonance energy.
(v) All canonical forms do not contribute equally to the actual molecule. Each form contributes in
proportion to its stability, the most stable form contributing the most.
(vi) Structures with more covalent bonds are generally more stable than those with fewer covalent
bonds.
(vii) Structures with formal charges are less stable than uncharged structures. For charged structures,
the stability is decreased by an increase in charge separation and the structure with two like
charges on adjacent atoms are highly unfavourable.
(viii) Structures that carry a negative charge on a more electronegative atom are more stable than
those in which the charge is on a less electronegative atom. For example,
Structure II is more stable than I. Similarly positive charges are best occupied on atoms of low
electronegativity.
(ix) Those structures in which octet of every atom (except for hydrogen which have duplet) is
complete are more stable than the others with non-complete octets. For example,
⊕ ⊕
R—C O R—C O
III IV
Structure IV is more stable than III.
❍❍❍
UnitO-63
-I
C HAPTER 2
Mechanism of Organic Reactions
1. Fundamental Concepts of Organic Reaction

The stoichiometry of a reaction consists of the chemical formulas and relative molecular proportions of
starting materials and products. Obviously these have a bearing on the mechanism of the reaction, for the
overall reaction course must proceed from starting materials to the products. The stoichiometry of the
reaction may be misleading, however, because the participants in the overall reaction may not be involved
directly in the rate-limiting step.
The discovery of intermediates in the course f a reaction is important because these point to the existence of
distinct stages, the mechanism of each of which must then be determined. The identification of intermediates
that persist only briefly or that are present in only small amounts depends on the availability of powerful,
sensitive, and rapid experimental techniques. For this purpose, a number of specialized instrumental
procedures (including ultraviolet, infrared,magnetic resonance, and mass spectrometry) are widely used to
supplement the more usual chemical and physical methods.
The identification of a new chemical substance formed transiently in a reaction mixture, however, does not
unambiguously imply that substance is an intermediate in the reaction. In many cases a newly found material
is only a temporary repository of the proportion of the reactants and ultimately produces the products by first
reverting to the starting material. The identification of the products of a reaction also helps to define the
reaction course, because the mechanism in question clearly must account for their formation. Mechanistic
theory has been greatly facilitated by the development of powerful methods of separation and purification
based on chromatography (separation of compounds on the basis of their relative degrees of adsorption to
certain solid substances, such as starch or silica) and also by modern methods available for the analysis of
small quantities of materials. These spectroscopic procedures are often used, as is another instrumental
method called polarimetry.
An important consideration with regard to the products of the reaction is whether the reaction is under kinetic
or thermodynamic control. A reaction is said to be kinetically, rather than thermodynamically, controlled
when the products are formed in proportions different from those that would prevail at equilibrium between
the same products under the same conditions. Thermodynamic control leads to the equilibrium ratio of the
products. Often, though not invariably, reactions under kinetic control give a greater amount of the
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thermodynamically less stable of two possible products; if thermodynamic control is then established, the
products shift to their equilibrium proportions, which might give a misleading picture of the reaction course.
Hence, inferences concerning the nature of the transition state can be drawn from the nature of the products
only with a good deal of circumspection.
1.1Reaction Mechanism and Curved Arrow Notation

Chemical reactions are a result of bonding changes. These bonding changes are most easily described by
considering the changes in electron sharing between atoms. For example, if one considers the collision
between two water molecules resulting into the ionization of water and the formation of hydroxide and
hydronium ion.
H
H—O + O H—O +H3O+

H H Hydroxide Hydronium
ion ion
In this reaction, as observed,the oxygen atom of one water molecule collides with a hydrogen atom of the
second water molecule. A lone pair of the oxygen atom becomes the new O-H bond in the hydronium ion.
Because a hydrogen can only be fully bond to one other atom at a time, the old O-H bond is lost. The
electron pair of the old O-H bond becomes a lone pair, sole property of the oxygen atom of hydroxide
ion.This very simplistic step-by-step bookkeeping description of all the bonding and electron changes in a
reaction is called the reaction mechanism. Study, understanding and prediction of reaction mechanisms is at
the very heart of reactions in organic chemistry. Mastering the fundamentals of reaction mechanisms is a
fundamental survival skill for students of organic chemistry. Above, it is observed that several lines of text has
been used to describe the bonding changes in a single step of a reaction mechanism. A reaction mechanism
might have 10-12 steps or more, making such descriptions very cumbersome. A shorthand notation that
summarizes these changes has to be developed. This notation, called curved arrow formalism, provides a
rapid way of drawing bond and electron changes in a given mechanism step. They are also useful to indicate
electron changes between a set of contributing resonance structures.Arrows in chemical drawing have
specific meanings. Just as it is important to learn the structural representation and names of molecules, it is
important to learn the language of arrow formalism in organic chemistry. Different prominent types are
discussed below,
1. Curved arrows are used to show how electrons are moved in resonance structures and in reactions.
Therefore, curved arrows always start at the initial position of electrons and end at their final position. It
is important to note that when a pair of electrons in a polar covalent bond is moved to one of the
bonded atoms, it is moved to the more electronegative atoms.
2. A curve arrow with half a head is called a fishhook. This kind of arrow is used to indicate the movement
of a single electrons.
3. Straight arrows point from reactants to products in chemical reactant equations. Straight arrows with
half-heads are commonly used in pairs to indicate that a reaction is reversible.
4. A double-headed straight arrow (↔) between two structures indicates that they are resonance
structures. Such an arrow does not indicates the occurrence of a chemical reaction.
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So, as stated earlier,each curved arrow with two barbs on the head represents the shift of one electron
pair. The curved arrows shows of Direction of electron flow. The tail shows the electron origin, and always
come from an electron source, usually a lone pair or bonding pair from a σ or π bond. In this representational
mode, the head of the arrow indicates the electron pair destination, either as a new lone pair or a new bond.
If the arrowhead points to another atom, that atom must either have an open octet or have an electron pair
that can be displaced by the incoming electron pair. It is important to remember that electrons never flow
from atoms which are electron-poor to atoms which are electron-rich, so a curved arrow will never point from
an atom with a positive charge to an atom with a negative charge.Some of the most common ways are,
(i) New bond formed to X: X
(ii) Bonding pair becomes lone pair; bond broken:
X
The use of curved arrows for the ionization of water is shown below.
This bonding pair becomes a lone

pair on oxygen of hydroxide ion. This lone pair was on O–H bond.
H H
H—O H—O +
H O H—O
H H
This lone pair becomes The bonding electron pair

the new O–H bond. was a lone pair on oxygen.
Fig.1: Ionisation of water
The tail of the curved arrow on the right hand side starts at the oxygen lone pair, meaning this curved arrow
shows a bonding change for this lone pair. The head of the curved arrow points to the space between the
oxygen and hydrogen atoms, meaning the electron pair ends in that space as a bond between the oxygen
and the hydrogen. The hydrogen that accepts a new bond to oxygen must give up a pair of electrons because
it cannot have more than two valence electrons at a time. Thus, the old O-H bond is being displaced by the
new electron pair from the other oxygen atom. The curved arrow on the left indicates the electron pair that
was the O-H bond becomes a lone pair on the oxygen of the hydroxide ion.
If the arrow starts at a bond between two atoms, then that bond is broken. If the arrow ends between two
atoms, then a new bond is formed between those atoms. If the atoms are already attached through a single
chemical bond, then a double or triple bond results.The process of drawing a curved arrow mechanism is also
commonly called "electron pushing."When drawing curved arrows, the start and stopping points of the
arrows are critical. Things that make no difference are where the arrows curve up or down, or whether they
start or stop at the top or bottom of an atom.
Note also the changes in formal charge that result from the electron changes. If an atom shares a lone pair
that it used to have all to itself then its charge decreases by one, so one can conclude that neutral atom
become +1 charged. If an atom gains a bonding electron pair all to itself as a lone pair then its charge
increases by one unit so that a neutral atom becomes -1charged. The charge is conserved in this mechanism
step. The total charge on the left, which is zero, is the same as the total charge on the right (-1 +1 = 0).
Charge is conserved in all mechanism steps. You should make a habit of checking your work against this
point to minimize errors.
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Lone pairs are often involved in reaction mechanisms, so one must be in the habit of drawing all lone pairs. It
is also important that curved arrows be drawn neatly and precisely, clearly showing the atomic origin of the
electron pair at the tail of the curved arrow and the electron pair destination at the head of the arrow.
Solved Examples
Example 1: Provide the curved arrows for the reaction of hydroxide and hydronium ions to form
two molecules of water.
H
H—O + H—O ⊕ H—O—H

H
Solution : A reasonable approach to an exercise like this is to analyze the bond changes are then draw the
corresponding curved arrows. The oxygen of hydroxide ion has shared a lone electron pair with the
hydrogen of hydronium ion, forming a new O-H bond. Thus one can draw a curved arrow with the tail at the
hydroxide ion lone pair and ending at the hydronium ion hydrogen. This hydrogen atom can only have one
covalent bond at a time, so it must sacrifice the bond to the hydronium ion. One can draw a curved arrow to
show the bonding electron pair between the hydrogen and oxygen of the hydronium ion moving to become
the sole property of the oxygen atom. The oxygen of the hydroxide ion is sharing a pair of electrons that it
had all to itself before, so its formal charge drops by one unit (-1 to neutral). The oxygen of the hydronium
ion gains a lone pair of electrons that is used to share with the hydrogen, so its formal charge decreases by one
unit (neutral to +1).
H
H—O + H—O ⊕ H—O—H

H
Example 2: Draw the product(s) of the following mechanism step based upon the curved
arrows.
H2C CH2 Br Br product(s)??
Solution : The curved arrow that starts at the carbon-carbon bond and ends at the bromine atom indicates
the bond electron pair has shifted to become a carbon-bromine bond. The left-hand carbon of the double
bond has lost an electron pair, so its formal charge becomes one unit more positive (neutral to +1). The
curved arrow on the right indicates that the electron pair of the bromine-bromine bond is shifting to reside
solely on the bromine on the right, resulting in rupture of the bond and formation of bromine with four lone
pairs and a negative charge.
⊕
H2C CH2 Br Br H2C— CH2—Br + Br
Example 3: Provide curved arrows that show how the following mechanism steps might occur.
H
(i) ⊕ O—H
O—H 2H2O
H
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NO2
⊕
(ii) + NO2
⊕
H
(iii) + OCH3 + HOCH3 + Cl
Cl
O O
C C ⊕
(iv) H + NH3 + NH4
H3C O H3C O
O O
(v) H3C S + Cl H3C—Cl + SO2 + Cl
Cl
Solution : (i) The O-H bond of the hydronium ion (H3O+) has been broken. The pair of electrons from this
bond have become a lone pair on oxygen of a water molecule, so one may need a curved arrow starting
at the O-H bond and ending at the oxygen. One lone pair of hydroxide ion (HO − ) has attacked the
hydrogen of the hydronium ion, resulting in a new O-H bond in the second water molecule. One can
indicate this with a curved arrow starting at the hydroxide ion lone pair and ending at the hydrogen of
the hydronium ion. This is an example of a proton transfer, a mechanism step that is quite common in
organic reactions.
H
⊕
O—H + O—H 2H2O
H
(ii) A new bond is formed between the nitronium ion (NO2+) and the carbon of the carbon-carbon double
bond. The bonding electrons come from the carbon-carbon double bond, so one can draw a curved
arrow starting at the π bond portion of the double bond and ending at the nitronium ion. The bottom
carbon of the double bond has lost a pair of electrons that it used to share, so its charge becomes one
unit more positive. This is a key step in the electrophilic aromatic substitution mechanism.
NO2
⊕
+ NO2
⊕
−
(iii) A lone pair on the oxygen atom of the methoxide ion (CH3O ) is now shared with a hydrogen that was
taken from the cyclohexane ring. We indicate this with a curved arrow starting at the oxygen lone pair
and ending at the hydrogen. The pair of electrons that used to be the C-H bond become the π
component of the C=C bond. One can indicate this with a curved arrow starting at the C-H bond and
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ending at the position of the new π bond, in the space between two carbons of the cycloehxane ring.
The electron pair that was the C-Cl bond becomes a lone pair on the departing chloride ion. We indicate
this by drawing a curved arrow starting at the C-Cl bond and ending at the chlorine atom. This is an
example of an E2 reaction.
H
+ OCH3 + HOCH3 Cl
Cl
(iv) The lone pair on the nitrogen atom of ammonia (NH3) attacks the hydrogen of acetic acid (CH3CO2H)
to form a new N-H bond. We indicate this with a curved arrow starting at the nitrogen lone pair and
ending at this hydrogen atom. The hydrogen of acetic acid gives up the pair of electrons that it shares
with the oxygen atom. This pair of electrons becomes the π bond component of the new C=O bond.
We indicate this with a curved arrow starting at the H-O bond and ending between the carbon and
oxygen atoms, the position of the new π bond. The old C=O π bond electron pair is displaced by the
incoming π bond, so the old C=O π electron pair shifts to the oxygen at the top of the structure. One
can indicate this with a curved arrow starting at the π bond and ending at the oxygen atom. This is
another example of a proton transfer reaction.
O O
C C ⊕
H + NH3 + NH4
H3C O H3C O
(v) The chloride ion forms a new bond with the carbon of the methyl group (CH3) by sharing a lone pair.
We indicate this with a curved arrow starting at the chloride ion and ending at the carbon of the methyl
group. The carbon of the methyl group has a full octet to begin with, so it must lose a pair of electrons to
avoid having ten valence electrons. The electron pair of the C-O bond is displaced, becoming the π
component of the new S=O bond. We indicate this with a curved arrow that starts at the C-O bond and
ends at the position of the new S-O π bond between the sulfur and oxygen atoms. The sulfur atom has
gained a pair of electrons that used to be the C-O bond. This new bonding pair displaces the S-Cl
bonding pair and the S-Cl bond is lost. We indicate this with a curved arrow that starts on the S-Cl bond
and ends at the chlorine atom. In this case, it was necessary to reposition of the reactants to make the
curved arrows easier to draw and understand. As such this is frequently necessary. This reaction is a key
stet in the reaction between an alcohol and thianylchloride (SOCl2) to produce a chloroalkane.
O O
Cl H3C S H3C—Cl + SO2 + Cl
Cl
1.2 Formal Charge

Generally, in chemistry, a formal charge (FC) is the charge assigned to an atomin a molecule, assuming that
electrons in a chemical bond are shared equally between atoms, regardless of relative electronegativity.
The formal charge of any atom in a molecule can be calculated by the following equation:
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B
Formal charge=V − N –
2
here V is the number of valence electrons of the atom in ground state; N is the number of non-bonding
valence electrons on this atom in the molecule; and B is the total number of electrons shared in covalent
bonds with other atoms in the molecule. There are two electrons shared per single covalent bond. When
determining the correct Lewis structure or predominant resonance structure for a molecule, the structure is
chosen such that the formal charge (without sign) on each of the atoms is minimized. Formal charge is a test
to determine the efficiency of electron distribution of a molecule. This is significant when drawing structures.
Some of the examples are discussed below:
1. Carbon in methane: FC = 4 - 0 - (8÷2) = 0
2. Nitrogen in NO2 − : FC = 5 - 2 - (6÷2) = 0
3. Single bonded oxygen in NO2 − : FC = 6 - 6 - (2÷2) = -1
4. Double bonded oxygen in NO2 − : FC = 6 - 4 - (4÷2) = 0
An alternative method for assigning charge to an atom taking into account electronegativity is by
oxidation number. Other related concepts are valence, which counts the number of electrons that an
atom uses in bonding, and coordination number, the number of atoms bonded to the atom of interest.
5. Ammonium NH4 + is a cationic species. By using the vertical groups of the atoms on the periodic table it
is possible to determine that each hydrogen contributes 1 electron, the nitrogen contributes 5 valence
electrons, and the charge of +1 means that 1 of the contributed electrons is absent. The final total is 8
total electrons (1 × 4 + 5 –1). Drawing the Lewis structure gives an sp3 (4 bonds) hybridized nitrogen
atom surrounded by hydrogen. There are no lone pairs of electrons left. Thus, using the definition of
formal charge, each hydrogen has a formal charge of zero (1- (0 + ½ × 2)) and the nitrogen has a
formal charge of +1 (5–(0 + ½ × 8)). After adding up all the formal charges throughout the molecule
the result is a total formal charge of +1, consistent with the charge of the molecule given in the first
place.
It is important to note that the total formal charge in a molecule must be as close to zero as possible, with
as few charges on the molecule as possible. To explain the concept, one can consider CO2 as an
example. CO2 is a neutral molecule with 16 total valence electrons. There are three different ways to
draw the Lewis structure
Mode 1: Carbon single bonded to both oxygen atoms (carbon = +2, oxygens = -1 each, total formal
charge = 0)
Mode 2: Carbon single bonded to one oxygen and double bonded to another (carbon = +1, oxygen
double = 0, oxygen single =–1, total formal charge = 0)
Mode 3: Carbon double bonded to both oxygen atoms (carbon = 0, oxygens = 0, total formal charge =0)
Even though all three structures gave us a total charge of zero, the final structure is the superior one
because there are no charges in the molecule at all.
1.3 Comparison of Formal Charge and Oxidation State

The concept of oxidation states constitutes a competing but slightly different 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:
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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 electrons in each covalent bond are assumed to be split exactly evenly between the
two atoms in the bond. It is because of this reason the division by two is performed in the formula used,
B
Formal charge=V − N –
2
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 hence 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
electronegativity. 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
electronegativity 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 modes of
charge distribution.
1.4 Types of Bond Cleavage

Bond cleavage or scission is the splitting of chemical bonds.A covalent bond between two atoms can be
broken in two ways
1. Homolytic cleavage R – X R+X
⊕
2. Heterolytic cleavage R – X R + X⊕ or R +X
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1. Homolytic cleavage: In this cleavage, each atom separates with one electron leading to the formation
of highly reactive intermediates called free radicals.
A B A +B
A B A +B
Fig. 2: Homolytic cleavage
Homolytic cleavage occurs generally in the gas phase or in solution in non polar solvents and is
catalysed by ultra violet light or high temperature or by radical initiators like peroxides. Cleavage of
benzoyl peroxide or hydrogen peroxideis an example of homolysis. Mechanism of the reaction in which
homolysis takes place is known as homolytic mechanism or free radical mechanism.
2. Heterolytic cleavage: In this type of fission, one atom may hold on both the electrons leaving none
for the other, resulting in a negative and a positive ion (or ion pair).
⊕
A B A +B
Fig. 3: Heter olytic cleavage
Heterolytic cleavage occurs in polar solvents because of the ease of separation of charge and stabilization of
the resultant ion pairs through solvation. In such heterolytic fission, the charged species formed are either
carbon bearing positive charge called carbocation or carbon bearing negative charge called carbanion.
Mechanism of the reaction in which heterolysis takes place is known as heterolytic mechanism or ionic
mechanism. The energy required for heterolysis is always greater than that for homolysis due to electrostatic
forces of attraction operational between ions in case of hetrolytic cleavage.
1.5 Types of Attacking Reagents

There are basically two types of attacking reagents used in organic chemistry, the electrophiles and
nucleophiles. Electrophiles and nucleophiles can be looked upon essentially as acceptors and donors of
electron pairs respectively, from and to other atoms which is mostly carbon.
1. Electrophiles: Electrophilic reagents or electrophiles are the electron–deficient species which tend to
attack the substrate at position (or positions) of high electron density.It is observed that electrophiles are
positively charged species or must have an atom that carries a partial positive charge that are attracted
to an electron rich centre. However, there are cases where electrophiles are found to be neutral as
well.In neutral form, the electron loving nature is due to the incomplete octet configuration. As
electrophiles accept electrons, they are Lewis acids. The electrophiles are attacked by the most
electron-populated part of one nucleophile. The electrophiles frequently seen in the organic syntheses
are cations such as H+ and NO+, polarized neutral molecules such as HCl, alkyl halides, acyl halides,
and carbonyl compounds, polarizable neutral molecules such as Cl2 and Br2, oxidizing agents such as
organic peracids, chemical species that do not satisfy the octet rule such as carbenes and radicals, and
some Lewis acids such as BH3 and DIBAL.Some of the common examples are
⊕ ⊕ ⊕ ⊕ * * *
H ⊕ ,H3O ⊕ ,N O 2 ,N O,PhN2⊕ ,R ⊕ ,R 2 C H,R 3C ⊕ ,Cl ⊕ ,R − C O,SO 3 ,C O 2 ,B F3 , AlCl3 ,
*
ICl,Br2 ,O 3 etc. It participates in a chemical reaction by accepting an electron pair in order to bond to a
nucleophile.
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2. Nucleophiles: Nucleophilic reagents or nucleophiles are nucleus loving reagents which are
electron–rich species and which tend to attack the substrate at a position of low electron density.All
molecules or ions with a free pair of electrons or at least one π bond can act as nucleophiles. For
* ••
example, H − , BH −4 , H S O 3− , OH − , RO − , RS − , CN − , RCO −2 , R–C ≡ C − , –CH(CO 2 Et) 2 , R − , H2 O ,
••
•• •• * * *
R O H, R O R , R MgBr ,R Li, R 2 Cd etc.The star indicates the atom that donates electrons to the
•• ••
substrate.Another way of describing is that a nucleophile is a chemical species that donates an electron
pair to an electrophile to form a chemical bond in a reaction. As nucleophiles donate electrons, they are,
by definition, Lewis bases.
3. Nucleophilicity: Nucleophilicity, sometimes referred to as nucleophile strength, refers to a
substance's nucleophilic character and is often used to compare the affinity of atoms. Neutral
nucleophilic reactions with solvents such as alcohols and water are named solvolysis. Nucleophiles may
take part in nucleophilic substitution, whereby a nucleophile becomes attracted to a full or partial
positive charge.Examples of nucleophiles are anions such as Cl − , or a compound with a lone pair of
electrons such as NH3 (ammonia).In the example below, the oxygen of the hydroxide ion donates an
electron pair to bond with the carbon at the end of the bromopropane molecule. The bond between the
carbon and the bromine then undergoes heterolytic fission, with the bromine atom taking the donated
electron and becoming the bromide ion (Br − ), because a SN2 reaction occurs by backside attack. This
means that the hydroxide ion attacks the carbon atom from the other side, exactly opposite the bromine
ion. Because of this backside attack, SN2 reactions result in a reversal of the configuration of the
electrophile. If the electrophile is chiral, it typically maintains its chirality, though the SN2 product's
configuration is flipped as compared to that of the original electrophile.
H H
C Br C O H + Br –
H O– H O–
H H
4. Ambident nucleophile: An ambident nucleophile is one that can attack from two or more places,
resulting in two or more products. For example, the thiocyanate ion (SCN–) may attack from either the S
or the N. For this reason, the SN2 reaction of an alkyl halide with SCN–often leads to a mixture of RSCN,
an alkyl thiocyanate and RNCS which is an alkyl isothiocyanate. Some other examples of ambident
nucleophiles are cyanide ion or nitrite ion.
1.5.1 Different Types of Nucleophiles

Carbon nucleophiles are alkyl metal halides found in the Grignard reaction, Reformatsky reaction,
organolithium reagents, and anions of a terminal alkyne. Enols are also carbon nucleophiles. The formation
of an enol is catalyzed by acid or base. Enols are ambident nucleophiles, but, in general, nucleophilic at the
alpha carbon atom. Enols are commonly used in condensation reactions, including the Claisen condensation
and the aldol condensation reactions. Oxygen nucleophiles are water (H2O), hydroxide anion, alcohols,
alkoxide anions, hydrogen peroxide, and carboxylate anions Nuclophilic attack does not take place during
intermolecular hydrogen bonding of sulfur nucleophiles, hydrogen sulfide and its salts, thiols (RSH), thiolate
O S
|| ||
anions (RS ), anions of thiolcarboxylic acids (R − C − S ), and anions of dithiocarbonates (RO − C − S− )
− −
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S
||
and dithiocarbamates (R 2N − C − S− ) are used most often. In general, sulfur is highlynucleophilicin nature
because of its large size, which makes it readily polarizable, and its lone pairs of electrons are readily
accessible. Similarly, nitrogen nucleophiles include ammonia, azide, amines, and nitrites.
1.6 Types of Organic Reactions

There is no limitation to the number of possible organic reactions and mechanisms. However, certain general
patterns are observed that can be used to describe many common or useful reactions. Each reaction has a
stepwise reaction mechanism that explains how it happens. Although this detailed description of steps is not
always clear from a list of reactants alone. Organic reactions can be organized into several basic types. Some
reactions fit into more than one category. For example, some substitution reactions follow an
addition-elimination pathway. This study does not intend to include every single organic reaction. Rather, it
is intended to cover all the basic types of organic reactions. The important basic types of reactions are,
1. Addition reaction
2. Elimination reaction
3. Substitution reaction
4. Rearrangement reaction
There is one more prominent type which refers to organic redox reactions. Organic redox reactions are redox
reactions specific to organic compounds and are very common. For example oxidation of aldehydes by
Tollen's reagent.
1. Addition reaction: An addition reaction, in organic chemistry, is in its simplest terms an organic
reaction where two or more molecules combine to form a larger one.
Cl Cl
H H
C=C + Cl–Cl H C C H
H H
H H
Addition reactions are limited to chemical compounds that have multiple bonds, such as molecules with
carbon-carbon double bonds(alkenes), carbon oxygen double bonds, or with triple bonds (alkynes).
Molecules containing carbon-hetero multiple bonds like nitrile groups, or imine (C=N) groups, can
undergo addition as they too have multiple bond character. An addition reaction expectedly is the
opposite of an elimination reaction. For instance the hydration reaction of an alkene and the
dehydration of an alcohol are addition-elimination pairs. There are two main types of addition
reactions.
(i) Polar addition reactions
(ii) Non polar addition reactions
Subsequently, there are two main types of polar addition reactions:
(a) Electrophilic addition and
(b) Nucleophilic addition.
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Two non-polar addition reaction exists as well called

● Free radical addition and
● Cycloaddition reaction.
2. Elimination reaction: An elimination reaction is a type of organic reaction in which two atoms or
groups of atoms or substituents are removed from a molecule. This removal of substituents can take
place either in one or two-step mechanism. The one-step mechanism is known as the E2 reaction, and
the two-step mechanism is known as the E1 reaction. The numbers 1 and 2 refers to the kinetics of the
reaction. These numbers refer whether the reaction is bimolecular or unimolecular respectively. These
numbers have nothing to do with the number of steps in the mechanism. An example of elimination
reaction is shown below,
OH
H2SO4
130–140°C
In most organic elimination reactions, at least one hydrogen is lost to form the double bond. It is also
possible that a molecule undergoes reductive elimination, by which the valence of an atom in the
molecule decreases by two. An important class of elimination reactions are those involving alkyl halides,
with good leaving groups, reacting with a Lewis base to form an alkene. Elimination may be considered
the reverse of an addition reaction. When the substrate is asymmetric, regioselectivity is determined by
Saytzeff's rule or through Hoffmann elimination rule.
3. Substitution reaction: Substitution reaction also known as displacement reaction is a chemical
reaction during which one functional group in a chemical compound is replaced by another functional
group. Substitution reactions are of prime importance in organic chemistry.
Substitution reactions in organic chemistry are classified either as electrophilic or nucleophilic
depending upon the reagent involved. There are other classifications as well. Organic substitution
reactions are classified in several main organic reaction types depending on whether the reagent that
brings about the substitution is considered an electrophile or a nucleophile, whether a reactive
intermediate involved in the reaction is a carbocation, a carbanion or a free radical or whether the
substrate isaliphatic or aromatic. A good example of a substitution reaction is halogenation. When
chlorine gas (Cl-Cl) is irradiated, some of the molecules are split into two chlorine radicals (Cl) whose
free electrons are strongly nucleophilic. One of them breaks a weak C-H covalent bond and grabs the
liberated proton to form the electrically neutral H-Cl. The other radical reforms a covalent bond with the
CH 3 . to form CH 3 Cl (methyl chloride) as shown below,
H H
hν
H C + Cl–Cl H C + H–Cl
H H H H
Cl
4. Rearrangement reaction: A rearrangement reaction is a broad class of organic reactions where the
carbon skeleton of a molecule is rearranged to give a structural isomer of the original molecule. Often a
substituent moves from one atom to another atom in the same molecule. In the example below the
substituent R moves from carbon atom 1 to carbon atom 2:
—C–C–C— —C–C–C—
R R
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Intermolecular rearrangements also take place. A rearrangement is not well represented by simple and
discrete electron transfers. The actual mechanism of alkyl groups moving, as in Wagner-Meerwein
rearrangement, probably involves transfer of the moving alkyl group fluidly along a bond, not ionic
bond-breaking and forming. In pericyclic reactions, explanation by orbital interactions gives a better
picture than simple discrete electron transfers. It is, nevertheless, possible to draw the curved arrows for
a sequence of discrete electron transfers that give the same result as a rearrangement reaction, although
these are not necessarily realistic. In allylic rearrangement, the reaction is indeed ionic. Three key
rearrangement reactions are 1,2-rearrangements, pericyclic reactions and Olefin metathesis.
Table 1: Different types of organic reactions and their characteristics
Reaction Type Subtype Comment
1. Addition reaction a.Electrophilic addition(polar Include such reactions as

addition) halogenation, hydrohalogenation
and hydration.
b.Nucleophilic addition (polar
addition)
c.Radical
d. Addition(non polar addition)
2.Elimination reaction Include processes such as

dehydration and are found to follow
an E1, E2 or E1cB reaction mechanism
3. Substitution reaction a. Nucleophilic aliphatic

substitution
b. Nucleophilic aromatic
substitution
c. Nucleophilic acyl substitution With SN1, SN2 and SNi reaction

mechanisms
d. Electrophilic substitution
e. Electrophilic aromatic
substitution
f. Radical substitution
4.Rearrangement reactions a.1,2-rearrangements
b. Pericyclic reactions
c. Metathesis
In addition to all these types of reactions, there are condensation reactions in which a small molecule, usually
water, is split off when two reactants combine in a chemical reaction. The opposite reaction, when water is
consumed in a reaction, is called hydrolysis. Many Polymerization reactions are derived from organic
reactions. They are divided into addition polymerizations and step-growth polymerizations.
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2. Various Reaction Intermediates

Whenever a reaction takes place in organic chemistry, the reactants are not directly transformed to the
products. The reaction proceeds via some intermediates which are formed during the course of reaction and
are not very stable species.The most common transient intermediates formed are radicals, carbocations and
carbanions but other reactive intermediates possible are carbenes, nitrenes and benzynes. The formations of
these intermediates and their characteristic reactions have been dealt here in brief.
H C
Structure of CH3(sp2 hybridised)
2.1 Free Radicals

Their formation is initiated mostly by ultra violet light. For example,
•
hν
Cl − Cl  
→ 2 Cl
• •
R − H + Cl → R + HCl
This alkyl group bearing an odd unpaired electron is called alkyl radical. The radicals are electron deficient
and paramagnetic in nature. A free radical has carbon in the sp2 hybridised state, thus exhibit planar (flat)
structure. This type of hybridization is possible in most of the cases especially in case of conjugated free
radicals. However, in case of un conjugated free radicals, the hybridization state may be sp3.
sp2 sp3
Planar Pyramidal
Fig. 4: Hybridization states and shape of free radical
If a free radical with three different atoms or group of atoms is attacked by another radical, it leads to the
generation of a stereocentre, existing as enantiomeric pair.
R R R
Cl
C R' Cl + Cl R'
R' R'' R'' R''
Enantiomeric pair
The free radicals can act as electrophiles which attack at the site of high electron density on the
substrate.Rearrangement among radicals is found to be much less common than otherwise similar
rearrangements that involve carbocations. In this they resemble carbanions and the reason for their
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resemblance becomes apparent when we compare the transition states (T.S.) of the three for a 1,2 alkyl shift
(for detail see carbocation section).
≠ ≠ ≠
⊕
R R R
C C C C C C
Carbocation T. S. Radical T. S. Carbanion T. S.
These transition states involve two, three and four electrons, respectively and electrons in excess of two can
be accommodated only in an anti–bonding molecular orbital of much higher energy. However as with
carbanions, 1,2–aryl shifts are also known in radicals, which involve stabilized, bridged transition state. The
driving force for the rearrangement is to attain stability.
Stabilty of Free Radicals

1. The stability of free radicals increases with increase in the number of alkyl groups. Thus the stability of
different free radicals is:
H CH3 CH3 CH3
C < C < C < C
H H H H H CH3 H3C CH3
Methyl radical Primary radical Secondary radical Tertiary radical
Least stable Most stable
As alkyl groups are electron donating, these groups satisfy the electron deficiency of the free radicals
and enhance their stability.
2. The radical stability can also be increased with adjacent lone pair of electrons as suggested by the order
below. Interestingly, smaller is the hemolytic bond dissociation energy, larger will be the stability of free
radical.
H–CH3 H–CH2F H–CH2OH H–CH2NH2

Strongest bond Weakest bond
104 kcal/mol 101kcal/mol 95 kcal/mol 93 kcal/mol
H3C. < H2C. < H2C. H2C.
F OH NH2
Least stable Most stable
3. The stability of allyl free radical can be explained on the basis of identical resonating forms as shown
below,
2.2 Carbocations
Carbocation intermediate formation is initiated by the presence of highly polarion–solvating medium. For
example,
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⊕
CH2=CH–CH2
H+ ⊕ –H2O
Carbocation
CH2=CH–CH2–OH CH2=CH–CH2–OH2
⊕
CH2–CH=CH2
Here, the resulting carbocation is stabilized by the delocalization of the charge over other carbon atoms.
Carbocation is the carbon containing intermediate bearing a positive charge and having a sextet of electrons
in its outermost shell. The carbocation can act as a electrophile.
Structure and shape of carbocation or carbonium ion

Carbocations has a trigonal planar structure as the carbon atom of carbocations is also sp 2 hybridised. The
shape of methyl carbocation is shown below,
⊕
H
H empty p orbital
H
methyl cation
Fig. 5: Planar shape pf methyl carbocation
A carbocation can act as a electrophilic reagent and if a carbocation with three different atoms or group of
atoms is attacked by a nucleophile, it leads to the formation of racemic mixture.
R R R
Nu–
C + R' Nu + Nu R'
R' R'' R'' R''
Racemic mixture
2.3 Stability of Carbocations

Normally, electron donating groups increase the stability of carbocations whereas electron withdrawing
groups decrease the stability of carbocations. Some of the stability order are discussed below,
1. The stability of carbonium ions increases with increase in number of alkyl groups due to their +I effect.
The alkyl groups release electrons to carbon, bearing positive charge and thus stabilize the carbocation.
The order of stability of carbocationsis :
R R H H
most stable R C+ > R C+ > R C+ > H C+ least stable
R H H H
a tertiary a secondary a primary methyl cation
carbocation carbocation carbocation
A primary (1°) carbocation is the one in which the carbon bearing the positive charge is attached to one
carbon.A secondary (2°) carbocation is the one in which the carbon bearing the positive charge is attached to
two carbons.A tertiary (3°) carbocation is the one in which the carbon bearing the positive charge is attached
to three carbons. According to the laws of physics, the stability of a charged system is increased by the
dispersal of charge. Any factor, which tries to spread out the positive chare of the electron deficient carbon of
carbocation must stabilize it.
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In the present case, it is observed that greater the number of alkyl groups attached to the positive carbon of
the carbocation, the more stable the carbocation will be. The reason is that electron donating groups (+I
groups, alkyl groups in this case) partially compensates for the electron deficiency of the positive carbon of
the carbocation.
2. The high stabilty of benzyl carbocation is due to resonance present as shown below,
+
CH2+ CH2+ CH2 CH2
+ +
Some application of enhanced stabilization through resonance are

⊕ is more stable than ⊕
⊕ ⊕
is more stable than
⊕ is more stable than ⊕
3. Stability is also enhanced due to aromaticity in a compound as shown here,
H H
H
⊕ H C⊕
H H
H
tropylium cation trityl cation
4. Adjacent atoms with lone pair of electrons stabilize carbocation
NH2
⊕
is more stable than
⊕
OH H
H is more stable than H
⊕ ⊕
Cl
is more stable than
⊕ ⊕
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⊕
NH2 NH2
Donation of a lone pair

⊕
by the atom allows for
formation of a new π bond,
⊕
which is a stabilizing influence OH OH
H H
⊕
Cl Cl ⊕
Even though Cl is fairly electronegative the lone pair still form a π bond!
An application of this theory is predicting stability order in the following case,
A B C D E–
δ
F
O – CH3 CH3 H F δ– δ+ δ–
F C F
> > > >
⊕ ⊕ ⊕ ⊕ ⊕
Most least
Stable stable
⊕ CH3 ⊕
O– Stability: F
A>B>C>D>E
All atoms have

a full valence shell
5. Stabilization of carbocation through hyperconjugation as shown below,
δ+ ⊕
⊕ δ+ H δ+
H H
H
Ethyl 2–Propyl H
H H
H H
H H
⊕ ⊕
H H
H ⊕ H ⊕ H
H C C C CH2
H2C C H2C CH2 H3C H2 H3C
H2
⊕
H H ⊕ H H C CH3
C CH3
C H2C HH
H2 H
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δ+
δ H
+ ⊕ H δ+
H
tert–Butyl H
H H
H
⊕
H H
H3C ⊕ H3C
C C C CH2
H3C H2 H3C
⊕
H3C ⊕ H H3C C CH3
H C CH3
C H2C
H2 H
⊕
H H
H2C ⊕ H2C
C CH3 C CH3
H3C
H3C
Some more cases of relative stabilty of compounds are,

H3C
CH2+
C+—CH3
is more stable than H3C
H3C F3C
C+—CH 3
is more stable than C+—CF3
H F3C
2.4 Rearrangement in Carbocations

The most characteristic feature of carbocations is that they undergo rearrangements readily if possible. The
driving force for the rearrangement is to attain stability. The rearrangement may or may not involve change in
carbon skeleton.First considering the case in which carbocation undergoes rearrangement without change in
carbon skeleton. For example, 1 propyl cation rearranges to 2–propyl cation by the migration of a hydrogen
atom with its electron pair (i.e. as H– ) from C2 to the carbocationic C1 by 1,2 hydride shift.
H H
⊕ ~H– ⊕
CH3–CH–CH2 CH3–CH–CH2 Products
Products
This reflects the greater stability of a secondary carbocation rather than a primary carbocation. However, shift
in the reverse direction can also take place where this makes available the greater delocalization possibilities
of the π–orbital system of a benzene ring. (i.e. Tertiary → Secondary),
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OH OH H
H2SO4 –H2O ⊕
C6H5–CH2–CMe2 C6H5–CH2–CMe2 C6H5–CH–CMe2
–HSO4–
~H–
H
⊕
C6H5–CH2–CMe2 Products
The reverse rearrangement of even tertiary to secondary or primary carbocation can take place in special
circumstances. For example,
H
Ph Me Ph Me
dil. H2SO4 –H2O ⊕
Ph C C H Ph C C H Ph C C Me
+H+
OH OH OH2OH Ph OH
3° Carbocation
~H+
H H H
–H+ ⊕
Ph C C Me Ph C C Me Ph C C Me
Ph OH Ph ⊕O – H Ph OH
(More stabilized because of 2°Carbocation

completion of octet of very
atom other than hydrogen)
Here, the rearrangement is facilitated because the 2° carbocation produced is stabilized by the lone pair
delocalization (as the carbon bearing positive charge is attached to an atom having lone pairs) due to which
the octet of every atom gets complete except for hydrogen which have a duplet. Now, considering the case in
which the carbocation rearrangement involves change in carbon length,
Me Me Me
Polar solvent ⊕ ⊕
Me – C – CH2 – Br Me – C – CH2 – Br ~Me– Me – C – CH2 – Br
–Br–
Me Me Me
Products
It must be remembered that rearrangement does not necessarily always involve change in carbon length.
Sometimes no rearrangement takes place as the initially generated carbocation is having greater stability than
the one obtained after rearrangement. For example,
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Me Me Me
Polar solvent ⊕ ⊕
Me – C – CH – Ph Me – C – CH – Ph Me – C – CH – Ph
–Br–
Me Br Me Me
Products
Example 4: Which of the following carbocations is expected to be most stable?

CH3 CH3
⊕
(i) (ii)
⊕
X H X H
CH3 CH3
⊕ ⊕
(iii) H (iv) H
X X
Solution : Here in the given problem, carbocation (b) is stabilized most, as the CH3 group is attached to the
carbon bearing positive charge.
Ans : (ii)
2.5 Carbanions
A carbanion is an anionic species in which carbon atom has an unshared pair of
electrons and bears a negative charge usually with three substituents for a total of
-
eight valence electrons. Formally, a carbanion is the conjugate base of a carbon
acid.
R 3C − H + B− → R 3C − + H − B
where B stands for the base. A carbanion is one of several reactive intermediates in organic chemistry. Their
generation is also initiated by polar reagents. For example,
O O
OH–
CH3–C–CH2 CH3–C–CH2
+H2O
H
O
CH3–C=CH2
Here, the carbanion formed is stabilized by delocalization.

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∆
R–C–O– R–+CO2
O
Sometimes by heating also the carbanion can be generated. In this case, CO2 is eliminated by heating which
is rapid because it is thermodynamically stable produced as it is gaseous and stabilized by resonance. Here,
CO2 leaves without electron pair, leaving it for R and thus producing R −
NaNH
2
Ph3C − H     → Ph 3 C −Na ⊕ + NH3
Blood red (ether soluble salt)
The carbanions act as nucleophile and can add to the groups like C = O, C ≡ N, etc.
C≡N, –C–OH, –C–OR etc.
O O
Carbanion formation is by far one of the most important reaction intermediate because of their participation
in a wide variety of reactions of synthetic utility.
2.6 Structure of a Carbanion

The carbanion exists in a trigonal pyramidal geometry.Carbanion assume a pyramidal
configuration as carbon atom is sp3 hybridised. The unshared electron pair would be C
R''
accommodated in an sp3 orbital. R
R'
2.7 Carbon Acids
Any molecule containing a C-H can lose a proton forming the carbanion. Hence any hydrocarbon containing
C-H bonds can be considered an acid with a corresponding pKa value. Methane is certainly not an acid in its
classical meaning yet its estimated pKa is 56. Compare this to acetic acid with pKa 4.76. The same factors that
determine the stability of the carbanion also determine the order in pKa in carbon acids. These values are
determined for the compounds either in water in order to compare them to ordinary acids, in dimethyl
sulfoxide in which the majority of carbon acids and their anions are soluble or in the gas phase. With DMSO
the acidity window for solutes is limited to its own pKa of 35.5.
Table 2. Carbon acid acidities in pKa in DMSO. Reference acids in bold.
Name Formula Structural formula pKa
Methane CH4 H 56
108.70 pm
C
H 109.5° H
H
Ethane C 2 H6 50
H
H 111.17° H
120.40 pm
C C
H 153.51 pm
H H
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Anisole C 7 H8 O CH3 49
O
Cyclopentane C5H10 45
Propene C 3 H6 44
Benzene C 6 H6 43
Toluene C6H5CH3 CH3 43
Dimethyl (CH3)2SO O 35.5

167.6 pm
sulfoxide 105.1°
S
CH3
188.2 pm 96.0°
CH3
Diphenylmethane C13H12 32.3
Aniline C6H5NH2 NH2 30.6

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Triphenylmethane C19H16 30.6
Xanthene C13H10O 30
Ethanol C2H5OH 29.8

OH
Phenylacetylene C 8 H6 28.8
Thioxanthene C13H10S S 28.6
Acetone C 3 H6 O O 26.5
H3C CH3
106.0 pm
Acetylene C 2 H2 25
H–C≡C–H
120.3 pm
7 1
Benzoxazole C7H5NO 7a O 24.4
6
5 3a
N
3
4
Fluorene C13H10 22.6
Indene C 9 H8 20.1
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Cyclopentadiene C 5 H6 18
Malononitrile C3 H2 N 2 N 11.2
Hydrogen cyanide HCN H −C ≡ N 9.2
Acetylacetone C 5 H8 O 2 H 8.95
O O O O
Dimedone C8H12O2 5.23
O O
Meldrum's acid C 6 H8 O 4 4.97
O O
O O
Acetic acid CH3COOH O 4.76
OH
Barbituric acid C4H2O3(NH)2 O 4.01
HN NH
O O
Trinitromethane HC(NO2)3 NO2 0.17
C
O2N NO2
H
⊕ ⊕
Fulminic acid HCNO H—C≡N—O H—C=N—O -1.07
Note that the anions formed by ionization of acetic acid, ethanol or aniline are not carbanions.
Important Inferences From the Table

It is observed that the acidity increases:
1. When the anion is aromatic, either because the added electron causes the anion to become aromatic (as
in cyclopentadiene), or because the negative charge on carbon can be delocalized over several
already-aromatic rings (as in triphenylmethane).
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2. When the carbanion is surrounded by strongly electronegative groups, through the partial neutralisation
of the negative charge (as in malononitrile).
3. When the carbanion is immediately next to a carbonyl group. The α-protons of carbonyl groups are
acidic because the negative charge in the enolate can be partially distributed in the oxygen atom.
Meldrum's acid and barbituric acid, historically named acids, are in fact a lactone and a lactam
respectively, but their acidic carbon protons make them acidic. The acidity of carbonyl compounds is an
important driving force in many organic reactions such as the aldol reaction.
2.8 Chirality in Carbanion

With the molecular geometry for a carbanion described as a trigonal pyramid the question is whether or not
carbanions can display optical activity. With 4 different groups of atoms around the negatively charged
carbon atom(the lone pair due to negative charge behaves as a separate chemical group), it is definitely chiral
but optical activity is not ensured.The optical inactivity is ascribed to rapid interconvertibility of the two forms
as shown below,
R3
C R1 R2
R3 C
R1
R2
As the activation barrier for inversion of this geometry is too low any attempt at introducing chirality will end
in racemization, similar to the nitrogen inversion. However, solid evidence exists that carbanions can indeed
be chiral.
Stability and reactivity of a carbanion

As carbanions are nucleophilic species, these are highly reactive in nature. Due to the negative charge present
on carbanionic centre, any electron donating group renders stability to carbanion whereas electron donating
species decrease the stability.
As stated earlier, carbanion is a reactive intermediate and is frequently encountered in organic chemistry for
instance in the E1cB elimination reaction or in Grignard reaction or in alkyl lithium chemistry or in aldol
condensation reactions etc. Stable carbanions do however exist. In 1984 Olmstead presented the lithium
crown ether salt of the triphenylmethylcarbanion from triphenylmethane, n-butyllithium and 12-crown-4 at
low temperatures:
O O
2
H
C O O
Li+ .THF
C–
n-BuLi THF 12–crown–4
O-89
Adding n-butyllithium to triphenylmethane in THF at low temperatures followed by addition of 12-crown-4

results in a red solution and the salt complex precipitates at? 20 °C. The central C-C bond lengths are 145 pm
with the phenyl ring propelled at an average angle of 31.2°. This propeller shape is less pronounced with a
tetramethylammonium counter ion. One tool for the detection of carbanions in solution is proton NMR. The
stability and reactivity of a carbanion is determined by several factors. The important factors and the
subsequent order of stability are discussed below,
The inductive effect: Electronegative atoms adjacent to the charge will stabilize the charge and hence
enhance the stability of incipient carbanion as shown below,
H H Cl Cl
H
C < Cl C < Cl C < Cl C
H H H
Cl
unstable more stable
(no electron due to chlorines
withdrawing
groups)
However the stability of carbanions decreases with increase in the number of alkyl groups since the electron
donating alkyl groups destabilize the carbanions by increasing the electron density. Thus the order of stability
of alkylated carbanions is:
H H
C
methyl > 1° > 2° > 3°
Hybridization of the charge-bearing atom: The greater the s-character of the charge-bearing atom, the
more stable the anion.
The extent of conjugation of the anion: Resonance effects can stabilize the anion so that its stability is
increased manifold as shown below in the case of benzyl carbanion,
–CH2 CH2 CH2 CH2
δO
δB H
δP C δB
δO H
One more example of the same concept and hence subsequent order of stability is,
<
< <
no resonence resonance resonance

(less stable) (more stable) (more stable)
Similarly, allyl carbanion is more stable than any non conjugated carbanion in the following order,
O-90
H H
C
allylic > methyl > 1° > 2° > 3°
Some more examples of greater stability are,
O O N≡ O
C
R1 R1 R1 N R1
RO R3 O ⊕
R2 R2 R2 R2
O O N= O
C
R1 R1 R1 N R1
RO R3 ⊕
O–
R2 R2 R2 R2
Aromaticity: The stabilization is particularly enhanced when the negative charge is delocalised through
aromaticity. An example is shown below,
–
or –
–
cyclopentadienyl anion
Example 5 : Compare the stabilities of phenyl (C6H5) and cyclohexyl (a) cations and (b) anions.
Solution: (a) C 6 H5+ is a vinyl type carbocation and is less stable than C 6 H11
+
(Cycloheroyl cation), a 2°
carbocation.
(b) In C 6 H5− :, the electron pair is in an sp2 hybrid orbital. The carbanion has more s–character and is more
–
stable than C 6 H11 : whose unshared electron pair is in an sp3 hybrid orbital.
sp3
+ H – H
+ sp2 +
–
C6H+ C6H5– :
+ C6H11
5 C6H11
2.9 Carbene
Carbenes are electrically neutral carbon containing reactive intermediates with two bond pairs and one
unshared pair of electrons. They are electron deficient species and acts as electrophiles. The common
O-91
reactions in which they are formed as intermediates are Reimer Tiemann reaction, carbylamine reaction
etc.Carbenes exist transiently due to their less stabilty.
Methods of preparation
Some familiar processes by which carbenes are generated are discussed below.
1. These intermediates are generated by the α–elimination of trihalomethane. For example,

Cl Cl
OH– or OR– –Cl–
H– C Cl C Cl Cl–C– Cl
–H2O
or–ROH dichloro carbene
Cl Cl
2. Thermolysis of trichloro acetate ion also gives rise to carbenes.

∆
CCl3–COO– CCl2+CO2+Cl–
3. Photolysis of ketene and diazomethane yield carbenes as well.
hν
⊕
CH2 = C = O CH2 + C ≡ O
⊕ hν
CH2 = N = N CH2 + N ≡ N
4. Scheme of one more method of preparation is given below,

H
Bronsted
R base R
N–Ts
C=N C + N2 + HTs
R R
2.10 Types of Carbenes
Carbenes are very reactive and it is often difficult to prove that they are actually present in a given
reaction.The two non bonded electrons of a carbene can be either paired or unpaired as shown below,
R R'
R R
Singlet carbene Triplet carbene
Fig. 6: Singlet and triplet carbenes
If they are paired, the species is a singlet while if they are unpaired, the species is referred as triplet.The carbon
of singlet and triplet carbenes are sp 2 and sp hybridized respectively.The structures of the two alongwith the
bond angles are represented as
180°
103°
H C H C H
singlet carbene triplet carbene
O-92
The singlet CCl2 and CBr2 are also bent with angles of 100° and 114° respectively. Singlet carbene is the less
stable form due to the interelectronic repulsion between the electrons kept in the same orbital. However, it is
often (not always) the singlet form which is first generated in the initial photolysis.
Chemical reactions involving carbenes

1. Ring closure reactions with alkenes are one of the most common reactions of carbenes as shown below,
R' R
R C
C C + C C C
R'
An alkene A carbene A cyclopropane
2. There are some reactions reported in which carbene is not isolated as such but involves carbene
formation. In these reactions, it is not the free carbene intermediate, the carbenes are generated in situ
called as carbenoids. A familiar example of this is Simmon–Smith reaction.
ZnI ZnI ZnI
C C C
+CH2 CH2 CH2
C C C
I I I
2.11 Nitrene
Generally it is assumed that a nitrene (R-N:) is the nitrogen analogue of a carbene. Nitrenes are electrically
neutral nitrogen containing species with two unshared pairs and one bond pair of electrons. Here, nitrogen is
electron deficient atom therefore it is considered as an electrophile. A nitrene is a reactive intermediate and is
involved in many chemical reactions.
As nitrenes are highly reactive, they are not isolated. Instead, they are formed as reactive intermediates
during a reaction. There are some common ways to generate nitrenes. Such intermediates result from the
elimination of a proton and a leaving group (generally halogen) from the same atom of a substrate. For
example,
OH– –Br–
R–CH2–NH–Br R–CH2–N–Br R–CH2–N
–H2O
Nitrene
Other ways of generating nitrenes are α–elimination of N alkyl sulphonate esters and from azides by
thermolysis or photolysis, with expulsion of nitrogen gas. This method is analogous to the formation of
carbenes from diazo compounds.These can also be prepared from isocyanates, with expulsion of carbon
monoxide. This method is analogous to the formation of carbenes from ketenes.
2.12 Types of Nitrenes

In the most simple nitrene, the linear imidogen (:N-H), two of the 6 available electrons form a covalent bond
with hydrogen, two other create a free electron pair and the two remaining electrons occupy two degenerate
p orbitals.
O-93
singlet triplet
R–N RN R–N
R R
C R2C C
R R
Fig. 7.Singlet and triplet nitrene compared with carbenes
Consistent with Hund's rule the low energy form of imidogen is a triplet with one electron in each of the p
orbitals and the high energy form is the singlet state with an electron pair filling one p orbital and the other one
vacant.
2.13 Benzyne
Benzyne is an example of an aryne. The word -yne definitely means a triple bond, so that benzyne is a
benzene ring containing a triple bond as shown in the structure below,
H
H
H
This is no ordinary triple bond as the second interaction results from a weak interaction of sp2 hybrid orbitals
lying in the plane of the ring. The triple bond is non-linear due to the constraints of the 6-membered ring.
Hence, benzyne is strained and highly reactive. Normally, arynes in general, are best described as having a
strained triple bond; however, they possess some biradical character as well. Benzyne was first postulated by
Georg Wittig in 1940.The discovery of benzyne led to rapid developments in synthetic methodologies to
make this highly reactive intermediate useful for organic synthesis.
Methods of preparation of benzyne

Due to extreme reactivity of arynes they must be generated in situ. In the early days of benzyne chemistry,
harsh conditions were needed to generate arynes–many of the methods require strong base or high
temperatures.
Aryl halide can be treated with strong base to remove an aromatic proton and generate benzyne via
elimination of two ortho substituents.The reaction scheme is shown below,
O-94
Cl NH2
NaNH2
NH3(1)
Benzyne
Mechanism:
As observed, these intermediates are generated by the elimination of a proton and a leaving group (generally
halogens) from the adjacent carbons from a benzene ring system.
Cl Cl
NH2 –Cl–
⊕
–NH3
H
Benzyne
1. Arenediazonium-2-carboxylates can serve as precursors to benzynes. The main drawback of this

method is the explosive nature of diazonium compounds.
⊕
N2
heat
CO2
2. Milder methods for benzyne generation have been developed. Aryl triflates have been widely used in
synthesis.Fluoride displacement of the trimethylsilyl group, as shown below, allows for generation of
benzyne under mild conditions.
TMS
Bu4NF
OTf
In a reaction where benzyne is formed, if the solution does not have sufficient nucleophile, they undergo
dimerization to give biphenylene.
Dimerization
Biphenylene
2.14 Bonding in Benzyne

Benzynes are very reactive. Neither benzyne nor any other aryne (substituted benzyne) has yet been isolated
under ordinary conditions. The triple bond in benzynes is not identical with the formal triple bond of alkynes
because here the two π bonds are formed by the overlapping of p z − p z and sp2–sp2 orbitals whereas in
alkynes, they are formed by the orbital overlap of p z − p z and p y − p y .
O-95
°
1.39 A
sp2 °
134 A
R–C≡C–R
1.41 A°
138° A
180° angle 120° angle
Poor overlap
–looks much like

a diradical
R R
–Bond formed is quite weak
–Hybridization sp 2
–Formed only as an internediale
Fig. 8. Comparison of bonding in benzyne and alkyne
It should be noted that the π bond (resulted from sp2–sp2 overlap) is a very weak bond which can be easily
ruptured by the attack of a nucleophile, thus making the benzynes very reactive.
Another feature to be noted is that the extra pair of electrons does not affect the aromaticity. The original
sextet still functions as a closed ring and the two additional electrons are merely located in a α orbital that
covers only two carbons.
Chemical reaction of benzynes

Even at low temperatures arynes are extremely reactive. Their reactivity can be classified into certain major
classes like nucleophilic additions, ring closure or pericyclic reactions, bond-insertion etc.
1. Nucleophilic additions Upon treatment with basic nucleophiles, aryl halides are deprotonated α to the
leaving group, resulting in dehydrohalogenation. The resulting benzyne forms addition products, usually by
initial protonation. Generation of the benzyne intermediate is the slow step in the reaction.
Br NH2 NH2
slow NH2
NH2
NH2 H–NH2
In case of disubstitution, the chemical behavior of benzynes is impacted by the group previously present
in the benzene ring as shown below,
O-96
OMe OMe OMe OMe OMe
Cl Cl H–NH2
H NH2 NH2 NH2 NH2
2. Coupling or aryne couplingre actions allow for generation of biphenyl compounds which are valuable
in pharmaceutical industry, agriculture and as ligands in many metal-catalyzed transformations.
Br Ar Ar
Li–Ar
Br Li Br
3. Pericyclic reaction:Benzynes can undergo [4+2] cyclization reactions. The concerted mechanism of the
Diels-Alder reaction between benzyne and furan is shown below. However, many benzyne [4+2]
cycloadditions are thought to proceed via a stepwise mechanism.
O O
3. Methods of Determination of Reaction Mechanism

In determining the mechanism of a reaction, one of the major problems is to deduce the spatial or
three-dimensional changes that occur to the molecules involved as they proceed from their initial state
through the intermediate stages and transition states to the final products. Knowledge about such changes
can generally be deduced from knowledge of the stereochemistry of the starting materials, intermediates, and
final products provided these are obtained under kinetic control. Information of this kind is obtained by
determinations of optical activity and analysis of the structures of the compounds by standard means.
In certain instances, information about the movement of atoms between molecules during the course of a
reaction can be gained by using compounds containing isotopes of certain of the atoms. These isotopes
behave much like the ordinary atoms they replace, but they can be identified by their behaviour. For
example, in the hydrolysis of ethyl acetate, it is crucial to a determination of the mechanism to be able to
establish which of the two reactants - ethyl acetate or water provides the oxygen atom that ends up in the
product - ethyl alcohol. In this case, the use of water labelled with oxygen-18 reveals that the oxygen atom in
the alcohol comes from the ethyl acetate molecule. Some of the prominent terms used in the methods to
determine the reaction mechanism are discussed below,
3.1 Isotope Effect
Isotope effect or kinetic isotope effect (KIE) refers to a difference in reaction rate due to a difference in
the isotope present in the substrate.
There is a definite change in the rate of a chemical reaction when one of the atoms in the reactants is
substituted with one of its isotopes. So, if hydrogen atom is replaced by deuterium, then there is a difference
in the value of rate of reaction. Definitionwise, it is the ratio of rate constants for the reactions involving the
light (kL) and the heavy (kH) isotopically substituted reactants:
O-97
kL
KIE =
kH
It is generally of two types,

1. Primary kinetic isotope effect
2. Secondary kinetic effect
1. Primary kinetic isotope effects: A primary kinetic isotope effect may be found when a bond to
the isotopicallylabeled atom is being formed or broken. For the previously mentioned nucleophilic
substitution reactions, primary kinetic isotope effects have been investigated for both the leaving
groups, the nucleophiles, and the α-carbon at which the substitution occurs. Kinetic isotope effects at the
α-carbon can be used to develop some understanding into the symmetry of the transition state in S N 2
reactions, although this kinetic isotope effect is less sensitive than what would be ideal, also due to
contribution from non-vibrational factors.
2. Secondary kinetic isotope effects: A secondary kinetic isotope effect is observed when no
bond to the isotopically substituted atom in the reactant is broken or formed in the rate-determining step
of a reaction. By its definition, secondary kinetic isotope effects tend to be much smaller than primary
kinetic isotope effects. However, since kinetic isotope effects can be calculated and measured to very
high precision, secondary kinetic isotope effects are still very useful for elucidating reaction
mechanisms. For the aforesaid nucleophilic substitution reactions, secondary hydrogen kinetic isotope
effects at the α-carbon provide a direct means to distinguish between SN1 and SN2 reactions.
Value of Kinetic Isotope Effect

It has been found that SN1 reactions typically lead to large secondary kinetic isotope effects, approaching to
their theoretical maximum at about 1.22, while SN2 reactions typically yield kinetic isotope effects that are
very close to or less than unity. Kinetic isotope effects that are greater than 1 are referred to as normal
kinetic isotope effects, while kinetic isotope effects that are less than one are referred to as inverse
kinetic isotope effects. In general, smaller force constants in the transition state are expected to yield a
normal kinetic isotope effect, and larger force constants in the transition state are expected to yield an inverse
kinetic isotope effect when stretching vibrational contributions dominate the kinetic isotope effect.
⊕
C
+Nu:
SN1 H(D)
–LG: Nu
H(D) H(D)
C H(D) C
LG SN2 Nu C LG
+Nu:
–LG:
The magnitudes of such secondary isotope effects at the α-carbon are largely determined by the C α − H(D)
vibrations. For an SN1 reaction, since the carbon is converted into an sp2 hybridized carbonium ion during the
transition state for the rate-redermining step with an increase in C α − H(D) bond order, an inverse kinetic
isotope effect would be expected if only the stretching vibrations were important. The observed large normal
O-98
kinetic isotope effects are found to be caused by significant out-of-plane bending vibrational contributions
when going from the reactants to the transition state of carbenium formation. For SN2 reactions, bending
vibrations still play an important role for the kinetic isotope effect, but stretching vibrational contributions are
of more comparable magnitude, and the resulting kinetic isotope effect may be normal or inverse depending
on the specific contributions of the respective vibrations.
3.2 Kinetic and Thermodynamic Study of Organic Reactions

Thermodynamic reaction control or kinetic reaction control in a chemical reaction can decide the
composition in a reaction product mixture when competing pathways lead to different products and the
reaction conditions influence the selectivity. The distinction is relevant when product A forms faster than
product B because the activation energy for product A is lower than that for product B, yet product B is more
stable. In such a case A is the kinetic product and is favoured under kinetic control and B is the
thermodynamic product and is favoured under thermodynamic control.
The conditions of the reaction, such as temperature, pressure, or solvent, affect which reaction pathway may
be favored: either the kinetically controlled or the thermodynamically controlled one. Note this is only true if
the activation energy of the two pathways differ, with one pathway having a lower Ea (energy of activation)
than the other.
Prevalence of thermodynamic or kinetic control determines the final composition of the product when these
competing reaction pathways lead to different products. The reaction conditions as mentioned above
influence the selectivity of the reaction - which pathway is taken. The concept of kinetic and thermodynamic
control can be exemplified with the help of Diels-Alder reaction.
The Diels-Alder reaction of cyclopentadiene with furan can produce two isomeric products. At room
temperature, kinetic reaction control prevails and the less stable endo isomer 2 is the main reaction product.
At 81°C and after long reaction times, the chemical equilibrium can assert itself and the thermodynamically
more stable exo isomer1 is formed. The exo product (1) is more stable by virtue of a lower degree of steric
congestion, while the endoproduct is favoured by orbital overlap in the transition state.
O H
O
H
+ O H
H 1 2
O-99
Exercise
5. Write short note on stability of tropyliumcation over
Long Answer Type Questions triphenylmethylcation. [Avadh 2008]
1. Write short notes on : 6. Discuss the stability of carbocations. [Avadh 2009]
(i) Inclusion compounds 7. Write notes on the following :
(ii) Nitrene (i) Carbene (ii) Nitrenes
(iii) Free Radical (iii) Benzyne [Kashi 2010]
(iv) Carbene 8. Write notes on the following :
(v) Charge transfer complexes. [Bund. 2009] (i) Benzyne (ii) Carbene [Kashi 2011]
2. What are carbenes? What do you understand by 9. What is carbene? How is it formed? Give the
singlet and triplet carbenes? [Agra. 2008] examples of the reaction with structure and stability.
3. Write notes on : [Lko. 2010,11]
(i) Cross over experiment. 10. What are free radical? Discuss their characteristics
(ii) Isotopic labeling. and order of stability? [Rohd. 2011]
(iii) Trapping of reactive intermediates. 11. Discuss the role of hyperconjugation to explain the
[Avadh 2009] relative stabilities of ethyl, isopropyl and
4. What is carbocation? Describe the geometry of tert.butylcarbocations. [D.D.U 2008]
electron deficient carbon of carbocation.Explain the 12. CH3C +H2 is planar whereas CH3 CH2 and
mechanism of any such reaction in which the rate •
determining step is the slow ionization of substrate CH3 CH2 are pyramidal. Why? [D.D.U 2009]
molecule which generates carbocation as an 13. Arrange with reason the following carbanions in
intermediate. [Lko. 2009] order of their decreasing stability.
5. (i) Explain heterolytic and hemolytic CH(CH3 )2 ,CH3 ,C(CH3 )3 ,CH2CH3
bond fission with suitable examples. [D.D.U 2011]
(ii) What are carbocations? Arrange the 14. Write short notes on
following carbocations in order of increasing (i) Homolytic and heterolytiec fission
stability: (ii) Electrophiles and Nucleophiles
+ + [Hazaribagh 2008]
C6H5CH+
2
,(C6H5 )2 CH,(CH3 )3 C,
+
Very Short Answer Type Questions
(CH3 )2 CH 1. Write short notes on nitrene.
(iii) Write a short note on isotopic effects. [Bund. 2008; Meerut 2009,10,11; Agra 2008;
Kanpur 2011]
[Hazaribagh 2011]
2. Discuss the stability of carbonium ion. [Bund. 2009]
Short Answer Type Questions 3. Explain the following :
1. Write notes on the following : (i) Electrophile (ii) Nucleophile
(i) Carbonium ion. [Bund. 2010]
(ii) Free radical. [Meerut 2008,10,11] 4. Calculate the formal charge at the carbon of +CH3
2. Write a short note on homolytic fission of a covalent and at the oxygen of H2O. [Bund. 2010]
bond. [Meerut 2011] 5. Explain homolytic and heterolytic bond fission.
3. What are cabocations? How do you account for the [Bund. 2010]
relative stability of 1°, 2° and 3° carbocations. 6. What are arynes? [Bund. 2010]
[Agra 2008] 7. Explain structure and stability of singlet and triplet
4. Write short note on structure and stability of carbene. [Bund. 2010]
carbenes. [Avadh 2008]
O-100
8. Why propyl carbonium ion less stable than 23. Types of hybridization of the following :
allylcarbonium ion? [Meerut 2008] (i) Carbonium ion
9. Write a note on carbene. [Meerut 2009,11,12] (ii) Free radical
10. Write a short note on carbanion. [Meerut 2009,10] (iii) Nitrene
11. The order of stability amongst the carbanions is : (iv) Ethyene [Lko. 2010]
24. Pick up electrophile and nucleophile from following :
Primary > Secondary >Tertiary.Explain.
[Meerut 2011; Agra 2009] (i) :CCl2 (ii) SO3
••
12. Which is more stable and why? (iii) N2+ (iv) R N H2
⊕ ⊕ [Lko. 2010]
CH2 − CH = CH2 and CH2 = CH 25. Why tertinary carbonium ion is more stable than
[Kanpur 2011] secondary and primary carbonium ion?
13. Why a tertiary carbocation is more stable than a [Lko. 2010]
primary carbocation? [Avadh 2010] 26. Why is a tertiary free radical more stable as
14. Write short note on homolytic and heterolytice compared to primary and secondary free radicals ?
fission. [Kashi 2008] [Rohd. 2010]
15. Write short note on electrophiles and nucleophiles. 27. Explain free radicals with suitable example.
[Kashi 2008] [Hazaribagh 2009]
16. Select electrophiles and nucleophiles from the 28. Arrange the following according to their increasing
following: stability :
NH3 , AlCl3 , BF3 , C −N,N +O2 and H2O

(i) CH3 − CH2 − CH2 − CH2⊕
[Kashi 2011] (ii) CH3 − CH2 − CH ⊕ − CH3

17. Arrange the following carbanions according to their (iii) (CH3 )3 − C ⊕ [Hazaribagh 2009]
decreasing order of statbility :
⊕ 29. What is benzyne? Give its structure.
(i) CH3 [Hazaribagh 2011]
⊕
(ii) CH3 − CH2
⊕
(iii) CH3 − CH – CH3 [Kashi 2011]
18. What is A in the given reaction? [Lko. 2008] Multiple Choice Questions
1. Which of the following is the most stable carbanion?
–
:CH3+
CH
2 Dimerization A (a) (b) :CH <CH3
3
– –
(c) :CH2CH3 (d) C(CH3 )3 [Agra 2008]
19. Select the most stable carbanion from the following : 2. Carbocations contain which type of hybridization
CH3 CH2 ,CH3 ,(CH3 )CH,(CH3 )3 C.[Lko. 2008] (a) sp 3 (b) sp 2
20. Write one method for the preparation of free (c) sp (d) sp 3 d [Kanpur 2009]
radicals. [Lko. 2008] 3. Nucleophiles are
21. Differentiate between singlet and triplet carbene. (a) Lewis acids (b) Lewis base
[Lko. 2008] (c) Amphoteric (d) None of the above
22. Describe hybrid orbitals of the underlined C in each of [Rohd. 2009]
the following species. Give approximate bond angle. 4. Which of the following contains three pairs of
↑↓ ↑↑ electrons ?
(i) H2 C (ii) H2 C
(a) Carbocation (b) Carbonion
••
(iii) H2 C − H (c) Free radicals (d) None of the above
[Lko. 2009]
[Rohd. 2009]
O-101
5. The correct order of stability of carbonium ions is 13. Which among the following statement is correct?
+ + + + •• ••
(a) CH3 > R CH2 > R 2 CH > R 3 C (1)
C F2 is more stable than C Cl2
+ + + +
(2) •• ••
(b) R 3 C >R 2 CH > R CH2 > CH3 C Cl2 is more stable than C Br2
+ + + +
•• ••
(c) R 3 C >R 2 CH < R CH2 > CH3 (3)
Singlet C H2 is more stable than triplet C H2
(d) None of these [Rohd. 2011] (4) Singlet carbene has planar geometry
6. A nucleophile is
+
(a) 1, 2 and 4 (b) 2 and 4
(a) BF3 (b) N H4 (c) 1, 2 and 3 (d) 2, 3 and 4
(c) NH3 (d) AlCl3 [Rohd. 2011]
7. Which of the following is not a nucleophile?
Fill in the Blank
(a) NH3 (b) CO 1. Tropylium carbocation is …… stable than benzyl
(c) CO2 (d) H2O carbocation.
[Rohd. 2012]
8. Which of the following is not an electrophile? 2. Benzyne contains …… π electrons in the plane
perpendicular to the molecular plane.
(a) CH+
3
(b) Cl+
3. Methyl carbocation is …… in shape.
(c) NO+
2
(d) NH3 4. A singlet carbene is …… stable than a triplet
[Rohd. 2013]
9. Which of the following reagents may be described carbene.
as electrophilic reagent? 5. Out of carbocations and carbanions, it is …… which
(a) NH3 (b) AlCl3 is more willing to rearrangement reactions.
(c) CH 3 CH −2 (d) CH3CH2OH 6. Propyl carbonium ion is …… stable than
[Rohd. 2013] allylcarbonium ion.
10. Which of the following species is most stable ? 7. Conversion of alcohol to alkene in the presence of
⊕
(a) p − NO2C6H4 − CH2 conc. sulfuric acid proceeds via…… .
⊕ 8. Chlorobenzene when treated with sodamide yields
(b) C6H5 CH2 aniline via …… mechanism.
⊕
(c) p − Cl2 – C6H4 − CH2 9. Dehydration of alcohol is a/an …… reaction.
•• ⊕ 10. Oxidation of aldehydes by Tollen's reagent is an
(d) H3CO − C6H4 − CH2
•• example of ……..
11. Which among the following carbocations is most
stable: True/False
⊕ 1. Addition reaction is just reverse of substitution
(a) C reaction.
2. Benzyne is a non aromatic compound.
3. Ammonia is a nucleophile.
4. All triplet carbenes are sp hybridized.
⊕ 5. •
(b) C 6H5 − C H2 CH3 CH2 are pyramidal.
⊕ 6. Nucleophiles are Lewis acids.
(c) C6H5 − CH − C6H5
7. SO3 is an electrophile.
⊕
(d) CH3 − C − CH3 8. Phenyl carbanion is less stable than benzyl
| carbanion.
CH3
+ + + +
9.
12. Which one of the nitrogen containing compounds is R 3 C > R 2 CH2 > R CH2 > CH3 is the order of
an electrophile? stability of carbonium ions.
(a) NH 2 − NH 2 (b) NH2–OH 10. Properly substituted carbanion can show optical
(c) NF3 (d) NH3 activity.
O-102
Answers
1. (d) 2. (b) 3. (b) 4. (a) 5. (b)
6. (c) 7. (b) 8. (d) 9. (b) 10. (d)
11. (a) 12. (c) 13. (a)
Fill in the Blank

1. more 2. 6 3. trigonal planar 4. less
5. carbocation 6. less 7. carbocation 8. benzyne
9. elimination 10. redox reaction.
True/False
1. False 2. False 3. True 4. True 5. True
6. False 7. True 8. True 9. True 10. True
Hints and Solutions

5. + + +
(iii) (C 6H5 )2 C H > C 6H5C H2 > (CH3 )3 C + > (CH3 )2 C H
Short Answer Type Questions
13. CH −3 > CH3CH2 − > (CH3 )2 CH − > (CH3 )3 C −
12. + +
CH2 = CH − C H2 > CH2 = C H
17. + + +
CH3C H CH3 > CH3 − C H2 > C H3
19. CH3
22. CH2 ↑ ↓ → sp2
CH2 ↑ ↑ → sp
⊕
C H3 → sp3

5. Electron donating group attached to carbonium ion increases stability.
11.
+
C is highly stable due to bent orbital overlap.
3
❍❍❍
Unit-I
O-103
C HAPTER 3
Alkanes and Cycloalkanes
1. Alkanes
The alkanes or paraffins (a still-used historical name that also has other meanings as well) are the saturated
hydrocarbons comprising of homologous series with the general formula, CnH2n+2 where n is an integer.
Many of them occur naturally and the chief source of the alkanes is mineral oil or petroleum. Alkanes consist
of hydrogen and carbon atoms and all bonds are single bonds. Alkanes belong to a homologous series of
organic compounds in which the members differ by a molecular mass of 14.00u (mass of a methanediyl
group, –CH2–, one carbon atom of mass 12.01u, and two hydrogen atoms of mass ≈1.01u each). Each
carbon atom has 4 bonds which may be either C-H or C-C bonds, and each hydrogen atom is joined to a
carbon atom. A series of linked carbon atoms is known as the carbon skeleton or carbon backbone. The
number of carbon atoms is used to define the size of the alkane. An alkyl group, generally abbreviated with
the symbol R, is a side-chain that, like an alkane, consists solely of single-bonded carbon and hydrogen
atoms, for example methyl or ethyl group. The simplest possible alkane is methane, CH4. There is no limit to
the number of carbon atoms that can be linked together, the only limitation being that the molecule is acyclic,
is saturated, and is a hydrocarbon. Saturated oils and waxes are examples of larger alkanes where the
number of carbons in the carbon backbone is greater than 10. Alkanes are not very reactive and have little
biological activity. All alkanes are colourless and odourless. Alkanes normally are viewed as a molecular tree
upon which can be hung the more biologically active portions (functional groups) of the molecule.
1.1 Isomerism and Nomenclature

The IUPAC nomenclature for alkanes is based on identifying hydrocarbon chains. Unbranched, saturated
hydrocarbon chains are named systematically with a Greek numerical prefix denoting the number of carbons
and the suffix "-ane".
2 4 3 1
1 3 4 2
2–methylbutane 3–methylbutane
(correct numbering) (incorrect numbering)
O-104
Some examples are,
H3C H3C H3C CH3

CH3
H3C CH3
C–3 Propane
CH3 H3C CH3 H3C CH3

CH3 2–methyl propane 2–methyl butane 2–dimethyl butane
H3C
C–4 Butane
CH3 CH3 CH3 CH3 CH3 CH3
H3C CH3 H3C CH3 H3C CH3

Pentane
C–5
CH3 CH3 CH3 CH3 CH3 CH3
CH3 2,2,3,3,4,4,5,5,6,6–decamethylheptane 2,2–dimethylpropane
H3C neopentane
C–6 Hexane CH3 CH3 CH3 CH3 CH3
H3C CH3 H3C CH3

H3C CH3
Heptane
C–7 CH3 CH3 CH3 CH3 CH3
2,2,3,3,4,4–hexamethylpentane 2,2,3,3–tetramethylbutane
CH3
H3C
CH3 CH3 CH3 CH3
Octane
C–8
H3C CH3
H3C CH3
Nonane
C–9 CH3 CH3 CH3 CH3
CH3
H3C 2,2,3,3,4,4,5,5–Octamethylhexane
Decane
C–10
Numbers in the name, referring to which carbon a group is attached to, should be as low as possible, so that
1- is implied and usually omitted from names of organic compounds with only one side-group. Some more
examples are,
7 6 5 4 3 2 1
CH3–CH2–CH–CH–CH–CH–CH3
5' CH3
CH3 CH2 CH3CH3
CH
6'
CH3
CH2 CH2
7'CH
3 methylcycloproane
2,3,5–trimethyl–4–propylheptane
(NOT: 2,3–dimethyl–4–sec–butylheptane)
CH3 CH3
CH3–CH2–CH–CH–CH2–CH3
CH3–CH–CH2–CH2–CH–CH2–CH–CH2–CH3
CH3 CH2
CH–CH3
CH3
CH2–CH3 3–ethyl–4–methylhexane
5–sec–butyl–2, 7–dimethylnonane
O-105
Alkanes with more than three carbon atoms can be arranged in various different ways, forming structural
isomers. The simplest isomer of an alkane is the one in which the carbon atoms are arranged in a single chain
with no branches. This isomer is sometimes called the n-isomer, here n is used for "normal", although it is not
necessarily the most common. However the chain of carbon atoms may also be branched at one or more
points. The number of possible isomers increases rapidly with the number of carbon atoms. For example C1 is
methane only,C2 is ethane only, C3 is propane only, C4 has 2 isomers : n-butane and isobutane, C5 has 3
isomers: pentane, isopentane, and neopentane, C6 has 5 isomers: hexane, 2-methylpentane,
3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane and C12 has a staggering 355 isomers.
Branched alkanes can give rise to chirality. For example 3-methylhexane and its higher homologues are
chiral due to their stereogenic center at carbon atom number 3. In addition to these isomers, the chain of
carbon atoms may form one or more loops. Such compounds are called cycloalkanes.
1.2 Methods of Preparation of Alkanes

A number of methods are available for the synthesis of alkanes. Some of these are discussed below,
1.2.1 Methods Involving No Change in the Carbon Skeleton

Substitution of halogen by hydrogen can be done in as discussed below,
1. Reduction by dissolving metals: Reduction can be achieved by dissolving metals like zinc and
acetic or hydrochloric acid, zinc and sodium hydroxide, zinc-copper couple and ethanol, etc. Initially, it
was presumed that nascent hydrogen is the actual reducing agent in this reaction. Now it is believed
that there is an electron–transfer from the metal to the substrate leading to the formation of carbanion
which is followed by the abstraction of a proton from the solvent. Thus, reduction with a zinc–ethanol
couple may be formulated as
Zn → Zn2+ + 2e–
e−
RX + e–→ X– + R.  
→ R :–
R:– + C2H5OH → R—H + –OC2H5

2. Reduction by reducing agents like LiAlH4, NaBH4 etc.: Primary and secondary alkyl halides
are readily reduced to alkanes by lithium aluminium hydride (LiAlH4) whereas reduction of tertiary
halides with LiAlH4 gives mainly alkenes. On the other hand, sodium borohydride (NaBH4) reduces
secondary and tertiary halides, but not primary, whereas TPTH, triphenyltin hydride (Ph3SnH)
reduces all three types of alkyl halides. So each reducing agent is specific in its action.
(i) 4R – X + LiAlH4 → 4R–H + LiX + AlX3 (X ≠ F)
Or,R–X + H:(–) →R–H + X–
Hydride ion comes from LiAlH4.

(ii) R–X + (n - C4H9)3SnH →R – H + (n - C4H9)3SnX
3. Using organometallic compounds: Alkyl halides react with either Mg or Li in dry ether to give
organometallic compounds having a carbanionic site. These organometallic compounds upon
hydrolysis yield corresponding alkanes.
dry ether
→ R– Li+ + LiX
R – X + 2Li    
O-106
then, R– Li+ + H2O →R – H + LiOH

dry ether
→ R– Mg+X
R – X + Mg    
then, RMgX + H2O → R – H + MgX(OH)

strong acid weak acid
The net effect is replacement of X by H. This reaction can be done with any compound that is more acidic
than alkane. Thus the net effect of the reaction is the displacement of a weak acid from its salt by a strong acid.
Using this reaction, we determine the number of acidic or active hydrogens present in a given compound.
This quantitative estimation of number of active hydrogens is called Zerewittnoff's method. For example,
O
3RMgX+HC≡C–CH(OH)–CO2H→3R–H+XMgC≡C–CH–C
OMgX
OMgX
Three moles of alkane formed shows that the compound contains three active or acidic hydrogens.
1.2.2 Hydrogenation of Alkenes in the Presence of Pd or Pt

This addition is an example of heterogeneous catalysis involving syn addition.
CH3 CH3
CH3–C=CH2+CH2+H2 Pt CH3–CH–CH3
Dihydrogen in the presence of Raney Ni is also used for the purpose of reduction. Raney Ni is use of nickel
aluminium alloy in the presence of caustic soda. The stereospecificity of the reaction is that the addition of
hydrogen to the double bond occurs in syn fashion without disturbing the configuration at the chiral carbon.
For example,
CH3 CH3 CH3
H OH H OH
D2 /Ni
H OH +
H D D H
CH=CH2 CH2D CH2D
Diastereomers
The addition of both the deuterium atom occurs from the same side. In some molecules, the attack is from the
bottom side and in other molecules, D2 attacks from the top side leading to the formation of two isomers
called diastereomers.
1.3 Methods Involving Change in the Carbon Skeleton

1.3.1 Methods in Which number of Carbons Atoms Increases w.r.t. Starting Compound
1. Wurtz reaction: An ethereal solution of an alkyl halide, preferably the bromide or iodide, is treated
with sodium, when alkane is obtained. For example,
O-107
dry ether
R1 − X + R 2 − X + 2Na    
→ R1 − R 2 + 2NaX
In this reaction , two R groups are coupled by reacting RBr, RCl or RI with Na or K. The yields of the product
are best for 1° alkyl halides (60%) and least for 3° alkyl halides (10%). Looking further in the above reaction,
it was found that in addition to the desired alkane R 1 − R 2 , there will also be present the alkanes R 1 − R 2
and R 2 − R 2 . Unsaturated hydrocarbons are also obtained. Obviously, then, the best yield of an alkane will
be obtained when R 1 & R 2 are same, i.e., when the alkane contains an even number of carbon atoms and is
symmetrical. It has been found that the Wurtz reaction gives good yields only for 'even carbon' alkanes of high
molecular weight, and that the reaction generally fails with tertiary alkyl halides. The reaction involves the
intermediate formation of free radicals. The suggested mechanism for the Wurtz reaction is shown as
Na → Na + + e−
R − Br + e − → R • + Br –
2R • → R − R
Na + + Br − → NaBr
(Alkane with even carbon atoms)
It is important that note metal other than sodium, which can be employed in Wurtz reaction are Ag and Cu in
finally divided state.
2. Corey House synthesis: A superior method for coupling is the Corey House synthesis which could
be employed for obtaining alkanes containing odd number of carbon atoms also known as
unsymmetrical alkanes. For example,
R – X + 2Li → R–Li++ LiX
2R–Li+ + CuX → (R)2CuLi + LiX
R2CuLi + 2R' – X → 2R – R' + LiX + CuX
Some examples of the reaction are shown below,

1. Li
CH3I (CH3)2CuLi
2. CuI
0°
(CH3)2CuLi+CH3(CH2)8CH2I CH3(CH2)9CH3
1. Li CH3–CH2–Cl
CH3–CH2–Cl 2. CuI (CH3–CH2)2LiCu
CH3–CH2–CH2–CH3
3. Kolbe's electrolytic method: A concentrated solution of the sodium or potassium salt of a

carboxylic acid or a mixture of carboxylic acids is electrolysed. For example,
R 1CO2K + R 2 CO2K + 2H2O → R 1 – R 2 + 2CO2 + H2 + 2KOH
If R1 and R2 are different, then hydrocarbons R 1– R 1 and R 2 – R 2 are also obtained along with R 1 – R 2 .
Earlier several mechanisms have been proposed for the Kolbe reaction. The free– radical theory is the one
O-108
now favoured, having strong evidences in support of it. For example, when sodium propionate is
electrolysed, n–butane, ethane, ethylene and ethyl propionate are obtained.
Mechanism
C2H5CO2Na → C2H5CO −2 +Na +
At anode, the propionate ion discharges to form a free radical.

C2H5CO −2 → C2H5CO •2 +e–
This propionate free radical then breaks up into the ethyl free radical and carbon dioxide.
C2H5CO •2 → C2H •5 + CO2
Then, the following type of dimerisation can take place,

(i) 2C2H •5 → C4H10
(ii) C2H •5 +C2H •5 → C2H6 + C2H4
(iii) C2H •5 +C2H5CO •2 → C2H5CO2C2H5
Reaction (i) gives n butane; (ii) gives ethane and ethylene by disproportionation and (iii) gives ethyl
propionate. Thus at anode, gases evolved are CO2, ethane, ethene and butane. At cathode, hydrogen ions
accept an electron and are converted to H2 gas.
2H+ + 2e– → H2
1.3.2 Methods in Which Number of Carbon Atoms Decreases w.r.t. Starting Compound:
1. Decarboxylation of carboxylate salts: By heating a mixture of the sodium salt of a carboxylic acid
and soda-lime, alkanes can be obtained.
∆
R CO2Na + NaOH (CaO) → RH + Na2CO3
This process of eliminating CO2 from a carboxylic acid is known as decarboxylation. This reaction can be
employed for decreasing the length of carbon chain i.e. to descend a homologous series. This
decarboxylation reaction probably involves following mechanistic steps.
Mechanism
O O
R–C OH R–C CO2 + R
OH O H–OH
R–H+OH
2. 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 ∆H°. In the reaction given below, the designated C – H bonds are
broken homolytically and the values of ∆H° for these bonds are also given.
CH3CH2CH2–H → CH3CH2CH •2 + H • ∆H° = + 98 k calmol–1

(n–propyl radical–a 1° radical)
O-109
CH2–C–CH2–H CH3CHCH3+H ∆H°=+94.5 k cal mol–1

(Isopropyl radical
H –a 2° radical)
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 mean that the primary radical has absorbed more
energy and thus has greater potential 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
(98–94.5) CH3 CH3
CH3–C–CH2–H CH3–C–CH3+H ∆H°=+91 k cal mol–1

tert–butyl radical (3°)
H
CH3 CH3
CH3–C–CH2–H CH3–CH–CH2+H ∆H°=+98 k cal mol–1

Isobutyl radical (1°)
H
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 as follows
Tertiary > Secondary > Primary > Methyl
Physical Properties of the Alkanes

1. The first four alkanes: Methane to butane are colourless gases, the next thirteen - pentane to
heptadecane are colourless liquids and those containing 18 carbon atoms and more are solids at
ordinary temperatures.
Table 1:Physical properties of alkanes
Alkane Formula Boiling point [°C] Melting point Density [g·cm–3]

[°C] (at 20 °C)
Methane CH4 –162 –182 gas
Ethane C 2 H6 –89 –183 gas
Propane C 3 H8 –42 –188 gas
Butane C4H10 0 –138 gas
Pentane C5H12 36 –130 0.626 (liquid)
Hexane C6H14 69 –95 0.659 (liquid)
Heptane C7H16 98 –91 0.684 (liquid)
Octane C8H18 126 –57 0.703 (liquid)
Nonane C9H20 151 –54 0.718 (liquid)

O-110
Decane C10H22 174 –30 0.730 (liquid)
Undecane C11H24 196 –26 0.740 (liquid)
Dodecane C12H26 216 –10 0.749 (liquid)
Hexadecane C16H34 287 18 0.773 (liquid)
Icosane C20H42 343 37 solid
Triacontane C30H62 450 66 solid
Tetracontane C40H82 525 82 solid
Pentacontane C50H102 575 91 solid
Hexacontane C60H122 625 100 solid
2. Boiling and melting point: The boiling point of alkanes show gradual rise as the carbon content
increases. In general, the boiling point difference between two successive members of the homologous
series, except for the first few members, is about 20–30°C. Among the isomeric alkanes, the straight
chain isomer has a higher boiling point than the branched chain isomer. The greater the branching of
the chain, the lower the boiling point.
In fact, the lowering of boiling point with the branching of the carbon chain is a feature characteristic of all the
families of organic compounds. The van der Waal's forces which hold non–polar molecules are weak and
have a very short range. Therefore, within a family of compounds the strength of intermolecular forces would
be directly proportional to the size or the surface area of the molecule. In other words, larger the molecule,
stronger the intermolecular forces would be. The process of boiling requires overcoming these intermolecular
forces of attraction. As the molecules become larger, the intermolecular forces increase and the boiling points
must rise with increase in the number of carbons atoms.
As the branching increases in a molecule, its shape approaches that of a sphere and there is a reduction in
surface area. This renders the intermolecular forces weaker and they are overcome at relatively lower
temperature. Therefore, a branched–chain isomer must boil at a temperature lower than that of a straight
chain isomer.
Their melting points also show a rise with the increasing number of carbon atoms, but the rise is not as regular
as in the case of boiling points. It is, however, significant that as we move from an alkane having an odd
number of carbon atoms to a higher alkane, the rise in melting point is much higher than that when we move
O-111
up from an alkane with an even number of carbon atoms. The intermolecular forces in a crystal depend not
only on the size of the molecules but also on how they are packed into a crystal. During melting, these
intermolecular forces have to be overcome. Since breaking of crystal structure is a more complicated process,
it is understandable that the rise in melting point with increasing molecular weight is not as regular as in the
case of boiling points.
3. Solubility: Alkanes are made up of carbon and hydrogen atoms only. Since these two elements have
almost similar electronegativities, alkanes are non–polar. Therefore, non–polar alkanes are soluble in
non–polar solvents like carbon tetrachloride, benzene, etc. but insoluble in polar solvents like water,
alcohol, etc.
4. Density: The densities of alkanes show a definite rise with increasing molecular weight, but they reach
a limiting constant value of about 0.8 with n hexadecane (C16H34). Thus, alkanes are always lighter
than water.
5. Molecular geometry: The molecular structure of the alkanes directly affects their physical and
chemical characteristics. It is derived from the electron configuration of carbon, which has four valence
electrons. The carbon atoms in alkanes are always sp3 hybridized, that is to say that the valence
electrons are said to be in four equivalent orbitals derived from the combination of the 2s orbital and
the three 2p orbitals. These orbitals, which have identical energies, are arranged spatially in the form of
a tetrahedron, the angle of 109º.28' between them.
H
H
H
Fig. 2: The tetrahedral structure of methane.
An alkane molecule has only C - H and C - C single bonds. The former result from the overlap of a sp3-orbital
of carbon with the 1s-orbital of a hydrogen; the latter by the overlap of two sp3-orbitals on different carbon
atoms. The bond lengths amount to 1.09×10–10 m for a C - H bond and 1.54×10–10 m for a C - C bond. The
spatial arrangement of the bonds is similar to that of the four sp3-orbitals-they are tetrahedrally arranged.
Structural formulae that represent the bonds as being at right angles to one another, while both common and
useful, do not correspond with the reality.
Chemical Properties of the Alkanes

1. Nitration: Under certain conditions alkanes react with nitric acid, when a hydrogen atom will be
replaced by a nitro–group, NO2. This process is known as nitration. Nitration of the alkanes may be
carried out in the vapour phase between 150° and 475°C, when a complex mixture of
mononitroalkanes is obtained. The mixture consists of all the possible mononitroderivatives and the
nitro compounds formed by every possibility of chain fission of the alkane. For example, propane gives
a mixture of 1–nitropropane, 2–nitropropane, nitroethane and nitromethane.
NO2
|
HNO3
CH3CH2CH3   → CH3CH2CH2NO 2 + CH3 − CHCH3 + C 2H5NO 2 + CH3NO 2
400 ° C
O-112
2. Sulphonation: It is the process of replacing hydrogen atom by a sulphonic acid group, SO3H.
Sulphonation of a normal alkane from hexane onwards may be carried out by treating the alkane with
oleum (fuming sulphuric acid). The ease of replacement of H– atoms in tertiary compounds is more
than secondary, and in secondary compounds replacement of H–atoms by sulfonic acid group is easier
than primary. Replacement of a primary hydrogen atom in sulphonation is very slow indeed.
Isobutane, which contains a tertiary hydrogen atom, is readily sulphonated to give t–butylsulphonic
acid.
(CH3)3CH + H2SO4/SO3 → (CH3)3CSO3H + H2SO4

3. Oxidation: All alkanes readily burn in excess of air or oxygen to form carbon dioxide and water.
(3n + 1) (2n + 2)
CnH2n+2+ O2(g) → nCO2(g) + H2O(l)
2 2
On the other hand, controlled oxidation under various conditions, leads to different products.
Extensive oxidation gives a mixture of acids consisting of the complete range of C1 to Cn carbon atoms.
Less extensive oxidation gives a mixture of products in which no chain fission has occurred. Under
moderate conditions mixed ketones are the major products, and oxidation in the presence of boric acid
produces a mixture of secondary alcohols. The oxidation of alkanes in the vapour state occurs via free
radicals, Oxidising reagents such as potassium permanganate readily oxidises a tertiary hydrogen
atom to a hydroxyl group. For example, isobutane is oxidised to t–butanol.
KMNO
(CH3)3CH + [O]    

4 → (CH ) COH
3 3
4. Halogenation: Chlorination is brought about by photo irradiation, heat or catalysts, and the extent of
chlorination depends largely on the amount of chlorine used. A mixture of all possible isomeric
monochlorides is obtained, but the isomers are formed in unequal amounts, due to difference in
reactivity of primary, secondary and tertiary hydrogen atoms.
The order of ease of substitution of different types of H is
Tertiary Hydrogen > Secondary Hydrogen > Primary Hydrogen
Chlorination of isobutane at 25°C gives a mixture of two isomeric monochlorides.

CH3 CH3
CH3–CH–CH2–Cl and CH3–C–CH3
Cl
(64%) (36%)
The tertiary hydrogen is replaced about 5 times as fast as primary hydrogen. 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.
CH4+I2 CH3I+HI
5HI+HIO3 3I2+3H2O
O-113
Iodides are more conveniently prepared by treating the chloro or bromo derivative with sodium iodide in
methanol or acetone solution. For example,
acetone
RCl + NaI   → 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 of halide exchange is known as Conant–Finkelstein reaction.
Direct fluorination is usually explosive. So, special conditions are necessary for the preparation of the fluorine
derivatives of the alkanes.
UV light
RH + X2    
→ RX + HX
or ∆
Reactivity of X2: F2 > Cl2 > Br2 > I2

The mechanism of chlorination of methane is as follows
Chain initiation step:

UV light
→ 2Cl • ; ∆H = + 243 kJ mol–1
Cl – Cl    
or ∆
The required enthalpy comes from Ultraviolet (UV) light or heat supplied.
Chain propagation step:
(i) H3C – H + Cl • → H3C • + H – Cl ; ∆H = – 4 kJmol–1 (rate determining step)
(ii) H3C • + Cl – Cl → H3C – Cl + Cl • ; ∆H = – 96 kJmol–1
The sum of the two chain propagation steps in the overall reaction is
CH4 + Cl2 → CH3Cl + HCl ; ∆H =–100 kJmol–1
In propagation steps, the same free radical intermediates, here Cl • and H3C • , being formed and consumed.
Chain termination step:
Chains terminate on those rare occasions when any two free-radical intermediates collide to form a covalent
bond.
Cl • + Cl • → Cl2
H3Cl • + Cl • → CH3 – Cl
H3C • + • CH3 → H3C CH3
Radical inhibitors stop chain propagation by reacting with free radical intermediates.
For example,
•• •• •• ••
H3C • + • O – O • → CH3 – O – O •
•• •• •• ••
O-114
The potential energy curve for the halogenation (chlorination) of alkane is shown as
Eact
Potential energy R–H+Cl

HCl+R
R+Cl2
R–Cl+Cl
Progress of reaction
Fig. 3: Potential energy curve for chlorination of alkane
In more complex alkanes, the abstraction of each different kind of hydrogen atom gives a different isomeric
product. Three factors determine the relative yields of isomeric product.
(i) Probability factor: This factor is based on the number of each kind of hydrogen atoms in the alkane
molecule. For example, in CH3CH2CH2CH3 there are six equivalent 1° H and four equivalent 2° H.
The probability of abstracting a 1°H to 2° H is 6 to 4, or 3 to 2.
(ii) Reactivity of H • : The order of reactivity of hydrogen atoms is 3° > 2° > 1°.
(iii) 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 determined by the probability factor as well as reactivity of
hydrogen atoms while if the species attacking is less reactive and more selective, the yield of the
product is governed exclusively by reactivity of hydrogen atoms.
Cl / hν
CH3CH2CH2CH3  2→ CH3CH2CH2CH2Cl + CH3CH2CH(Cl)CH3
25 ° C
n butane (28%) (72%)
Cl / hν
(CH3)2CHCH3  2→ (CH3)2CHCH2Cl + (CH3)3C – Cl
25 ° C
isobutane (64%) (36%)
Br2 / hν
CH3CH2CH2CH3   → CH3CH2CH2CH2Br + CH3CH2CH(Br)CH3
127° C
n butane (2%) (98%)
Br2 / hν
(CH3)2CHCH3   → (CH3)2CHCH2Br + (CH3)3C Br
127° C
isobutane traces (over 99%)
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 favours 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
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hydrogen are successful as collisions with the primary hydrogens. The Eact is less for abstraction of a tertiary
hydrogen than for the abstraction of a primary hydrogen.The rate of abstraction of hydrogen atoms is always
found to follow the sequence 3° > 2° > 1°. At room temperature (25°C), the relative rates in chlorination are
5.0 : 3.8 : 1.0 respectively for 3°, 2° and 1° hydrogen atoms. Using these values, we can predict the ratio of
isomeric chlorination products from a given alkane. For example,
2 Cl
CH3CH2CH2CH3   → CH3CH2CH2CH2Cl + CH3CH2CHClCH3
light, 25 ° C
n – butylchloride number of 1° H reactivity of 1° H

= ×
sec − butyl chloride number of 2 ° H reactivity of 3 ° H
6 1.0 3 28%
= × = equivalent to
4 3.8 7.6 72%
Inspite of these differences in reactivity, chlorination rarely yields a great excess of any single isomer. In most
cases, both the products are formed in considerable amounts.
The same sequence of reactivity, 3° > 2° > 1°, is found in bromination, but with enormously larger reactivity
ratios. At 127° C the relative rates per hydrogen atom in bromination are 1600 : 82 :1 respectively for 3°, 2°
and 1° hydrogen atoms. Here, differences in reactivity are so marked that it outweighs probability factor.
Hence bromination almost exclusively gives selective product. In bromination of isobutane at 127°C,
isobutyl bromide number of 1° H reactivity of 1° H

= ×
tert − butyl bromide number of 3 ° H reactivity of 3 ° H
9 1 9 0.5%
= × = equivalent to
1 1600 1600 99.5%
Hence, tert butyl bromide happens to be the exclusive product (over 99%) with traces of isobutyl bromide.
The reason for the higher selectively in bromination as compared to chlorination is due to the following
explanation.
According to the general principle, 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. In the attack by the comparatively unreactive bromine atom, the transition state is reached late in the
reaction process, after the alkyl group has developed considerable radical characater. In the attack by the
highly reactive chlorine atom, the transition state is reached early, when the alkyl group has gained very little
radical character. Thus bromination is more selective than chlorination.
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δ δ
R–H+Br R H Br R+H+Br
low reactivity, Transition state
high selectivity reached late, much
radical character
δ δ
R–H+Cl R H Br R+H–Cl
Transition state
reached early, little
radical character
2. Cycloalkanes
Cycloalkanes also called naphthenes(but different from naphthalene)are saturated hydrocarbons in which
the carbon atoms are joined by single covalent bonds to form a ring. Cycloalkanes consist of only carbon (C)
and hydrogen (H) atoms and there are no multiple C-C bonds to hydrogenate. They are also called alicyclic
compounds. The prefix ali-is added because of their similarity to aliphatic compounds. The first member of
the series is cyclopropane,C3H6 . Cycloalkanes might have one or more rings of carbon atoms in the chemical
structure of their molecules. A general chemical formula for cycloalkanes would be CnH2(n+1-g) where n =
number of C atoms and g = number of rings in the molecule. Cycloalkanes with a single ring are named
analogously to their normal alkane counterpart of the same carbon count. So, these are named as
cyclopropane, cyclobutane, cyclopentane, cyclohexane, etc. The larger cycloalkanes, with greater than 20
carbon atoms are typically called cycloparaffins. Cycloalkanes are classified into small, common, medium,
and large cycloalkanes. So, cyclopropane and cyclobutane are the small ones, cyclopentane, cyclohexane,
cycloheptane are the common ones. On the other hand, cyclooctane through cyclotridecane are the medium
ones, and the rest are the large ones.
2.1 Nomenclature
The IUPAC rules for naming cycloalkanes are as follows :
2.1.1 Monocyclic Alkanes

Rule 1: The name of an unsubstituted cycloalkanes is obtained by attaching the prefix cyclo-to the name of
the corresponding normal alkane having the same number of carbon atoms as in the ring. For convenience
and simplicity, cycloalkanes are often represented by simple geometric figures :
cyclopropane cyclobutane cyclopentane cyclohexane cycloheptane
A triangle is used for for cyclopropane, a square for cyclobutane, a pentagon for cuyclopentane a hexagon for
cyclohexane and so on. It is understood that each corner represents one carbon and two hydrogens.
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Rule 2 : Substituents on the ring are named and their positions are indicated by numbers. The ring is
numbered so that the carbon bearing the substituents will have the lowest numbers. If possible
stereochemistry is also indicated.
Br Me
Me
Cl H
H Cl
OH Et
1– Ethyl– Trans-1,2-
3–Methylcyclo 3–Bromo
3– methyl dichloro
hexanol cyclopentene
cyclohexane. cyclopropane
Rule 3: This rule primarily deals with naming of alkyl-subsituted cycloalkanes. One has to count the number
of carbon atoms in the ring and also in the largest alkyl substituent. If the number of carbon atoms in the ring is
equal to or greater than the number in the largest substituent, the compound is named as alkyl-substituted
cycloalkane (case 1 shown below). If the number of carbon atoms in the ring is less than the number of carbon
atoms in the substituent, it is named as a cycloalkyl-substituted alkane (case 2).
Ethyl cyclo 1–Cyclopropyl 1–P

ropyl
propane butane Cyclopropane
(case 1) (case 2) (case 3)
If there is a tie between the number of carbons on the cycloakanes part of the molecule and the acyclic alkane
part, choose the cycloalkane as the parent or main chain(case 3).Some other examples are,
CH3–CH–CH2–CHO
Br
2–Cyclopropyl 1–Bromo–2–butyl 3–Cyclobutyl
butane cyclobutane. butanal
2.1.2 Polycyclic Alkanes

The naming of polycyclic alkanes such as bicyclic alkanes and spiro alkanes is more complex, with the base
name indicating the number of carbons in the ring system, a prefix indicating
the number of rings (e.g., "bicyclo"), and a numeric prefix before that indicating
the number of carbons in of each ring, excluding of junctions. For instance, a
bicyclooctane that consists of a six-member ring and a four-member ring,
which share two adjacent carbon atoms that form a shared edge, is
Fig. 4: [4.2.0]–bicyclooctane
[4.2.0]-bicyclooctane.
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That part of the six-member ring, excluding of the shared edge has 4 carbons. That part of the four-member
ring, exclusive of the shared edge, has 2 carbons. The edge itself, excluding of the two vertices that define it,
has 0 carbons. As IUPAC nomenclature system is constantly being revised, so in the above example
[4.2.0]-bicyclooctane would be written as bicyclo[4.2.0]octane.
Another example of the IUPAC method is discussed below. In this example the base name is listed first, which
indicates the total number of carbons in both rings including the carbons making up the shared edge is
heptane, which means hept or 7 carbons, and ane, which indicates only single bonding between carbons.
Then in front of the base name is the numerical prefix, which lists the number of carbons in each ring,
excluding the carbons that are shared by each ring, plus the number of carbons on the bridge between the
rings. In this case there are two rings with two carbons each and a single bridge with one carbon, excluding
the carbons shared by it and the other two rings. There is a total of three numbers and they are listed in
descending order separated by dots, thus: [2.2.1]. Before the numerical prefix is another prefix indicating the
number of rings (here the prefix is bicyclo). Thus, the name is bicyclo [2.2.1]heptane.
Fig. 5: Bicyclo [2.2.1] heptane
Methods of Preparation
There are a number of methods available for the preparation of cycloalkanes. Some of the important
methods of preparation are discussed below,
1. From calcium salts of dicarboxylic acids : When the calcium or barium salts of dicarboxylic acids
are heated, cyclic ketones are formed. The cyclic ketones can be readily converted into the
corresponding cycloalkanes by Clemmensen reduction.
O
CH2–C–O– Clemmensen
Ca2+ ∆
O
–CaCO3 reduction
CH2–C–O–
O Cyclopropane
Calcium succienate
Another example is
O
CH2–CH2–C–O– Clemmensen
Ca2+ O
∆
reduction
CH2–CH2–C–O–
O Cyclopentane
Calcium adipate
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2. From dihalides : Terminal dihalides when allowed to react with sodium or zinc from cycloalkanes.
This reaction is an extension of Wurtz reaction. However, there is a limitation that the reaction is useful
for the preparation of 3-to 6 membered rings only.
CH2–CH2–Cl
∆
+2Na +2NaCl
CH2–CH2–Cl
1,4– Dichlorobutane
Another example is: –Cl
∆
+2Na +2NaCl
–Cl
1,3–Dichloropropane
3. From esters of dicarboxylic acids: Esters of dicarboxylic acids when treated with sodium metal
undergo intramolecular acetoacetic ester condensation and a β − kentoester is formed. This is an
important name reaction termed as Dieckmann Reaction. The β −ketoesters on hydrolysis yield
cyclic ketones. These on reduction yield the corresponding cycloalkanes.
O
CH2–CH2–C–OE Na H3O+
–C2H5OH
O O
CH2–CH–H
COOEt
COOEt COOH
Diethyl adipate
heat,
–CO2
Zn(Hg)
conc O
HCl
Cyclopentane
4. From aromatic hydrocarbons: Six-membered cycloalkanes can be prepared by the catalytic
reduction of benzene and its derivatives. The reaction scheme is shown below,
H2, Ni
∆, High pressure
Benzene Cyclohexane
CH3 CH3
H2, Ni
∆, High pressure
Toluene Methylcyclohexane
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5. From alkenes: When alkenes are allowed to react with methylene iodide (CH2I2) in the presence of
zinc-copper couple, cyclopropane derivatives are formed. Some of the examples are shown here,
Zn+Cu
CH3–CH2CH=CH2+CH2I2 Ether
CH3–CH2–CH–CH2+ZnI2
But–l–ene
CH2
Ethyl cyclopropane
Zn+Cu
CH3–CH=CH–CH3+CH2I2 Ether
CH3–CH–CH–CH3+ZnI2
But–2–ene
CH2
1,2–Dimethyl
cyclopropane
It is again a commonly used name reaction used in synthetic organic chemistry known as Simmons-Smith
Reaction. This reaction is stereospescific with respect to an alkane. Substituents which are trans in the
alkenes are trans in the cyclopropane as well. The reaction scheme is shown below:
Me Me
Me Me
CH2I2
C=C Zn–Cu,Ether
HC — CH
H H
CH2
cis–2–Butene cis–1,2– Dimethyleydo
propane
Me Me
Me
CH2I2
C=C Zn–Cu,Ether
HC — CH
H H
CH2 Me
trans–1,2– Dimethyl
cyclopropane
Mechanism: It is a one step or concerted reaction. Both new carbon-carbon bonds are formed
simultaneously. The nucleophilic carbon-carbon double bond causes loss of the iodide leaving group and the
electrons from the nucleophilic C – Zn bond is used to form the other carbon-carbon bond.
Cu
I − CH 2 − I + Zn  
→ I − CH 2 − ZnI
ether
Me Me
Me Me
C=C C—C + Zn I2
H H
H CH2 H
I–CH2–ZnI cis–1,2– Dimethylcyclopropane
Physical Properties
1. Physical state: Cyclopropane and cyclobutane are expectedly gases at room temperature due to
subdued intermolecular forces. The remaining cycloalkanes are liquids.
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2. Solubility: Cycloalkanes are insoluble in water but dissolve in ethanol and ether. It is solely due to
their non-polar nature.
3. Melting and boiling points: Melting and boiling points of cycloalkanes show a gradual increase with
the increase in molecular weight just like their acyclic counterparts.
Table 2: Melting and boiling point of some cycloalkanes
Compound bp°C mp°Cc
Cyclopropane –32.8 –127.4
Cyclobutane 12.5 –90.7
Cyclopentane 49.3 –13.9
Cyclohexane 80.7 6.6
4. IR spectrum: Like alkanes, they show characteristic C - H stretching absorption at 2850-3050 cm −1.
Wavelength (µm)
2.5 3 4 5 6 7 8 9 10 12 14 16 20 24
100
80
Transmittance(%)
60
40
20
0
4000 3500 3000 2600 2200 2000 1800 1600 1400 1200 1000 800 600 400
Wavenumber (cm–1)
Fig. 6: IR spectrum of cyclohexane
Chemical Properties
Cycloalkanes resemble alkanes in their chemical inertness towards various reagents. However, cyclopropane
and cyclobutane are the exceptions due to a clear cut reason. It is the high bond angle strain which makes
these two compounds highly reactive towards a host of reagents. With certain reagents they undergo
ring-opening and give addition products.
Ring–Opening Reactions:
1. Addition of Cl2 and Br2 : Cyclopropane can add to halogens like chlorine and bromine in the dark to
form addition products. CCl4 is used as a solvent.
CH2
CCl4
CH2 +Br2
dark Br Br
CH2 1,3–Dibromo
propane
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Cyclobutane and higher homlogues do not give this reaction due to the relaxed bond angle strain.
2. Addition of HBr and HI: Cyclopropane reacts with concentrated HBr and HI to yield
1-bromopropane and 1-iodopropane respectively. Cyclobutane and higher members do not give this
reaction.
I
+HI
1–Iodopropane
3. Addition of H2SO4 : Cyclopropane reacts with concentrated H2SO4 to yield acyclic sulfonic acid
formed in the following manner. It is important to remind that cyclobutane and higher members again
like the previous cases do not give this reaction.
4. Addition of hydrogen: Cyclopropane and cyclobutane reacts with hydrogen in the presence of Ni
catalyst to give propane and n-butane respectively. It is important to note that higher temperature is
required for cyclobutane to take part in the reaction.
5. Oxidation: Cycloalkanes undergo oxidation with hot alkaline potassium permanganate to form
dicarboxylic acids. One such example is shown below,
CH2–CH2–COOH
alk. KMnO4
∆ CH2–CH2–COOH
Adipic acid
Cyclohexane
6. Addition to an unsymmetrical cycloalkane: The addition of a unsymmetrical reagent such as HX

like concentrated H2SO4 or HBr etc to an unsymmetrical substituted cyclopropane ring such as
methylcyclopropane causes the breaking of a C-C bond in the ring along the dotted line to yield a
2-substituted butane as the major products. This product is derived from the most stable carbocation
intermediate according to a reaction scheme which is being shown here,
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CH3 CH3 CH3

H+ x–
CH CH+ CH — X
H2C CH2 H2C CH2 CH2–CH3
H
Substitution Reactions:
Substitution with Cl2 and Br2: Cycloalkanes react with halogens like chlorine and bromine even in the
presence of UV light to given substitution products.
UV
+Cl2 Cl +HCl
radiation
Cyclopropane Chlorocyclopropane
UV
+Cl2 Cl +HCl
radiation
Cyclopentane Chlorocyclopentane
Mechanism : Following steps are involved:

Step 1. Initiation: Chlorine undergoes hemolytic fission to form chlorine free radicals.
Step 2. Chain-Propagation Steps: (a) Chlorine free radical attacks the cyclohexane molecule to give HCl
and cyclohexyl free radical. Here, it is important to note that generally fish-hook arrows are used to indicate
the migration of single electrons. Steps (a) and (b) are continuously repeated.
Cl• + H H–Cl + •
Cyclopentane Cyclopentyl
free radical
Step 3. Chain-Termination Steps: The above chain reaction comes to halt when any two free radicals
combine. For example,
Cl• +Cl• Cl–Cl
• + • —
• + Cl• —Cl
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3. Stability of Rings and Ring Strain

The carbon atoms in cycloalkanes are sp3 hybridized and therefore a deviation is observed from the ideal
tetrahedral bond angles of 109°28'. This causes an increase in potential energy and an overall destabilizing
effect. Eclipsing of hydrogen atoms is an important destabilizing effect, as well. The strain energy of a
cycloalkane is the theoretical increase in energy caused by the compound's geometry, and is calculated by
comparing the experimental standard enthalpy change of combustion of the cycloalkane with the value
calculated using average bond energies.
Cycloalkanes tend to give off a very high and non-favorable energy, and the spatial orientation of the atoms
causes the ring strain. When atoms are close together, their proximity is highly unfavorable and causes steric
hindrance. The reason why one does not want ring strain and steric hindrance is because heat will be released
due to an increase in energy; therefore, a lot of that energy is stored in the bonds and molecules, causing the
ring to be unstable and reactive. Another reason we try to avoid ring strain is because it will affect the
structures and the conformational function of the smaller cycloalkanes. One way to determine the presence of
ring strain is by its heat of combustion. By comparing the heat of combustion with the value measured for the
straight chain molecule, one can determine the stability of the ring. There are different types of strain, but the
types which are the most important are eclipsing or torsional strain and bond angle strain. Bond angle strain
causes a ring to have a poor overlap between the atoms, resulting in weak and reactive C-C bonds. An
eclipsed spatial arrangement of the atoms on the cycloalkanes results in high energy.
3.1 Types of Strain

There are different types of ring strain, as discussed earlier. Some of these are,
1. Transannular strain is defined as the crowding of the two groups in a ring.
2. There is also eclipsing strain, also known as torsional strain, which means that the intramolecular
strain present is due to the bonding interaction between two eclipsed atoms or groups.
3. Another type of strain is called the bond angle strain, and it is present when there is a poor overlap
between the atoms. There must be an ideal bond angle to achieve the maximum bond strength and
that will allow the overlapping of the atomic orbitals.
Cyclopropane is necessarily planar or flat, with the carbon atoms at the corners of
an equilateral triangle. The 60º internal bond angles are much smaller than the
optimum 109° 28' angles of a normal tetrahedral carbon atom. Consequently there is
huge angle strain as stated by Baeyer strain theory and the resulting angle strain
dramatically influences the high chemical reactivity of cyclopropane.
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Cyclopropane also suffers substantial eclipsing strain or torsional strain, since all the carbon-carbon bonds
are fully eclipsed.
Cyclobutane reduces some bond-eclipsing strain by folding so that the out-of-plane dihedral angle is about
25º, but the total eclipsing and angle strain remains high.
Cyclopentane has very little angle strain as the internal angles of a regular pentagon are 108º, but its
eclipsing strain would be large (about 10 kcal/mol) if it remained planar.
Consequently, the five-membered ring adopts non-planar puckered conformations whenever possible, as
shown above.
Rings larger than cyclopentane would have angle strain if they were planar. However, this strain, together
with the eclipsing strain inherent in a planar structure, can be relieved by puckering the ring. Cyclohexane is
a good example of a carbocyclic system that virtually eliminates eclipsing and angle strain by adopting
non-planar conformations, such as those shown below. Cycloheptane and cyclooctane have greater strain
than cyclohexane. The major contributory of this strain is due to steric hindrance by groups on opposite sides
of the ring also termed as transannular crowding as stated earlier.
cyclohexane cycloheptane cyclooctane
O-126
Solved Examples
Example 1: Trans-1,2-dimethylcyclopropane is more stable than cis-1,2-dimethyl–
cyclopropane. Why? Drawing a picture of the two will help your explanation.
Solution : The cis isomer suffers from steric hindrance and has a larger heat of combustion.
Example 2: Out of all the cycloalkanes, which one has the most ring strain and which one is
strain free? Explain.
Solution : Cyclopropane- ring strain. Cyclohexane chair conformation- ring strain free.
Example 3: What does it mean when people say "increase in heat leads to increase in energy"
and how does that statement relate to ring strains?
Solution : When there is an increase in heat there will be an increase of energy released therefore there will
be a lot of energy stored in the bond and molecule making it unstable.
Example 4: Why is that the bigger rings have lesser strains compared to smaller rings?
Solution : Smaller rings are more compacts, which leads to steric hindrance and the angles for these smaller
rings are harder to get ends to meet. Bigger rings tend to have more space and that the atoms attached to the
ring won't be touching each other as much as atoms attached to the smaller ring.
3.2 Ring Strain Energy

Ring strain is highest for cyclopropane, in which the carbon atoms form a triangle and therefore have 60°
C-C-C bond angles. There are also three pairs of eclipsed hydrogens. The ring strain is calculated to be
around 120 kJ/mol. Cyclobutane has the carbon atoms in a puckered square with approximately 90°bond
angles; "puckering" reduces the eclipsing interactions between hydrogen atoms. Its ring strain is therefore
slightly less, at around 110 kJ/mol. For a theoretical planar cyclopentane the C-C-C bond angles would be
108°, very close to the measure of the tetrahedral angle. Actual cyclopentane molecules are puckered, but
this changes only the bond angles slightly so that angle strain is relatively small. The eclipsing interactions are
also reduced, leaving a ring strain of about 25 kJ/mol. In cyclohexane the ring strain and eclipsing interactions
are negligible because the puckering of the ring allows ideal tetrahedral bond angles to be achieved. As well,
in the most stable chair form of cyclohexane, axial hydrogens on adjacent carbon atoms are pointed in
opposite directions, virtually eliminating eclipsing strain. After cyclohexane, the molecules are unable to take
a structure with no ring strain, resulting in an increase in strain energy, which peaks at 9 carbons (around 50
kJ/mol). After that, strain energy slowly decreases until 12 carbon atoms, where it drops significantly; at 14,
another significant drop occurs and the strain is on a level comparable with 10 kJ/mol. After 14 carbon atoms,
sources disagree on what happens to ring strain, some indicating that it increases steadily, others saying that it
disappears entirely. However, bond angle strain and eclipsing strain are an issue only for smaller rings.
3.3 Baeyer Strain Theory

In 1885, Baeyer enunciated a theory to explain the relative stability of the first few cycloalkanes. He based his
theory on the fact that the normal angle between any pair of bonds of a carbon atom is 109°28' . Baeyer
postulated that any deviation of bond angles from the normal tetrahedral value would impose a condition of
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internal strain on the ring. He also assumed that all cycloalkanes were planar and thus calculated the angles
through which each of the valence bond was deflected from the normal direction in the formation of the
various rings. This he called bond angle strain, which determined the stability of the ring.
In cyclopropane, the three carbon atoms occupy the corners of an equilateral triangle. Thus cyclopropane
has C-C-C bond angles of 60°. This implies that the normal tetrahedral angle 109°28' between any two bonds
1 24.75°
is compressed to 60° , and that each of the two bonds involved is pulled in by 5° (109° 5°−60° ) =
2 24 ° 44
(Fig. 7) The value 24°44' then represents the bond angle strain or the deviation through which each bond
bends from the normal tetrahedral direction. The angle strain for other cycloalkanes can be calculated in the
same way. The value are given in Table 3. Whether the angle strain is positive or negative, its magnitude
determines the extent of strain in the ring.
Table 3: Strain of some common cycloalkane ring–sizes
Ring size Strain energy (Kcal/mol) Ring size Strain energy (Kcal/mol)
3 27.5 10 12.4
4 26.3 11 11.3
5 6.2 12 4.1
6 0.1 13 5.2
7 6.2 14 1.9
8 9.7 15 1.9
9 12.6 16 2.0
The angle strain is maximum in the case of cyclopropane. Thus according to the Baeyer strain theory,
cyclopropane must be highly strained molecule and consequently most unstable. The cyclopropane ring
should therefore be expected to open-up on slightest provocation and thus releasing the strain within it. This
is actually so. Cyclopropane undergoes ring-opening reactions with Br2,HBr and H2(Ni) to give open-chain
addition products. The angle strain in the case of cyclobutane is less than that in case of cyclopropane. This
results into enhanced stability. Thus as expected, cyclobutane undergoes ring opening reactions but only
under more drastic conditions. The angle strain is minimum in the case of cyclopentane. This implies that
cyclopentane is under least strain and should be most stable. Thus it is not surprising that cyclopentane does
not undergo ring-opening reactions. The angle strain in the case of cyclohexane is higher than that in case of
cyclopentane. This strain increases continuously with increases in the number of carbon atoms in the ring.
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According to the Baeyer Strain theory, cyclohexane and the higher cycloalkanes should becomes
increasingly unstable and hence more reactive. Contrary to this prediction, cyclohexane and the higher
members are found to be quite stable. They do not undergo ring-opening reactions. Instead they resembles
open-chain alkanes in being highly unreactive. Like acyclic alkanes, these compounds react by substitution.
Thus the Baeyer Strain theory satisfactorily accounts for the exceptional reactivity of cyclopropane,
cyclobutane.
3.4.Sache-Mohr Theory
In order to account for the stability of cyclohexane and other higher members, Sache and Mohr (1918)
proposed that such rings can becomes free form strain if all the ring carbons are not forced into one plane, as
was assumed by Baeyer. If the ring assumed a 'folded' or 'puckered' condition and the normal tetrahedral
angles of 109°28' are retained then as a result, the strain within the ring is relieved. For example, cyclohexane
can exist in two non-planar puckered conformations both of which are completely free from strain. These are
called the chair form and the boat form because of their shape. Such non-planar strain-free rings in which the
ring carbons can have normal tetrahedral angles are also possible for higher cycloalkanes.
The chair form of cyclohexane reveals that the hydrogen atoms can be divided into two categories. Six of the
bonds to hydrogen atoms point straight up or down almost perpendicular to the plane of the moelcule. These
are called axial hydrogens. The other six hydrogens lie slightly above or slightly below the plane of the
cyclohexane ring, and are called equatorial hydrogens.
3.5 Molecular Orbital Theory and Banana Bonding

One can explain the relative stability of cycloalkanes in terms of MO theory. It is known that a covalent bond
between two atoms is formed by the overlap of orbitals of the atoms involved. The greater the extent of
overlap the stronger is the bond formed. The atomic orbitals overlap to the maximum extent if they overlap
along their axes. As the axes of sp3 orbitals are at angles of 109°28' to each other, the C – C bonds will have
their maximum strength if the C - C - C bond angles have a value of 109°28′ .
O-129
Cyclopropane has C - C - C bond angles of 60°. Cyclobutane has C - C - C bond angles have a value of 90°.
The higher cycloalkanes and alkanes have C - C - C bond angles of 109°28′ . As shown in figure no 9. the
small bond angles of cyclopropane indicate that the overlap of sp3 orbitals of carbon in alkanes for example in
propane.
The bond angles of cyclopropane are less than the bond angles of cyclobutane, which in turn are less than the
bond angles of higher cycloalkanes or n-alkanes. Therefore, the overlap of orbitals in cyclopropane is less
than that in cyclobutane, which in turn is less than that in higher cycloalkanes or n-alkanes. The overlap of sp3
orbitals of carbon in cyclopentane, higher cycloalkanes or n-alkanes is maximum because in these cases it is
possible for the sp3 orbitals to overlap along their axes, the bond angle being approximately equal to 109°28' .
This implies that the C - C bonds in cyclopropane are weaker than the C - C bonds of cyclobutane, which in
turn are weaker than the C - C bonds in higher cycloalkanes and n-alkanes. Thus, it is not surprising that
cyclopropane undergoes ring-opening reactions very readily and more drastic conditions are required to
bring about the cleavage of the cyclobutane ring. Cyclopentane and higher members, as expected, do not
undergo ring opening reactions and behave very much like the alkanes.
O-130
Exercise
(iv) H2SO4 Br2
CH3–CH2–C H–CH3 A B
1. Describe Baeyer's strain theory. What are the Cl alc KOH alc KOH
defects in it and what modification have been made C D
by Sachse in it. [Bund. 2008; Meerut 2010] 6. (i) Identify the product and give a
2. (i) Explain the mechanism of chlorination of plausible mechanism :
methane. CH3 conc
H2SO4
(ii) Explain the mechanism of Kolbe reaction.
∆
(iii) How cyclo hexanol is converted to cyclo OH
hexane. [Kashi 2010]
(ii) Write short notes on the following :
3. (i) Write the mechanism of free radical
(a) Acidity of alkynes
halogneation of alkane.
(b) Kinetic and thermodynamic
(ii) Write Baeyer's strain theory for cycloalkanes.
control. [Lko. 2011]
What are the limitations of this theory?
[Kashi 2011] 7. Explain the mechanism of free radical
4. (i) Account for the ring strain of halogenations of alkanes taking chlorination of
cyclopropane in terms of orbital methane as an example. [Hazaribagh 2008, 2010]
overlap.
(ii) Why Corey House reaction is better than Short Answer Type Questions
Wurtz reaction ? Identify A, B, C and D. 1. Discuss stability of cycloalkanes on the basis of
Li / ether
2 Cholorobutane  → Baeyer's strain theory.
cut
A  → B  
C H 1Br
5 1 → D + C or
(iii) Which of the isomeric pentane can form only Discuss banana bond in cyclopropane.
[Bund. 2009; Agra 2008]
one monochloro substitution product?
justify. [Lko. 2009] 2. What is Corey House synthesis ? [Meerut 2012]
5. Identify the products A, B, C and D formed in each 3. Give the mechanism of the halogenation reaction.
of the following reactions and also name the type of [Agra 2008,09]
reaction involved in each step : [Lko. 2011] 4. Discuss the stability of cycloalkanes on the basis of
CH3 Baeyer's strain theory.
(i)
HBr [Kanpur 2010; Hazaribagh 2009]
CH3–CH2–C=CH–CH2–CH3 A
5. Explain the following :
aq KOH H2SO4
B C (i) Sachse-Mohr theory.
170°c
aq KOH
(ii) Alkanes are relatively unreactive.
(ii) CH3–CH2–C H–CH2–CH3 A [Kanpur 2011]
6. Write short note on Baeyer strain theory.
Cl
H2SO4 C6H5COOOH4 CH3OH [Avadh 2008, 10]
B C 7. Give two methods for the preparation of large ring
H2SO4
cycloalkanes. [Avadh 2010]
(iii) OH
H2SO4 8. Explain the mechanism of free redical halogenation
NBS
A B of alkanes taking chlorination of methane as
alc KOH alc KOH
C D example. [Kashi 2008]
O-131
9. What is Saytzeff rule? Explain it taking example of 9. Why boat form of cyclo hexane is less stable than
the mechanism of dehydration of alcohols. chair form? [Kashi 2010]
10. Write a note on peroxide effect. [Kashi 2008] 10. Write IUPAC name of the given compound:
11. Draw structure of all possible isomers of alkane H3C–CH–CH2–CH3
having molecular formula C5H12. [Kashi 2011] CH3–CH–CH–CH2–CH3
12. What is the difference between conformation and
H3C–CH–CH3
configuration? Give boat and chair conformation of [Lko. 2008]
cyclohexane. Explain the potential energy 11. Chlorination of methane in presence of light is an
relationship among conformation of cyclohexane. exothermic reaction.Why? [Lko. 2009]
[Lko. 2010]
12. Why butene-2, is more stable than butene-1?
13. Give the mechanism of the following : [Lko. 2010]
(i) Kolbe reaction 13. Explain banana bonds. [Lko. 2010]
(ii) Chlorination of methane in the presence of
14. The melting point of n-alkanes with even number of
sunlight. [Lko. 2011] carbon atoms is higher than those with odd number
14. Write a short note on banana bond. [Lko. 2011] of carbon atoms.Why? [Lko. 2011]
15. Prove that the mechanism of chlorination of 15. Write down all possible isomers of n-pentane and
methane involves the formation of free radicals as arrange than is decreasing order of their boiling
intermediates. [Rohd. 2009, 10] point. [Lko. 2011]
16. Give the mechanism of Wurtz reaction. It this 16. Give the name and structure of alkanes that yield
reaction suitable for the preparation of the following products on ozonolysis.
unsymmetrical alkane? [Rohd. 2009,10] (i) Only acetone
17. Write a note on cracking. [Rohd. 2011] (ii) Acetaldehyde and formaldehyde
18. n-Alkanes generally have higher boiling and melting [Rohd. 2009]
points than corresponding branched chain alkanes, 17. Write short note on Baeyer and Perkin's synthesis.
why? [Rohd 2012,13] [Rohd. 2010]
19. What is Clemmensen reduction?
[Hazaribag 2009,11]
20. Calculate the angle strain in cyclobutane ring.
1. Why propane is more stable than ethane?
[Hazaribag 2010]
[Meerut 2010]
2. Give the mechanism of the Wurtz reaction. Objective Type Questions
[Meerut 2011]
3. Give the reaction mechanism of Kolbe reaction. Multiple Choice Questions
[Kanpur 2008]
1. Which of the following shows no ring strain :
4. Write notes on Clemmensen's reduction reaction.
(a) Cyclo propane
[Kanpur 2008]
°C (b) Cyclo butane
5. CH3CH2CH3 + HNO3 400
 →? + ? + ? + ?
(c) Cyclo heptanes
[Kanpur 2010]
(d) Cyclo hexane [Bund. 2008]
6. Write notes on stability of cycloalkanes?
[Avadh 2009] 2. Sodium salt of an acid on distillation with sodalime
gives ethane. The acid is
7. Define Wurtz reaction.
[Kashi 2008; Hazaribag 2008] (a) CH3COOH
8. What is Wolff-Kishner reduction? (b) HCOOH
[Kashi 2008, 10; Hazaribag 2008] (c) CH3CH2COOH
(d) C6H5COOH [Rohd. 2011]
O-132
3. If an acyclic alkane hydrocarbon contains n carbon

atoms, how many hydrogen atoms it must contain? Fill in the Blank
(a) n (b) 2n 1. The reducing agent used in case of Clemmenson
(c) n+2 (d) 2n + 2 reduction is……….
4. During debromination of meso–dibromobutane, 2. The chlorination of ethane proceeds via………
the major compound formed is mechanism.
(a) n–butane (b) 1– butene 3. n–hexane can be aromatized to ………. .
(c) cis–2–butene (d) trans–2–butene 4. The chlorination of butane yields……… structural
5. The reaction conditions leading to the best yield of isomers.
C2H5Cl are 5. In Zerevitinoff reaction, methyl magnesium
(a) UV light
C2H6(excess) + Cl2  → bromide is converted into ………. .
(b) dark
C2H6 + Cl2  
→ 6. Branched chain alkanes have………boiling point
room temperature than isomeric straight chain isomer.
(c) UV light
C2H6 + Cl2(excess)  → 7. Red P and HI converts propanoic acid into ………. .
(d) UV light
C2H6 + Cl2  → 8. The bond angle strain is the highest in………. .
6. The highest boiling point is expected for 9. The value of bond angle strain is calculated with the
(a) Isooctane help of………. .
(b) n–octane 10. Decarboxylation of cyclopropane carboxylic acid
(c) 2,2,3,3–tetramethylbutane with soda lime yields………. .
(d) n–butane
7. Bromination of an alkane as compared to True/False
chlorination proceeds 1. Kolbe's electrolytic process can be used to prepare
(a) At a slower rate methane.
(b At a faster rate 2. Amalgmated zinc and conc HCl can be used to
(c) With equal rate convert propanoic acid into propane.
(d) With equal or different rate depending upon 3. To prepare odd carbon alkane, Wurtz reaction is
the temperature preferred over Corey House synthesis.
8. Which of the following radicals has maximum stability ? 4. Bigger rings have lesser strains compared to smaller
(a) 3° (b) 2° rings.
(c) Vinyl (d) Benzyl 5. Soda lime is used for decarboxylation of aldehydes
9. Which of the following will have least hindered to alkanes.
rotation about carbon carbon bond? 6. Hydrogenation of alkene to alkane is a syn
(a) Ethane (b) Ethylene hydrogenation.
(c) Acetylene (d) Hexachloroethane 7. Wurtz reaction proceeds via free radical
10. Electrolysis of concentrated solution of sodium mechanism.
propanoate produces the hydrocarbon 8. A side product of Kolbe's electrolytic process is
(a) Methane (b) Ethane formation of ester.
(c) Propane (d) Butane 9. The bond angle strain value for cyclopropane is 30°.
11. The reactivity of hydrogen atom in an alkane 10. Bromination of alkanes is more selective than
towards substitution by bromine atom is chlorination.
(a) 1° H > 2° H > 3° H
(b) 1° H < 2° H < 3° H
(c) 1° H > 2° H < 3° H
(d) 1° H < 2° H > 3° H
O-133
Answers

1. (d) 2. (c) 3. (b) 4. (d) 5. (a)
6. (b) 7. (a) 8. (d) 9. (a) 10. (d)
11. (b)
Fill in the Blank

1. amalgmated zinc 2. free radical 3. benzene
and conc. HCl
4. 4 5. methane 6. lower
7. propane 8. cyclopane 9. Baeyer strain theory
10. cyclopropane
True/False
1. False 2. False 3. False
4. True 5. False 6. True
10. True
O-134
Hints and Solutions

CH 3
|
HBr
5. (i) CH 3 − CH 2 − C = CH − CH 2 − CH 3  →
CH 3
|
CH 3 − CH 2 − C − CH 2 − CH 2 − CH 3
|
Br
↓ aq KOH
CH 3
|
CH 3 − CH 2 − C − CH 2 − CH 2 − CH 3
|
OH
Conc.
↓ H 2 SO4 , 170° C
CH 3
|
CH 3 − CH = C − CH 2 − CH 2 − CH 3
6. (i) CH3
conc.
H2SO4, ∆
OH

18. Due to more surface area.
Very Short Answer Type Question

5. It is an example of vapor phase nitration
11. C–Cl bond is very strong.
19. O
||
R − C− R ′      → R − CH 2 − R ′
NH 2 −NH 2,
KOH, CH 2 − OH
|
CH − OH
2

2. (c) It is a decarboxylation technique and the carboxylate carbon is last in the form of carbon dioxide.
8. (d) Stability order of C free radical benzylic 3°>2°>1°> vinyl
9. (a) C–C (Single bond) has least hindrance
❍❍❍
Unit-II
O-135
C HAPTER 4
Stereochemistry of Organic
Compounds
1. Introduction
In organic chemistry, a number of organic compounds having different physical and chemical properties can
be represented by the same molecular formula. The property by virtue of which organic compounds possess
different physical and chemical properties and have the same molecular formula is known as isomerism and
the different compounds are known as isomers or isomerides.Since the isomers are constituted of the same
number of atoms, so it is clear that the difference in their properties must be due to the difference in the
relative arrangement of the atoms within the molecules.
1.1 Types of Isomerism

The difference in the relative arrangement refers to either different structural arrangements or different spatial
arrangements. On this basis, two types of isomerism are observed mainly. These are
1. Structural isomerism
2. Stereoisomerism
The complete flow sheet of classification of isomerism is,

Isomerism
Structural isomerism Stereoisomerism
Chain Position Functional Metamerism Geometrical Optical

isomerism isomerism group isomerism isomerism
isomerism
Some more types of isomerism are also possible like tautomerism. It is also considered as a type of structural
isomerism. Some text treats conformational isomerism as a type of stereoisomerism although it is not a true
type because conformational isomers are rapidly interconvertible.
O-136
2. Structural Isomerism
If the isomers have the same molecular formula but they differ in the relative arrangement of atoms, it is called
structural isomerism. In structural isomers, the structural formulae of the isomers differ whereas the molecular
formula remains same. This type of isomerism is further divided into various types.
2.1 Chain Isomerism

Chain isomerism arises due to the difference in the structure of carbon chain. It is sometimes also referred as
nuclear isomerism. The difference is in the length of the carbon chain or in the size of the carbon ring. For
example,
1. n–butane and isobutane are chain isomers.
CH3 – CH2– CH2 – CH3 CH3 – CH – CH3
|
n–butane CH3
isobutane
2. Cyclohexane and methylcyclopentane are nuclear isomers.
CH3
CH2 CH
CH2 CH2 CH2 CH2
CH2 CH2
CH2 CH2
CH2
cyclohexane methycyclopentane
3. C5H12 has three chain isomers.

CH3
CH3CH2CH2CH3 CH3CH2–CH–CH3 CH3 C CH3
CH3 CH3
n–pentane Isopentane neopentane
4. C4H9NH2 also shows chain isomerism. Some of the examples are,

CH3
CH3CH2CH2NH2 CH3 C–NH2
CH3
n–butylamine tert.butylamine
2.2 Positional Isomerism

This isomerism arises due to the difference in position of either substituent like halogen atom or nitro group or
functional group in the same carbon chain.For example,
1. CH3–CH2 –CH = CH2 and CH3–CH = CH–CH3 → →
1-Butene 2-Butene
are positional isomers.
O-137
2. CH3– CH2– CH2– I and CH3 –CH–CH3

|
I
1–iodopropane 2–iodopropane
are also positional isomers.

3. CH3–CH2–CH–CH2–CH3 and CH3–CH–CH2–CH2–CH3
| |
CH3 CH3
3–methylpentane 2–methylpentane
are positional isomers.
4. C6H4(NO2)2 exhibits following three positional isomers.
NO2 NO2 NO2
NO2
NO2
NO2
o–dinitrobenzene m–dinitrobenzene p–dinitrobenzene
2.3 Functional Isomerism

Functional isomers have the same molecular formula but they differ due to the presence of different
functional groups. As an example, carboxylic acids and esters are functional isomers. Similarly,alcohols and
ethers are also functional isomers. Even aldehydes, ketones, unsaturated alcohols, unsaturated ethers, cyclic
ethers and cyclic alcohols are functional isomers to each other. Cyanides and Isocyanides are also functional
isomers. Some more examples are shown below,
1. C3H6O exhibits the following functional isomers.
O O
CH3–CH2–C–H , CH3–C–CH3 , CH3–OCH=CH2 , CH2=CHCH2OH
Propanal Propanone Methoxyethene 2–propen–1–o1
(allyl alcohol)
2. C3H6O2 shows following functional isomers.

O O O
CH3–CH2–C–OH , CH 3–C–OCH3 , H–C–OC 2H5
Propanoic acid Methyl ethanoate Ethyl methanoate
(I) (II) (III)
3. C2H6O exhibits two functional isomers.
CH3–CH2 –OH ; CH3–O–CH3
Ethanol Dimethyl ether
O-138
2.4 Metamerism
It is caused by the attachment of different radicals/groups to a polyvalent atom (i.e. an atom having more
than one valency). A metamer can be obtained by shifting one or more CH2 groups from one side of the
polyvalent functional group to the other side. These isomers are of same homologous series. Metamerism is
found to occur in amines, ethers, ketones, esters etc.
For example,
(i) C4H10O exhibits two metameric ethers as shown below,
CH3 – CH2 – O– CH2 – CH3 and CH3 – CH2 – CH2 – O – CH3
Diethyl ether Methyl n–propyl ether
(ii) C5H10O2 exhibits following metamers as shown,
O O
CH3CH2CH2–C–OCH3 , CH3CH2–C–OCH2CH3
Methyl butanoate Ethyl propanoate
O O
CH3–C–OCH2CH2CH3 , H–C–OCH2CH2CH3
n–propyl ethanoate n–butyl methanoate
(iii) Similarly, C4H10NH exhibits following metamers.

C2H5–NH–C2H5 CH3–NH–CH2CH2CH3
Diethyl amine N–methylpropyl amine
2.5 Tautomerism
This is a special type of functional isomerism where, functional isomers exist in equilibrium with each other.
Such isomers are called tautomers. The necessary condition for this type of isomerism is the presence of
hydrogen, α − (a hydrogen on a carbon adjacent to carbon of functional group) to the carbonyl group.A very
common, form of tautomerism is that between a carbonyl compound containing an α hydrogen and its enol
form. This type of isomerism is also known as keto enol isomerism.
R' R'
R – C – C – R'' R – C = C – R''
O O
H H
Keto form Enol form
In simple compounds (when R" = H, alkyl, OR, etc) the equilibrium lies more towards the left. The reaction
can be seen by examining the bond energies of various bonds. The keto form differs from the enol form in
possessing a C–H, a C–C, and a C = O bond whereas the enol form has a C = C, a C–O and an O–H bond.
The keto form is thermodynamically more stable than enol form and enol forms are normally not isolated.
However in certain cases, a larger amount of the enol form is present, and it can even be the predominant
form.The percentage of enol form increases in the order simple aldehydes and ketones <β – keto esters <β –
diketones <β – diketones having phenyl group < phenols. This increase in the enol content is due to the fact
O-139
that the enol form of the above type of compounds is increasingly stabilized by resonance and hydrogen
bonding than the corresponding keto form. There are four main types of the more stable enol forms.
1. Molecules in which the enolic double bond is in conjugation with another double bond. For example in
molecules like acetoacetic ester, the enol form is stabilized by internal hydrogen bonding, which is
unavailable to the keto form.
CH
OEt
CH3– C C
O—H O
2. Molecules that contain two or three bulky aryl groups. For example, in 2,2–dimesitylethanol, the keto
content at equilibrium is only 5%.
Me
Ar Ar
C=C–H CH–C–H Ar=Me
Ar Ar
OH O
Me
In such cases, the steric hindrance destabilizes the keto form. In the enol form, two aryl groups are
about 120° apart, but in keto form they must move closer together (~109.5°). Such compounds are
often called Fuson–type enols.
3. Highly fluorinated enols are also stable than their corresponding keto form.
200°C
CF2=C–CF3 CF2H–C–CF3
OH O
The enol form of such compounds can be kept at room temperature for long period of time becaue the
tautomerization reaction is very slow, owing to the electron–withdrawing nature of the fluorines.
4. The enol content would be more than the keto form if the former is stabilized by aromaticity. For
example, phenol is an enol form.
O–H O
H
H
Phenol Cyclohexadienone
In those equilibria, where the enol content is higher than the keto form, the solution produces
red/green/blue colour with neutral FeCl3 solution. The appearance of such a colour on addition of
neutral FeCl3 solution is a test for any enol. Phenol also responds to this test.
Note: The tautomers are not counted while finding the total number of isomers for a given molecular
formula. It means that if an aldehydic compound is an isomer then its enolic form is not considered as
separate isomer.
O-140
Solved Examples
Example 1: (i) Which of the compounds A through K here are enoltautomers of 2-butanone?
OH OH OH OH
CH3 CH3 CH3
CH3
A B C D
OH OH OH OH
E F G H
OH
OH OH
I J K
Solution: (i) E,F,J
Example :(ii) Which of the compounds A through K as shown above are enoltautomers of
2-methylcyclohexanone?
Solution: (ii) A,B
3. Stereoisomerism
In this isomerism the molecular formula as well as the structural formula are same, but the difference lies in
their spatial arrangement. It means that the orientation of the atoms or group of atoms in three dimensional
space is changeable. This is further divided into two sub categories,
1. Optical isomerism 2. Geometrical isomerism
3.1 Optical Isomerism

3.1.1 Optical Activity
Any compound that rotates the plane of plane polarized light in either clockwise or anticlockwise direction is
said to be optically active. The compound which rotates the plane of plane polarized light in clockwise
direction is said to be dextrorotatory(d or + isomer) and the compound which rotates the plane of plane
polarized light in anticlockwise direction is said to be laevorotatory(l or - isomer).
O-141
3.1.2 Non Superimposability and Chirality

If a pure compound is optically active, the molecule is non superimposable on its mirror image. If a molecule is
superimposable on its mirror image, the compound does not rotate the plane of polarized light, it is optically
inactive. The property of non superimposability of an object on its mirror image is called chirality(from the Greek
cheir meaning hand). The relationship between optical activity and chirality is absolute, no exceptions are known.
Chiral object Achiral object

Mirror Mirror
The mirror The mirror

images are not images are
superimposable superimposable
Laft hand Right hand Flask Flask
Fig. 1: Non superimposability and superimposability
As such, the ultimate criterion for optical activity is chirality or non superimposability of the compound on its
mirror image. This is both a necessary and a sufficient condition for a compound to exhibit optical activity.
Any carbon atom which is attached to four different atoms or groups of atoms are termed as chiral or
asymmetric carbon atom.
Y C W
chiral center
Z
Fig. 2: Chiral carbon atom
Some examples of compounds containing chiral and non chiral carbon atoms are shown below,
CH3 CH3 CH3 O
H C Cl H C Cl H C CH2CH3 C
Br Br CH2CH2CH3 H CH3
chiral achiral chiral achiral
Has 4 different atoms Does not have 4 different
bonded to the carbon atoms Has 4 different groups Only has 3 atoms
Y W or groups bonded
bonded to the carbon bonded to the carbon.
to the carbon
Fig. 3: Certain compounds containing chiral and achiral carbon atoms
O-142
3.1.3 Asymmetric Carbon

As discussed earlier a chiral or asymmetric carbon cantains carbon atom that is bonded to four different
atoms or groups loses all symmetry, and is often referred to as an asymmetric carbon. Some more examples
are shown below containing anasymmetric carbon atom. The asymmetric carbon atoms are shown below,
OH
Br
OH
C D
OH OH
A B
Cl
H
O
H
H
3.1.4 Plane Polarised Light
Light contains radiations of different frequencies or wavelengths which can be separated with the help of
prism. The light having radiations of only one frequency is called monochromatic light. In this
monochromatic light the radiations propagate in different planes. If this monochromatic light is passed
through a nicol prism,the radiations traveling in one plane can be obtained. It is important to know that nicol
prism has characteristic so that radiations of only one particular plane can pass through it. The radiations or
light are traveling in only one plane such that all electrical and magnetic vibrations are perpendicular to the
plane of propogation of light, is called plane polarized light. Amangement to obtain plane polarised light is
shown below,
Fixed
polarizer
Plane–polarized
Light
field vector
Electric & source
magnetic
0° field Vectors
α
Sample cell
Movable
Detector [polarizer
Fig. 4: Arrangement to obtain optical activity

O-143
3.1.5 Observed Rotation (α) and Specific Rotation [α]

In chemistry, specific rotation ([α]) is a property of a chiral chemical compound.It is defined as the change
in orientation of monochromatic plane-polarized light, per unit distance-concentration of product, as the light
passes through a sample of a compound in solution.Specific rotation is an intensive property, distinguishing it
from the more general phenomenon of optical rotation. As such, the observed rotation (α) of a sample of a
compound can be used to quantify the enantiomeric excess of that compound, provided that the specific
rotation ([α]) for the compound is known.
Chemists use polarimeters to investigate the influence of compounds in the sample cell on plane polarized
light. Samples composed only of achiral molecules e.g. water or hexane, have no effect on the polarized light
beam. However, if a compound containing chiral carbon is examined the plane of polarization is rotated in
either a clockwise (positive) or counter-clockwise (negative) direction. One enantiomer will rotate polarized
light in a clockwise direction, termed dextrorotatory or (+), and its mirror-image partner in a
counter-clockwise manner, termed a levorotatory or (-). The prefixes dextro and levo come from the Latin
dexter, meaning right, and laevus, for left, and are abbreviated d and l respectively. Since it is not always
possible to obtain or use samples of exactly the same size, the observed rotation is usually corrected to
compensate for variations in sample quantity and cell length. Thus it is common practice to convert the
observed rotation, a, to a specific rotation, [α], by the following formula:
α degrees
[α]TD =
(l dm)×C (gmL–1)
where l (dm)P = cell length in dm, c = concentration in g/ml, D line of sodium spectrum is having the
wavelength 589 nm.Compounds that rotate the plane of polarized light are termed optically active. Specific
rotations are useful in that they are experimentally determined constants that characterize and identify pure
enantiomers.
Example 2: A sample of pure (S)-2-butanol was placed in a 10.0 cm polarimeter tube. Using
the D line of a sodium lamp, the observed rotation at 20°C was α = +104°. The density of this
compound is 0.805 g ml-1. What is the specific rotation of (S)-2-butanol?
Solution: Plugging the numbers into [α]λ T = α /lc we get: [α]DT= (+104°) / (1.00 dm) (0.805 g ml-1) =
+129°. Thus one would write [α]D20 = +129°
Example.3: Calculate the observed rotation of a solution of 0.5245g of

(S)-1-amino-1-phenylethane diluted to a volume of 10.0 ml with methanol at 20°C, using the D
line of a sodium lamp and a 1.00 dm tube. Specific rotation of this material: [α]D23 = -30.0°.
Solution: Solving the specific rotation equation for observed rotation, one will get α= [ α]DT lc. The sample
size is 0.5245 g, but this has been diluted to 10.0 mL, so the sample concentration is 5.245 g in 100 ml.
Plugging in the numbers, we get α = (–30.0°) (1.00 dm) (5.245 g in 100 ml). Solving, we find α = –157°.
3.1.6 Enantiomers
If a molecule is non superimposable on its mirror image, the mirror image must be a different molecule. In
each case of optical activity of a pure compound there are two and only two isomers are possible and these
O-144
are called enantiomers (sometimes enantiomorphs). Enantiomers (from the Greek enantion meaning
opposite)differ in structure only in the left and right–handedness of their orientations like I and II.
Mirror
a a
C C
b e e b
d d
(I) (II)
So, pair of optically active compounds which are mirror images of each other are enantiomers. Physical and
chemical properties of enantiomers are as follows,
1. Enantiomers have identical physical properties like boiling and melting point, solubility etc.
2. They rotate the plane of polarized light in opposite directions, though in equal amounts. The isomer
that rotates the plane to the left (counterclockwise) is called the laevo isomer and designated (–), while
the one that rotates the plane to the right (clockwise) is called the dextro isomer and is designated (+).
Because they differ in this property they are often called optical antipodes.
3. The chemical properties of enantiomers are the same towards achiral reagents, solvents, catalysts, and
conditions. Towards chiral reagents, solvents, catalysts, and conditions enantiomers react at different
rates. The transition states produced from the chiral reactant and the individual enantiomers are not
mirror images. The ∆H ≠ values are different for the two and hence the rates of reaction and the
amounts of product formed. Their rates may be so far apart that one enantiomer undergoes the
reaction at a convenient rate while the other does not react at all. This is the reason that many
compounds are biologically active while their enantiomers are not.
3.1.7 Diastereomers
Such stereoisomers which are optically active isomers but not mirror images with the same set of groups
around, are called diastereoisomers or diastereomers. The following pair of compound constitute
diastereomers.
O O
HC HC
H C OH H C OH
H C OH OH C H
CH2OH CH2OH
Diastereomers
3.1.8 Racemic Mixture or Racemic Modification

A 50:50 mixture of enantiomers has no observable optical activity. Such mixtures are called racemates or
racemic modifications or racemic mixture, and are designated (±). When chiral compounds are created from
achiral compounds, the products are racemic unless a single enantiomer of a chiral co-reactant or catalyst is
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involved in the reaction. The addition of HBr to either cis- or trans-2-butene is an example of racemic product
formation.
•
CH3CH=CHCH3 + HBr (±) CH3CH2C HBrCH3
Chiral organic compounds isolated from living organisms are usually optically active, indicating that one of
the enantiomers predominates (often it is the only isomer present).
3.1.9 Meso Compounds

A meso compound is a compound that contains two or more chiral centres but is optically inactive. It has an
internal plane of symmetry and we can superimpose it on its own mirror image. To identify a meso
compound, you look for two or more chiral centres and an internal plane of symmetry. In the two examples
below, cis-1,2-dihydroxycyclohexane is a meso compound. It has two chiral centres and an internal plane of
symmetry. However, trans-1,2- dihydroxycyclohexane is not a meso compound as it lacks the internal plane
of symmetry.
σ
HO OH HO OH
meso chiral
Fig. 5. Chiral and meso forms of 1, 2–dihydroxycyclohexane
Resolution: A racemate or racemic mixture can be separated into its component enantiomers. The process
is referred as resolution.
3.2 Different Types of Molecules Displaying Optical Activity

Although the ultimate criterion to know whether a compound will exhibit optical activity or not is the non
superimposability of the mirror image (chirality) but other tests may also be used that are simpler to apply.
One such test is the presence of any element of symmetry like plane of symmetry, centre of symmetry and an
alternating axis of symmetry.
1. Plane of symmetry: A plane of symmetry also called a mirror plane is a plane passing through the
molecule such that the molecule is divided into 2 equals parts, one part being the mirror image of other
(the plane acting as a mirror). For example,
b
a d
plane of symmetry
a d
b
Such an isomer is called meso isomer which is optically inactive due to the presence of plane of
symmetry.
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2. Centre of symmetry: A center of symmetry is a imaginary point within the molecule such that a
straight line drawn from any part or element of the molecule to the center and extended an equal
distance on the other side encounters an equal part or element. For example, 2,4–dimethyl
cyclobutane–1,3–dicarboxylic acid possess a centre of symmetry which is the centre of the ring.
CH3 CO2H
H
H H H
CH3
CO2H
Another important example of the compound having a centre of symmetry is the trans–form of dimethyl
ketopiperazine. The compound exists in two forms–cis and trans. The cis–form has no element of symmetry
and hence exists in two enantiomeric forms but on the other hand the trans–form has a centre of symmetry
and therefore, it is optically inactive.
H3C CH3 H3C CO NH H
CO NH
NH CO H H NH CO CH3
H
cis–dimethyl ketopiperazine trans–dimethyl ketopiperazine

having a centre of symmetry
Similarly α–truxillic acid is optically inactive because of the presence of a centre of symmetry.
Ph COOH
H H
H H
COOH Ph
α–truxillic acid
It must be noted that only even–membered rings can possibly possess a centre of symmetry.
3.2.1 Classification of Optically Active Compounds

Optically active compounds may be classified into several categories.
1. Compounds with a chiral carbon atom: If there is only one such atom, the molecule must be
optically active. This is so no matter how slight the differences are among the four groups. For example,
optical activity is present in
BrCH2CH2CH2CH2CH2CH2–CH–CH2CH2CH2CH2CH2Br
CH3
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Optical activity has been detected even in cases such as 1– butanol–1–d, where one group is hydrogen and
another is deuterium.
H
CH3CH2CH2–C–OH
However, the amount of optical rotation is greatly dependent on the nature of the four groups, in general
increasing with increasing differences in polarizabilities among the groups. Alkyl groups have very similar
polarizabilities and the optical activity of 5–ethyl –5–propyl undecane is too low to be measurable at any
wavelength between 280 and 580 nm.
2. Compounds with other quadrivalent chiral atoms: Any molecule containing an atom that has
four bonds pointing to the corners of a tetrahedron will be optically active if the four groups are
different. Among atoms in this category are Si, Ge, Sn and N (in quaternary salts or N–oxides),
Sulphur and Phesphorus, In sulfones the sulphur bonds tetrahedrally, but since two of the groups are always
oxygen, no chirality normally results. However, the preparation of an optically active sulfone (I) in which one
oxygen is 16O and the other 18O illustrates the point that slight differences in groups are all that is necessary.
This has even been reflected in the ester (II) and phosphates (III), both of which are optically active.
16 16 16 O 2–
O O
17 17
—CH2–S— —CH3 PhCH2–O–S– O O–P–OR
18O 18O 18O
(I) (II) (III)
3.2.2 Dissymmetry and Asymmetry

The existence of a reflective symmetry element (a point or plane of symmetry) is sufficient to assure that the
object having that element is achiral. Chiral objects, therefore, do not have any reflective symmetry
elements, but may have rotational symmetry axes, since these elements do not require reflection to operate.
In addition to the chiral vs achiral distinction, there are two other terms often used to refer to the symmetry of
an object. These are:
Dissymmetry: The absence of reflective symmetry elements. All dissymmetric objects are chiral.
Asymmetry: The absence of all symmetry elements. All asymmetric objects are chiral.
3.2.3 Fischer Projections

When we attempt to depict configurations of a chiral centre, we face the problem of representing three
dimensional structures on a two dimensional surface. To overcome this difficulty we use the so-called Fischer
projections. This is the structure of an asymmetric carbon atom drawn in a prescribed orientation and then
projected into a planar surface.
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CH3
CH3
H C Cl
C
CHO
H Cl
CHO
Thus planar formulas of the asymmetric carbon are obtained by placing it so that the two substituents are
horizontal and project towards the viewer (shown by thick wedge-like bonds), while the two other
substituents are vertical and project away from the viewer (shown by dotted bonds). Hence we may draw the
two configurations of lactic acid by Fischer projection as
Mirror
CH3 CH3
H C OH OH C H
COOH COOH
(I) (II)
In these formulas the horizontal bonds i.e., C-OH and C-H project towards us out of the plane of the paper
whereas the vertical bonds i.e., C-COOH and C-CH3 project away from us. Furthermore, since the vertical
bonds are actually behind the plane of the paper, the formula may be rotated by an angle of 180° (not by 90°
or 270°). Inspection of the models shows that odd interchange of a pair of substituents inverts the
configuration (changes one enantiomer into its mirror image), whereas even number of such interchanges
does not produce enantiomer. Thus interchanging of -H for -OH in I gives the enantiomer II, while the
interchange of CH3 for -COOH and-H for -OH leaves the configuration unchanged.
3.2.4 Relative Configuration

While discussing optical isomerism, we must distinguish between relative and absolute configuration
(arrangement of atoms or groups) about the asymmetric carbon atom. Let us consider a pair of enantiomers,
say (+) and (-) lactic acid.
CH3 CH3
H C OH OH C H
COOH COOH
(+) or (–) (+) or (–)
lactic acid lactic acid
We know that they differ from one another in the direction in which they rotate the plane polarised light. In
other words, we know their relative configuration in the sense that one is of opposite configuration to the
other. But we have no knowledge of the absolute configuration of the either isomer. That is, we cannot tell as
to which of the two possible configuration corresponds to (+)- acid and which to the (-) - acid. A given isomer
is dextro or laevo, can only be known using optical measurements. If compounds rotates the plane polarized
light in clockwise direction, it is dextro otherwise laevo isomer.
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3.2.5 D and L System

The sign of rotation of plane-polarized light by an enantiomer cannot be easily related to either its absolute or
relative configuration. Compounds with similar configuration at the asymmetric carbon atom may have
opposite sign of rotations and compounds with different configuration may have same sign of rotation. Thus
d-lactic acid with a specific rotation +3.82° gives l-methyl lactate with a specific rotation -8.25°, although the
configuration (or arrangement) about the asymmetric carbon atom remains the same during the change.
CO2H CO2CH3
H C OH H C OH
CH3 CH3
+ 3.82° –8.25°
Obviously there appears to be no relation between configuration and sign of rotation. Thus D-L-system has
been used to specify the configuration at the asymmetric carbon atom. In this system, the configuration of an
enantiomer is related to a standard, glyceraldehyde. The two forms of glyceraldehyde were arbitrarily
assigned the configurations as shown below.
CHO CHO
H C OH H C OH
CH2OH CH2OH
(+)–glyceraldehydes (–)–glyceraldehydes
D configuration L configuration
If the configuration at the asymmetric carbon atom of a compound can be related to D (+)-glyceraldehyde, it
belongs to D-series and if it can be related to L(-)-glyceraldehyde, the compound belongs to L-series. Thus
many of the naturally occurring α–amino acids have been correlated with glyceraldehyde by chemical
transformations. For example, natural alanine (2-aminopropanoic acid) has been related to L(+)-lactic acid
which is related to L(-)-glyceraldehyde Alanine, therefore, belongs to the L-series.
In general, the relative configuration of a substituent (X) at the asymmetric centre is specified by writing the
projection formula with the carbon chain vertical and the lowest number carbon at the top. The D
configuration is then the one that has the substituent 'X' on the bond extending to the 'right' of the asymmetric
carbon, whereas the L configuration has the substituent 'X' on the 'left'. Thus,
R1 R1
H C X X C H
R2 R2
D configuration L configuration
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When there are several asymmetric carbon atoms in a molecule, the configuration at one
1CHO
centre is usually related directly or indirectly to glyceraldehyde. In the configurations of
the natural (+)-glucose there are four asymmetric centres (marked by asterisk). By 2
H C* OH
convention for sugars, the configuration of the highest numbered asymmetric carbon is
related to glyceraldehyde to determine the overall configuration of the molecule. For HO 3 C* H
glucose, this atom is C-5 and therefore, OH on it is to the right. Hence the naturally 4
H C* OH
occurring glucose belongs to the D-series and is named as D-glucose. Must naturally
occuring carbohydrates have the D configuration.However, the above system of 5
H C* OH
nomenclature based on Fischer projection formula, has certain disadvantages. Firstly 6
before a name can be assigned to a compound, we must specify how its projection CH2OH
formula is oriented. D(+) glucose
1
Secondly, sometimes the two asymmetric carbon atoms having the same kind of CH3
arrangements of substituents are assigned opposite configurational symbols. As in ( – ) 2,3– Cl 2 H
dichlorobutane. H 3
Cl
4
CH3
3.2.6 Erythro and Threo Isomers

The descriptors erythro and threo are used to distinguish between diastereomers containing X X
only two chiral centers, which are adjacent and bearing two pairs of common ligands as
shown here in the example below, A C C B
Y Y
If, in the Fischer projection, like groups are on the same side of the bond linking the chiral
centers, the compound is identified as the erythro isomer. If these are on the opposite sides, the compound is
identified as the threo isomer.
A A
X Y X Y
X Y X Y
B B
erythro isomer threo isomer
This can be explained with the help of an example - 2,3-dichloroethane.The two isomers are shown below,
CH3
CH3
H Cl H Cl
CH3
H H
CH3 H Cl
erythro–2,3–dichloroethane
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When drawn as a zig-zag chain, the erythro isomer has two identical substituents on different sides of the
plane (anti).
CH3
CH3
H Cl H Cl
CH3
Cl H
CH3 Cl H
threo–2,3–dichloroethane
Even 3–chloro 2–butanol can show this type of isomerism as it contains two identical ligands H and Me. By
the way, these are older prefixes still commonly used to distinguish diastereomers in carbohydrate chemistry.
The names are derived from the diastereomeric aldoses erythrose (a syrup) and threose (melting point 126
°C). These prefixes are not recommended for use outside of the realm of carbohydrates because their
definitions can lead to conflicting interpretations.
3.2.7 Optical Isomerism in Compounds with More than one Asymmetric Carbon Atom
In the above discussion we have seen that an asymmetric carbon atom can produce molecular asymmetry.
Thus the molecules containing an asymmetric carbon exist in two optically active forms, (+)-isomer and
(-)-isomer, and an equimolar mixture of the two which is called (±)-mixture, is optically inactive. When there
are two or more asymmetric carbon atoms in a molecule, the problem is complicated considerably.An
organic compound which contains two dissimilar asymmetric carbons, can give four possible stereoisomeric
forms. Thus 2-bromo-3-chlorobutane may be written as
* *
CH3—CH—CH—CH3
1 2 3 4
Br Cl
The two asymmetric carbons in this molecule are dissimilar in the sense that the groups attached to each of
these are different.
C2 has CH3, H, Br, CHClCH3
C3 has CH3, H, Cl, CHBrCH3
Such a substance can be represented by four isomers in Fischer projection.

CH3 CH3 CH3 CH3
H Br Br H H Br Br H
H Cl Cl H Cl H H Cl
CH3 CH3 CH3 CH3
(I) (II) (III) (IV)

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The forms I and II are optical enantiomers (related as object and mirror image) and so are forms III and IV.
These two pairs of enantiomers will give rise to two possible racemic modifications.It may be noted that forms
I and III are not mirror images or enantiomers, and yet they are optically active isomers. Similarly, the other
two forms i.e., II and IV are also not enantiomers but optically active isomers. As stated earlier, such
stereoisomers which are optically active isomers but not mirror images, are called diastereoisomers or
diastereomers.
3.3 Number of Optical Isomers

As it has been discussed above, a compound containing two dissimilar carbon atoms can exist in four optically
active forms. Reasoning in the same fashion, we will find that a compound containing three such asymmetric
carbon atoms can exist in eight different configurations which represent optical isomers. Thus in general, the
number of stereoisomers for a compound with n distinct (different) asymmetric carbon atoms is 2n .
When an organic compound contains two similar asymmetric carbon atoms in its molecule, abd C–C abd,
the number of optically active isomers decreases. Thus tartaric acid [HO2CCH(OH)CH(OH)CO2H] has two
similar asymmetric carbon atoms and exists in only three forms (optical isomers), of which two are optically
active and one is optically inactive (meso form). Thus the general guidelines for predicting the number of
optical isomers is given as under.
1. When the molecule is unsymmetrical

Number of d and lisomers (a) =2n
Number of meso forms (m) = 0
∴ Total number of opical isomers (a + m) =2n

Where n is the number of chiral carbon atom(s).
Common example is CH3CHBrCHBrCOOH
2. When the molecule is symmetrical and has even number of chiral carbon atoms.
Number of d and lisomers (a) = 2(n-1)
Number of meso forms (m) =2(n/2-1)
∴ Total number of optical isomers = (a+ m)
Common example is tartaric acid, HOOCCHOHCHOHCOOH
3. When the molecule is symmetrical and has an odd number of chiral carbon atoms.
Number of d and lforms (a) =2(n-1)–2(n/2-1/2)

Number of meso forms (m) =2(n/2-1/2)
∴ Total number of optical isomers = (a + m) =2(n-1)

CH3CHOHCHOHCHOHCH3
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Example 4 :
(i) Draw all the stereoisomers of 3–chloro 2–pentanol, CH3CH(OH)CHClCH2CH3.
(ii) Give the stereochemical relationships of the stereoisomers.
Solution:
(i) There are four stereoisomers. A and B are enantiomers, as are C and D.
(ii) A and B are diastereomers of C and D.
CH3 CH3 CH3 CH3
HO H H HO HO H H HO
H Cl Cl H Cl H H Cl
C2H5 C2H5 C2H5 C2H5
(A) (B) (C) (D)
(racemate)1 (racemate)2
3.4 Isomerism of Tartaric Acid

Let us now proceed to discuss the optical isomerism of tartaric acid which contains two similar asymmetric
carbon atoms, in detail.The two asymmetric carbon atoms in tartaric acid,
*CH(OH)COOH
|
*CH(OH)COOH
are attached to the groups H, OH, COOH and CH(OH)COOH. The end groups being identical, four
arrangements are possible as one or both H groups and OH groups, are on the left or on the right. These
arrangements are shown by Fischer projections.
COOH COOH COOH COOH
H OH HO H H OH HO H
HO H H OH H OH HO H
COOH COOH COOH COOH
(I) (II) (III) (IV)
Of these, formula (IV) when rotated through 180° in the plane of the paper becomes identical with formula III.
Therefore, for tartaric acid we can have only three different arrangements, viz. (I), (II) and (III).
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COOH COOH COOH
H OH HO H H OH
HO H H OH H OH
COOH COOH COOH

dextro or laevo form laevo or dextro form meso form
(I) (II) (III)
Structure III will represent optically inactive tartaric acid, since it has a plane of symmetry. The optical rotation
of the upper half of the molecule is balanced by that of the lower half.
It may also be noted that formulae I and II are mirror images of each other and thus one of them is dextro and
the other is laevo. Formula III, however represents an inactive isomer of tartaric acid called meso form.In
actual practice, four types of tartaric acids are known.
(i) (+)-Tartaric acid
(ii) (-)-Tartaric acid
(iii) Inactive or i-tartaric acid (this is also known as meso-tartaric acid or m-tartaric acid).
(iv) (±) Tartaric acid (this form of tartaric acid being a mixture of equal amounts of (+)- and
(-)-isomers).
The physical properties of the four tartaric acids are tabulated as
Table1: Physical properties of the four tartaric acids
Name Melting point(°c) Density (g/cc) Optical rotation
(+)-Tartaric acid 170 1.760 +12°
(-)-Tartaric acid 170 1.760 -12°
(±)-Tartaric acid 206 1.697 0°
m-Tartaric acid 140 1.666 0°
The three tartaric acids, (+)-, (-)-, m-, are all space isomers but m-tartaric acid is not a mirror image of either
of the active forms. Hence it differs from them in melting point, density and other physical properties.
3.5 External and Internal Compensation

If equimolecular amounts of d- and l-isomers are mixed in a solvent, the solution is inactive. The rotation of
each isomer is balanced or compensated by the equal but opposite rotation of the other. Optical inactivity
having this origin is described as due to external compensation.
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COOH
H OH
H OH
COOH
III
Inactivity of meso tartaric acid
by internal compensation.
3.6 Stereogenic Element

A useful first step in examining structural formulas to determine whether stereoisomers may exist is to identify
all stereogenic elements. A stereogenic element is a center, axis or plane that is a focus of stereoisomerism,
such that an interchange of two groups attached to this feature leads to a stereoisomer. Stereogenic elements
may be chiral or achiral. An asymmetric carbon is often a chiral stereogenic center, since interchanging any
two substituent groups converts one enantiomer to the other.
3.7 Asymmetric Synthesis

Generally speaking, asymmetric synthesis deals with synthesis of chiral molecules, which are
non-superimposable on its mirror images. So, asymmetric synthesis is applied for any chemical reaction that
affects the structural symmetry in the molecules of a compound, converting the compound into unequal
proportions of compounds that differ in the dissymmetry of their structures at the affected centre.
Definition wise, chiral synthesis or asymmetric synthesis also called asenantioselective synthesis, is defined as
a chemical reaction or a series of chemical reactions in which one or more than one elements of chirality are
introduced in a substrate molecule. As a result of the reaction it produces the enantiomeric or
diastereoisomeric products in unequal amounts. More simply, it refers to the synthesis of a compound by a
method that favors the formation of a specific enantiomer or diastereomer. Asymmetric syntheses often are
called stereoselective. If one of the products is formed exclusively, the reaction is called stereospecific. One of
the example is shown below,
O OH O
O
cat. (10 mol%) Ph
Ph H PEt3.THF,–10°C
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The catalyst used in the reaction is,
Ar
OH
OH
Ar
cat.
Enantioselective synthesis is a key process in modern chemistry and is particularly important in the field of
pharmaceuticals, as the different enantiomers or diastereomers of a molecule often have different biological
activity.
3.8 R,S Nomenclature (Absolute Configuration)

R,S nomenclatureis an absolute method of configuring chiral atoms.System which indicates the absolute
configuration was given by three chemists R.S. Cahn, C.K. Ingold and V. Prelog. This system is also known as
the Cahn-Ingold Prelog method of configuring chiral atoms. The letter (R) comes from the Latin word rhectus
(meaning right) while (S) comes from the Latin word sinister (means left). Any chiral carbon atom has either a
(R) configuration or a (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. The two steps involved in R, S nomenclature are:
Step 1: By a set of sequence rules given below, the atoms or groups connected to the chiral carbon are
assigned a priority sequence.
Step 2: The molecule is then visualised so that the group of lowest priority (4) is directed away from the
observer. 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 one looks 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 as R. If
arrangement of groups is in anticlocwise direction, the configuration is designated as S.For example:
2 2
1 C 3 1 C 3
4 4
Clockwise arrangement of anticlockwise arrangement of
1 , 2 and 3 ⇒R 1 , 2 and 3 ⇒S
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 lower
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atomic number is given the priority (2), the group with next lower atomic number is given the next priority
which is (3) and the group with least atomic number is given priority (4). Thus,
Cl 3
COOH 4
F C I ≡ 4 C 1
H2N C Br ≡ 3 C 1
Br 2
F Cl Br I OH 2
Increasing atomic number
C N O Br
4 3 2 1 Increasing priority with atomic number
Increasing priority
Rule 2: If two or more than two isotopes of the same element is present, the isotope of higher atomic mass
receives the higher priority.
1H11H21H3
Increasing priority
3 2 1
Rule 3 : If two or more of the atoms directly bonded to the chiral carbon are identical, the atomic number 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 among C,H and Br and thus CH2Br has highest priority among these three groups
(i.e., priority no. 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 among these atoms, so that has the
next priority (i.e., priority no. 3) and the leftover propyl group is given the fourth priority.
I 1
I–CH2–CH2–C–CH2–Br ≡ 3 C 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.
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–C = O ≡ – C – O; – C ≡ N ≡ – C – N; – C – OH ≡ – C – OH
N O
By this rule, we obtained the following priority sequence:
–CH=CR2, –CN, CH2OH, CHO, CO, COOH
Increasing priority
Application of the rules

Let us apply the whole sequence rule for the configuration of bromochlorofluoro methane.
F 3
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 done 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 interchange will takes place between 2 and 4.
Interchange 1: 3 3
First interchange
1 C 4 1 C 2
Between 2 and 4
2 4
(A) (B)
Interchange 2:
3 1
Second interchange
1 C 2 3 C 2
between remaining
4 groups, i.e., 2 and 3
4
(B) (A)
Arrangement of 1 2 and 3 are
clockwise, hence configuration is R
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Example 5: Now the two isomers of glyceraldehydes is subjected to R,S configuration as below,
Solution H O
CHO C
O
H C OH ≡ H C OH ≡
CH2OH CH2OH
D–glyceralde hyde
2 2
First interchange
4 C 1 3 C 1
Between 3 and 4
3 4
1
Second interchange
3 C 2
Between 1 and 2
4
⇓
Clockwise
R–configuration
CHO 2 1
(i) First interchange between 3 and 4
HO C H ≡ 1 C 4 2 3
C
(ii) Second and interchange between 1 and 2
CH2OH 3 4
L–glyceralde hyde
Anticlockwise
⇓
S–configuration
Glyceraldehyde has one asymmetric carbon, hence it has two configurational isomers (D) and (L).One can
draw a number other configurations for glyceraldehyde but each of them will be a repetition of either (D) or
(L). In this connection it is important to note that if two projection formulae 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.
4. Geometrical Isomerism
In organic chemistry, cis, trans isomerism also known as geometric isomerism is a form of
stereoisomerism describing the relative orientation of functional groups within a molecule. In general, such
isomers contain double bonds, which cannot rotate around the double bond. However, this type of
stereoisomerism can also arise from ring structures, wherein the rotation of bonds is greatly restricted just like
a double bond. Cis and trans isomers occur both in organic molecules and in inorganic coordination
complexes. The terms cis and trans are from Latin, in which cis means "on this side" and trans means "on the
other side" or "across". The term "geometric isomerism" is considered as an obsolete synonym of "cis/trans
isomerism" by IUPAC. These compound do not rotate the plane polarized light (unless they happen to be
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chiral), and the properties of the isomers are not identical. It is important to note that the geometric isomers
are always diastereomers to each other.
It must not be confused with E-Z isomerism, which is the related absolute stereochemical description, only
to be used with alkenes and not at all in any other case of double bond. Cis and trans descriptors are not used
for cases of conformational isomerism where the two geometric forms easily interconvert, such as most
open-chain single-bonded structures; instead, the terms syn and anti would be used.
4.1 Conditions to Show Geometric Isomerism

The sufficient and necessary conditions for a compound to show geometrical isomerism are
1. There must be restricted rotation in the molecule either due to C = C, C = N, N = N, C = S bonds or
alicyclic compounds.
2. The atoms or group of atoms attached to each doubly bonded carbon must be different.
As an example, in the given compound, the two carbon atoms of C = C double bond and the four atoms
directly attached to them are all in the same plane and that rotation around the double bond is prevented.
x y x y
C C
C C
x y x y
In the present case the isomer in which same groups are on same sides of the two carbon atoms, is called cis
isomer and the one in which the same groups are on opposite side of the two carbon atoms, is called trans
isomer.The simple examples of this kind of isomerism are
(i) H CH3 H CH3
C and C
C C
H CH3 CH3 H
cis–2–Butene trans–2–Butene
(ii) CH3
H CH3 H
C and C
C C
H CH2CH3 H CH2CH3
cis–2–pentene trans–2–pentene
(iii) H Cl Cl H
C and C
C C
H Cl H Cl
cis–1,2–dichloroethene trans–1,2–dichloroethene
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(iv) H COOH H COOH

C and C
C C
H COOH HOOC H
Maleic acid Fumaric acid
(cis–isomer) (trans–isomer)
It may be noted that cis and trans nomenclature cannot be applied in those cases when the four groups are
different. For such cases, the E and Z nomenclature system proposed by Cahn Ingold and Prelog is followed.
For example,
CH3 H
CH3 H
C and C
C C
CH2CH3 Br CH2CH3
Br
Here, we cannot use cis and trans isomerism because all four groups attached to C = C are different, thus E–Z
nomenclature is applicable to them.
4.2 Geometrical Isomerism in other Compounds

Geometrical isomerism is also possible with other double bonds such as C = N, N = N, or even C = S,
though in these cases only two or three groups are connected to the doubly bonded atoms. In case of imines,
oximes and other C = N compounds if w = y, III may be called syn and IV may be called anti. In azo
compounds, there is no ambiguity; V is always syn regardless of the nature of w and y.
w y w w y w
C=N C=N N=N N=N
x x y y
(III) (IV) (V) (VI)
The presence of a ring, like that of a double bond, prevents free rotation. Cis and trans isomers are possible
whenever there are two carbons on a ring, each of which is substituted by two different groups. The two
carbons need not be adjacent. For example,
w y w z
w w
y y
x z x y x x
z z
As with double bonds, w may equal y and x may equal z, but w may not equal x and y may not equal z if cis
and trans isomers are to be possible. There is an important difference from the double bond cis trans
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isomerism. The substituted carbons are chiral carbons. This means that there are not only two isomers. In the
most general case, where w, x, y and z are all different, there are four isomers since neither the cis nor the
trans isomer is superimposable on its mirror image. This is true regardless of ring size or which carbons are
involved, except that in rings of even numbered size when w, x, y and z are at opposite corners, no chirality is
present.
4.3 Number of Geometrical Isomers

1. When only one double bond is present in the molecule, the number of geometrical isomers are 2n
where n = number of double bonds for molecules having identical ends as well as for molecules having
different ends. For example, 2– butene having 1 double bond and similar ends have 2 isomers.
CH3–C–H CH3–C–H
CH3–C–H H–C–CH3
cis–2–butene trans–2–butene
and 2–pentene having 1 double bond and different ends also have 2 isomers.
C2H5–C–H H–C–C2H5
2. If a compound has 2 or more double bonds and ends are different, then the number of geometrical
isomers are 2n where n = number of double bonds. For example, 2,4–heptadiene has 4 isomers.
H CH3 H CH3 CH3 H CH3 H
C C C C
C H C H C H C H
H C H C H C H C
C C C C
C2H5 H H C2H5 C2H5 H H C2H5
cis–cis cis–trans trans–cis trans–trans
(Four isomers)
For example, 2,4,6–nonatriene has 3 double bonds and ends are different, therefore number of
geometrical isomers are 23 =8 isomers.
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H CH3 H CH3 H CH3 CH3 H

C C C C
C C H C H C
H H
H C H C H C H C
H C H C C C
H H
C H C H H C C H
C C C C
H C2H5 C2H5 H C2H5 H H C2H5
cis–cis–cis cis–cis–trans cis–trans–cis trans–cis–cis
CH3 H CH3 H H CH3 CH3 H

C C C C
C C C H C
H H H
H C H H C H
C C
C H C C H C
H H
H C C H H C H C
C C C C
C2H5 H C2H5 H H C2H5
H C2H5
trans–cis–cis trans–cis–trans cis–trans–trans trans–trans–trans
(Eight Isomers)
3. If a compound has 2 or more double bonds and ends are identical, then the number of geometrical
isomers are 2n − 1 + 2p − 1.
where p = n/2 when number of double bonds are even. (n = Number of double bonds)
n +1
and p = when number of double bonds are odd.
2
For example, 2,4–hexadiene having 2 double bonds and identical ends have only 3 geometrical
isomers.
H CH3 H CH3 CH3 H

CH3 H
C C C C
C H C H C C
H H
H C H C H C H C
C C C C
CH3 H H CH3 CH3 H H CH3
cis–cis cis–trans trans–cis trans–trans
Note: cis– trans and trans–cis are same isomers. Therefore, in all there are three geometrical isomers.
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4. When a molecule contains a double bond and an asymmetric carbon, there are four isomers, a cis pair
of enantiomers and a trans pair of enantiomers.
H CH3 CH3 H CH3 H H CH3
C C C C
C CH3 CH3 C C CH3 C

CH3
H C C H H C C H
H C2H5 C2H5 H H C2H5
C2H5 H
Z or cis dl pair E or trans dl pair
4.4 Stability of Cis, Trans or Geometrical Isomers

The trans isomer of alkenes are usually more stable than their corresponding cis isomer. The reason for this
becomes clear if we consider the cis and trans isomers of the alkene wxC= Cwx in which 'w' is a bulky group
as compared to 'x' (e.g., CH3-HC=CH-CH3). In the cis isomer, the two bulky 'w' groups are very close to each
other. The steric repulsion due to the overlapping of the electron clouds of the two bulky 'w' groups will make
this isomer less stable than trans isomer in which the bulky 'w' groups are far apart (being on the opposite
sides of the double bond). The bulky 'w' groups in the cis isomer being very near will overlap, while in the
trans isomer the 'w' groups lie far apart and do not overlap.
w x w x
C C
w C x x C w
cis isomer trans isomer
4.5 Determination of Configuration of Isomers from Study of their Physical Properties

There is no absolute method for the determination of the configuration of cis and trans isomers. Several
elementary relationships are, however, helpful for the beginners.The difference in the structure of cis and
trans isomers is reflected in their physical properties. Some such properties are illustrated below.
1. Dipole moments: The trans isomers have normally less dipole moments than their corresponding cis
isomers. The reason for this is clearly understood if we consider the cis and trans isomers of
1,2-dichloroethylene. The trans isomer has a dipole moment of zero. This is due to the fact that the two
bond moments of C-Cl bonds are opposed because of the symmetry of the molecule. On the other
hand, the cis isomer being non-symmetrical has a definite dipole moment because here the bond
moments are not opposed.
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H Cl H Cl
C C
C C
Cl H H Cl
trans (µ=0 D) cis (µ=1.89 D)
In such alkenes which have one polar substituent different from the other, the dipole moment will not
normally be zero but would be smaller than the corresponding cis isomer. However if one of the substituent is
electron-donating and the other is electron-withdrawing, the bond moments are fully additive in trans isomer.
Thus the trans isomer in this case has a higher dipole moment than the corresponding cis isomer.
H Cl H Cl
C C
C C
CH3 H H CH3
trans (µ=1.97 D) cis (µ=1.71 D)
Therefore, it is possible to assign configuration to a pair of isomers on the basis of dipole measurements,
provided the nature of substituents is known to us.
2. Melting points and related phenomena: In general, a trans isomer has greater symmetry than the
corresponding cis isomer. Thus it packs more closely in the crystal lattice and hence has higher melting
points. Cis compounds, on the other hand, have low melting points since they being less symmetrical
do not pack closely in the crystal lattice. Moreover, the poor packing leads to weaker forces of attraction
between the molecules in the crystal lattice. The weaker forces of attraction can be easily broken by the
dielectric constant of the solvents and hence the cis isomers have greater solubilities than their trans
isomers. cis compounds have also been found to have higher heats of formation and ionization
constants as acids. Due to these differences in properties, it is sometimes possible to assign
configurations to a pair of geometrical isomers.
3. By chemical methods: The formation of a cyclic molecule from an open chain molecule takes place
easily only when the reacting groups are close to each other. This fact has been most useful in assigning
configuration to cis-trans isomers in which the doubly bonded carbon atoms carry groups that are
capable of reacting with each other. In the configuration of maleic acid, the two –CO2H groups are
nearer to each other than they are in fumaric acid i.e.
H–C–COOH H–C–CO
∆ O+H2O
H–C–COOH H–C–CO
maleic acid maleic anhydride
H–C–COOH
∆ No anhydride formed
HOOC–C–H
fumaric acid
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Obviously maleic acid is the cis form and fumaric acid is the trans form.In addition to the methods
given above, other physical measurements such as the measurement of the distances between certain
atoms by means of X-rays, measurement of absorption spectra etc. may be helpful for deciding the
configuration in some cases.
4.6 Interconversion of Geometrical Isomers

Although geometrical isomers are stable at ordinary temperatures, one can be converted into the other or to
an equilibrium mixture of both by heat, by exposure to ultraviolet light, or by the use of catalysts. Thus,
350°–450°
CH3–C–H H–C–CH3
47% 53%
This interconversion of cis to trans isomer involves the breakage of carbon-carbon π– bond. The cleavage of
the carbon-carbon π–bond requires approximately 40 kcal/mole of energy. At room temperature, only a
small fraction of collisions possesses this energy and hence the rate of interconversion is very slow but can be
increased by employing higher temperatures. The interconversion normally follows a pathway which can be
schematically shown as below,
CH3 CH3 CH3 CH3
∆/hν Rotate
C C C C
H H H H
cis
CH3 H CH3 H
C C C C
H CH3 H CH3
trans
4.7 E - Z System of Nomenclature of Geometric Isomers

Need of E-Z nomenclature
The problem with the cis-trans system for naming geometric isomers is enormous. If one considers a simple
case of geometric isomerism which is already been discussed like below,
H Cl H H
C C C C
Cl H Cl Cl
trans–1,2–dichloroethene cis–1,2–dichloroethene
One can easily tell which is the cis and which the trans form just by looking at them. So why do we need
another system is the question of importance. Problem arises as compounds get more complicated. For
example, for the two isomers below, it becomes difficult to use cis and trans nomenclature. It is because all the
groups attached to the carbon-carbon double bond are different.
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Br Cl Br H
C C C C
F H F Cl
The E-Z system gets around this problem completely sorted out- but unfortunately makes things slightly more
difficult for the simple examples you usually meet in introductory courses.
How to use E-Z system

The last two compounds will be used as an example to explain how the system works. One has to look at what
atom or group of atoms is attached to each end of the double bond.Afterwards, the two groups are assigned a
"priority" according to a set of rules given by Cahn Ingold Prelog rules which will be discussed shortly. In the
example above, at the left-hand end of the bond, it turns out that bromine has a higher priority than fluorine.
And on the right-hand end, it turns out that chlorine has a higher priority than hydrogen.
higher priority higher priority
on second C on first C
higher priority
on first C Br H
Br Cl C C
C C F Cl
F H
higher priority
on second C
If the two groups with the higher priorities are on the same side of the double bond, that is described as the
(Z)- isomer. So one would write it as (Z)-isomer. The symbol Z comes from a German word (zusammen)
which means together.
So the two isomers are:

Br Cl Br H
C C C C
F H F Cl
(Z)–rest of name (E)–rest of name
Rules for determining priorities (Cahn-Ingold-Prelog rules)

These are known as Cahn-Ingold-Prelog rules after the set of scientists who developed the system.
1. The first rule is meant for very simple compounds. One has to look first at the atoms attached directly to
the carbon atoms at each end of the double bond - thinking about the two ends separately.The atom
which has the higher atomic number is given the higher priority. As an example,
Br H
C C
F Cl
Just consider the isomer above - and look separately at the left-hand and then the right-hand carbon
atom. Compare the atomic numbers of the attached atoms to work out the various priorities.
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Bromine has a higher Chlorine has a higher

atomic number than atomic number than
fluorine. hydrogen.
Bromine has the Br Cl Chlorine has the
higher priority. C C higher priority.
F H
Notice that the atoms with the higher priorities are both on the same side of the double bond. That
makes it the (Z)- isomer.
Br H
C C
F Cl
The second isomer shown above is obviously the (E)- isomer. It still has the same atoms at each end,
but this time the higher priority atoms are on opposite sides of the double bond. That's why it is referred
as the (E)- isomer.
2. Now the more familiar examples like 1,2-dichloroethene or but-2-ene are considered. Here's
1,2-dichloroethene.
H Cl H H
C C C C
Cl H Cl Cl
As one thinks about the priority of the two groups on the first carbon of the left-hand isomer, it is
observed that chlorine has a higher atomic number than hydrogen, and so has the higher priority.
That, of course, is equally true of all the other carbon atoms in these two isomers.In the first isomer, the
higher priority groups are on opposite sides of the bond. That must be the (E)- isomer. The other one,
with the higher priority groups on the same side, is the (Z)- isomer.
H Cl H H
C C C C
Cl H Cl Cl
(E)–1,2–dichloroethene (Z)–1,2–dichloroethene
And now but-2-ene is considered as another example.This is a slightly complicated case viz a viz
previous examples because it is not a single atom attached to the double bond, but a group of atoms.
But anyhow, that isn't a problem. One has to concentrate on the atom directly attached to the double
bond - in this case the carbon in the CH3 group. Here is one of the isomers of but-2-ene:
The carbon atom in the CH 3

group is directly attrached to the
double bond carbon. That's the H CH3
only thing you have to worry C C
about in this group. CH3 H
The CH3 group has the higher priority because its carbon atom has an atomic number of 6 compared with an
atomic number of 1 for the hydrogen also attached to the carbon-carbon double bond.The isomer drawn above
has the two higher priority groups on opposite sides of the double bond. The compound is (E)-but-2-ene. For this
simple case, one can ignore the hydrogen atoms in the CH3 group entirely. However, with more complicated
groups one may have to take care of atoms not directly attached to the double bond too.
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3. A minor addition has to the rule has to be done to allow for isotopes. As an example, deuterium is an
isotope of hydrogen having a relative atomic mass of 2. It still has an atomic number of 1. However, it
isn't the same as an atom of "ordinary" hydrogen, and so these two compounds are geometric isomers:
H Cl H H
C C C C
D H D Cl
The hydrogen and deuterium have the same atomic number - so on that basis, they would have the
same priority. In a case like that, the one with the higher relative atomic mass has the higher priority. So
in these isomers, the deuterium and chlorine are the higher priority groups on each end of the double
bond.That means that the left-hand isomer in the last diagram is the (E)- form, and the right-hand one
the (Z)-.
4. Now the rules will be extended to more complicated and scary-looking molecule molecules like below,
CH3 CH2OH
C C H
CH3CH2 C
Focussing on the left-hand end of the molecule,it becomes easier to know which group is attached
directly to the carbon-carbon double bond. In both of the attached groups, a carbon atom is attached
directly to the bond. Those two atoms obviously have the same atomic number and therefore the same
priority. So that doesn't help.In this sort of case, you now look at what is attached directly to those two
carbons (but without counting the carbon of the double bond) and compare the priorities of these next
lot of atoms. One can do this in your head in simple cases, but it is sometimes useful to write the
attached atoms down, listing them with the highest priority atom first. It makes them easier to compare
as in the case of the CH3 group,the atoms attached to the carbon are H HH.In the CH3CH2 group, the
atoms attached directly to the carbon are C H H. In the second list, the C is written first because it has
the highest atomic number.
Now compare the two lists atom by atom. The first atom in each list is an H in the CH3 group and a C in the
CH3CH2 group. The carbon has the higher priority because it has the higher atomic number. So that gives the
CH3CH2 group a higher priority than the CH3 group.
Now,one has to look at the other end of the double bond. The extra thing that this illustrates is that if you have
a double bond, you count the attached atom twice. Here is the structure again.
CH3 CH2OH
C C H
CH3CH2 C
O
So, again, the atoms attached directly to the carbon-carbon double bond are both carbons. We therefore
need to look at what is attached to those carbons.In the CH2OH group the atoms attached directly to the
carbon are O H H. In the CHO group, the atoms attached directly to the carbon are O O H. Remember that
the oxygen is counted twice because of the carbon-oxygen double bond.In both lists, the oxygens are written
first because they have a higher atomic number than hydrogen.So, what is the priority of the two groups - the
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first atom in both lists is an oxygen - that doesn't help. One has to move on and look at the next atom in both
lists. In the CH2OH group, that is a hydrogen; in the CHO list, it's an oxygen.The oxygen has the higher
priority - and that gives the CHO group a higher priority than the CH2OH group.The isomer is therefore a (Z)-
form, because the two higher priority groups (the CH3CH2 group and the CHO group) are both on the same
side of the bond. So, this becomes a fairly long-winded explanation just to make clear how it works. With a bit
of practice, it takes a few seconds to work out in any but the most complex cases.
4.8 Geometric Isomerism in Oximes

The oximes are formed when carbonyl compounds are treated with hydroxyl amine. These are OH
represented as: N
Where R & R1 may be hydrogens; or alkyl or aryl groups. 1

R R
The oximes are of two types:
oxime
1. Aldoximes: These are derived from aldehydes. In this case, at least either R or R1 is
hydrogen.
2. Ketoximes: These are derived from ketones. In this case, both R or R1are alkyl or aryl groups only.
The oximes show geometrical isomerism due to restricted rotation of C=N bond. Two geometrical forms are
possible for the oximes as shown below.
OH HO
N N
R R1 R R1
The descriptors, syn and anti are used to distinguish them.
In case of aldoximes, the syn form is the one in which both the hydrogen and the hydroxyl (-OH) group
are on the same side of the C=N, whereas in the anti form, they are on the opposite side. As an example,
the syn and anti forms of acetaldoxime are shown below,
OH HO
N N
H3C H H3C H
syn oxime anti oxime
However with ketoximes, the syn and anti descriptors indicate the spatial relationship between the first group
cited in the name and the hydroxyl group. For example, the following ketoxime of butanone can be named as
either syn methyl ethyl ketoxime or anti ethyl methyl ketoxime.
HO
N
H3C C2H5
E-Z notation of oximes

The geometrical isomers are better differentiated by using E-Z notations. The Z oxime has hydroxyl group
and the group with higher priority on the same side of C=N. However in the E oxime, they are arranged on
the opposite sides of the C=N. For example, the synacetaldoxime is named as (E)-acetaldoxime, since the
hydroxy group and the group with higher priority i.e., methyl group are on the different sides of the C=N.
Expectedly, the anti form is named as (Z)-acetaldoxime.
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IUPAC System of Nomenclature of Oximes

In the IUPAC system of nomenclature, the oximes are named as: N-hydroxyalkanimines, where the C=N
group is represented by the suffix, imine and the -OH group on nitrogen is represented by the prefix,
N-hydroxy. For example, the syn and anti forms of acetaldoxime are named as follows:
syn form anti form
OH HO
N N
H3C H H3C H
(1E)–N–hydroxyethanimine (1Z)–N–hydroxyethanimine
4.9 Geometric Isomerism in Alicyclic Compounds

In the case of cyclic compounds, it is definitely interesting to know that the free rotation, around the single
bond, is restricted. Consequently, disubstituted cycloalkanes are prone to exhibit geometric or cistrans
isomerism. Different stereoisomers arise from different substituent arrangements relative to the ring side,
because they are incapable of becoming superimposable through conformational changes. It is important to
note whether substituents are on the same side or on the opposite sides of the ring. So, if the substituents are
on the same side of the ring, the compound is a cis isomer. If they are on opposite sides, they are called trans
isomers. For example 1,4-dimethylcyclohexane is considered. There are two geometrical isomers - cis &
trans which are possible in case of 1,4-dimethylcyclohexane as shown below:
CH3 CH3
CH3
H3C
or
cis–1,4–dimethylcyclohexane
CH3
H3C
or
CH3
CH3
trans–1,4–dimethylcyclohexane
In the above geometrical isomers, the methyl groups are arranged differently about the plane of the
cyclohexane ring. These isomers are not interconvertible since it is not possible to rotate the bonds in the
cyclohexane ring.
Stereoisomerism in 1,2-dimethylcyclopentane
1,2-Dimethylcyclopentane, for instance, consists of three stereoisomers:
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mirror plane
H Me Me H
Me H H Me
Fig. Trans-(1R,2R)-1,2-dimethylcyclopentane (left) and trans-(1S,2S)-1,2-dimethyl– cyclopentane (right).

mirror plane
H H
Me Me
Fig. Cis–1,2–dimethylcyclopentane
The trans isomers of 1,2-dimethylcyclopentane are enantiomeric and are therefore different compounds.
Cis-1,2-dimethylpentane contains a plane of symmetry. It is superimposable on its mirror image. It follows
then that cis-(1R,2S)-1,2-dimethylcyclopentane and cis-(1S,2R)-1,2-dimethylcyclopentane are identical and
that cis-1,2-dimethylpentane is thus a meso compound.
As a result of geometric isomerism in disubstituted cyclic compounds, these ccompounds contain several
specific characteristics. Due to identical connectivity but lacking mirror-image relationship, the cisisomer is
diastereomeric to the trans isomers. Therefore, the cis isomer, in comparison to the trans isomers, possesses
different physical and chemical properties. Cis-cyclopentane-1,2-dicarboxylic acid can, for example, be
easily dehydrated. This leads to the formation of its anhydride as shown below,
COOH
O
COOH O
C
C
O
Fig. 6: Anhydride formation of a cyclic cis–1,2–dicarboxylic acid
In contrast, the transisomer is impossible to be converted into its anhydride, because the carboxyl groups are
present at large spatial distance, which cannot be shortened by conformational changes.
Example 6: Draw the structures of the cis-trans isomers for each compound and label them cis
and trans. If no cis-trans isomers exist, write none.
(i) 2-bromo-2-pentene
(ii) 3-heptene
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(iii) 4-methyl-2-pentene
(iii) 1,1-dibromo-1-butene
(iv) 2-butenoic acid (CH3CH=CHCOOH)

Solution:
(i) H3C CH2CH3 H3C H
C C C C
Br H Br CH2CH3
cis trans
(ii) CH3CH2 H CH3CH2
CH2CH3
C C C C
H CH2CH3 H H
cis trans
(iii) None
(iv) None
(v) H3C COOH H3C H
C C C C
H H H COOH
cis trans
5. Conformational Isomerism
Carbon–carbon single σ bonds are symmetrical around the axis and can be rotated freely in open chain
molecules. Due to this free rotation of carbon–carbon single bonds, indefinite number of orientations in space
are possible. These indefinite possibilities result in the formation of indefinite number of spatial isomers.
These are called conformational isomers or rotomers which arises due to free rotation about a σ bond. An
important aspect is that these conformational isomers are rapidly interconvertible at room temperature. And
it is because of this rapid interconvertibilty that these are not referred as true type of isomerism. Out of these
indefinite arrangements only two extreme cases, which are known as staggered form and eclipsed form, are
important. The conformational isomerism in compounds can be adequately represented via Sawhorse
representation or through Newman projection. These two ways of expressing a compound is shown below
using the representative cases of ethane and n– butane.
H1 H2 H3
H H
H3 H2 H1
H H H H
Eclipsed Staggered
Fig. 7: Sawhorse representation of ethane
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HH H
1
H2 H3
H3
H H H H
H2
H1
Eclipsed Staggered
Fig. 8: Newman representation of ethane
CH3 H H
CH3 CH3
H H CH3
H H H H
Eclipsed Staggered
Fig. 9: Sawhorse representation of n–butane
Me Me
Me
H H
H
H H H H
H
Me
Eclipsed Staggered
Fig. 10: Newman representation of n–butane
In eclipsed conformer, the various groups will be at the minimum possible distance from each other whereas
in staggered conformer the various groups will be at maximum distance from each other. The steric
repulsions due to bulkiness of the groups attached will be maximum in eclipsed and minimum in staggered
due to which the energy of the staggered conformer is lesser than that of eclipsed conformer. The staggered
conformer is most stable whereas the eclipsed conformer is least stable. But the energy difference between
the conformational isomers is very less which can be acquired by the molecular collisions at room
temperature as stated earlier. So the various conformational isomers keep on changing into one another and
it is not possible to separate these conformational isomers.
5.1 Conformations of Ethane

As stated earlier, while there are an infinite number of conformations about any sigma bond, in ethane two
particular conformers are noteworthy and have special names. In the eclipsed conformation, the C-H bonds
on the front and back carbons are aligned with each other with dihedral angles of 0 degrees. In the staggered
O-175
conformation, the C-H bonds on the rear carbon lie between those on the front carbon with dihedral angles
of 60 degrees.
0°
60° H H H
H H Dihedral angle
is actually 0,
H but is tilted
slightly to make
H H H rear bonds visible.
H
H
H
Staggered Eclipsed
Fig. 11: The eclipsed and staggered conformations of ethane
Energetically, not all conformations are equally favored. The eclipsed conformation of ethane is less stable
than the staggered conformation by 3 kcal/mol. The staggered conformation is the most stable of all possible
conformations of ethane, since the angles between C-H bonds on the front and rear carbons are maximized
at 60 degrees. In the eclipsed form, the electron densities on the C-H bonds are closer together than they are
in the staggered form. When two C-H bonds are brought into a dihedral angle of zero degrees, their electron
clouds experience repulsion, which raises the energy of the molecule. The eclipsed conformation of ethane
has three such C-H eclipsing interactions, so we can infer that each eclipsed C-H "costs" roughly 1 kcal/mol.
H H Eclipsing interaction:
steric hindrance between
H H C–H bonds at 0 degree
dihedral angles
H H
Fig. 12: Eclipsing interactions in ethane
Steric hindrance
Eclipsing interactions are an example of a general phenomenon called steric hindrance, which occurs
whenever bulky portions of a molecule repel other molecules or other parts of the same molecule. Because
such hindrance causes resistance to rotation, it is also called torsional strain. The 3 kcal/mol needed to
overcome this resistance is the torsional energy. Note that this figure is very small compared to the energy
required to rotate around double bonds, which is 60 kcal/mol. At room temperature, ethane molecules have
enough energy to be in a constant state of rotation. Because of this rapid rotation, it is impossible to isolate
any particular conformation in the way that cis- and trans- alkenes can be individually isolated. The energy
profile for rotation about the C-C bond in ethane is shown below,
O-176
3 kcalmol
E
0
180 360
dihedral angle
Fig. 13: Energy diagram for rotation about the C–C bond in ethane
5.2 Conformation of Butane

The study of the relative energies of conformational isomers can be done nicely taking butane as an example.
Here for the sake of explanation, butane is represented through Newmann projection formula and analysed
for conformational isomerism around the C(2) C(3) single bond of butane.
H
CH3
1 2 3 4 H
CH3–CH2–CH2–CH3 C—C
H
CH3
H
Let us assume that relatively large methyl groups will best be kept as far from each other as CH3
possible then we have the conformation called the anti form shown in fig. (A). 120° H H
clockwise rotation passes over a transition state to a new minimum energy conformation of
butane shown in fig. (B). H H
CH3
Fig. (A)
Conformation (B) will be less stable than (A) because in (B) the two methyl groups are CH3
closer than they are in (A). Conformation (2) is called 'gauche' or 'skew' form. Gauche H3C H
form of butane (B) is about 0.6 kcal mol–1 higher in energy than the anti form (A). There
was an eclipsed transition state for the interconversion of (A) to (B) which lies about 3.4 H H
kcal mol–1 higher than (A). H
Fig. (B)
Another 120° clockwise rotation brings us to a second gauche form of butane (B). The
transition state for the conversion of (B) to (B') involves an eclipsed state of two C–CH3 CH3
bonds shown in fig. (C) and lies 3.8 kcal mol –1 above (B) and (B'), a total of about 4.4 H CH3
kcal mol –1 above (A). Final 120° clockwise rotation return us to (A).
H H
H
Fig. (B')
O-177
H3C
CH3
H
H
H H
Fig. (C)
The angle versus energy plot for butane can be shown as.
H3C
CH3
H3C H H H H3C H
H C H
H3C H H
Potential energy
CH3 H H
H 3.8 kcal H
H H H3C
mol–1
H H 3.4 kcal 3.4 kcal

mol–1 mol–1
CH3 B B'
CH3 CH3
A H CH3 A
H3C H
H H H H
H H
0° 60° 120° 180° 240° 300° 360°

Rotation about the central C2–C3bond
Fig. 14: Energy diagram for rotation about the C–C bond in butane
5.3 Conformation in Cyclohexane Ring

A planar structure for cyclohexane is definitely improbable. The bond angles would necessarily be 120º,
10.5º larger than the ideal tetrahedral angle. Also, every carbon-carbon bond in such a structure would be
eclipsed.
O-178
H H
H H
H H H
H H
H H
H H H H
H H H
Planar structure
H
H H
severe angle strain (120°) Boat conformation
severe eclipsing strain (all bonds)
small steric strain slight angle strain
eclipsing strain at two bonds
steric crowding of two hydrogens
H H H
H
H
H H
H H H H
H
H
H H
H
H H H
H
H
H H H
Twist boat conformation Chair conformation
slight angle strain no angle strain
small eclipsing strain no eclipsing strain
small steric strain small steric strain
The resulting angle and eclipsing strains would severely destabilize this structure. If two carbon atoms on
opposite sides of the six-membered ring are lifted out of the plane of the ring, much of the angle strain can be
eliminated. This boat structure still has two eclipsed bonds (colored magenta in the drawing) plus the huge
steric crowding of two hydrogen atoms on the "bow" and "stern" of the boat. This steric crowding is often
called steric hindrance. By twisting the boat conformation, the steric hindrance can be partially relieved,
but the twist-boat conformer still retains some of the strains that characterize the boat conformer. Finally, by
lifting one carbon above the ring plane and the other below the plane, a relatively strain-free chair
conformer is formed. This is the predominant structure adopted by molecules of cyclohexane.
An energy diagram for these conformational interconversions is drawn below. The activation energy for the
chair-chair conversion is due chiefly to a high energy twist-chair form (TC), in which significant angle and
eclipsing strain are present. A facile twist-boat (TB)-boat (B) equilibrium intervenes as one chair conformer
(C) changes to the other.
O-179
TC = twist chair
B = boat
TB = twist boat
C = chair
TC TC
10
8
Relative energy
(Kcal/mol)
B B
B
6 1.6 C=Chair
10.7
TB
TB TB TB
5.3
2
C C
0
Bond twisting
Fig. 15: Energy profile of various forms of cyclohexane
5.4 Substituted Cyclohexane Compounds

Investigations concerning the conformations of cyclohexane were initiated by H. Sachse (1890) and E. Mohr
(1918), but it was not until 1950 that a full treatment of the manifold consequences of interconverting chair
conformers and the different orientations of pendent bonds was elucidated by D. H. R. Barton (Nobel Prize
1969 together with O. Hassel). The following discussion presents some of the essential features of this
conformational analysis. On careful examination of a chair conformation of cyclohexane, one can find
that the twelve hydrogens are not structurally equivalent. Six of them are located about the periphery of the
carbon ring, and are termed equatorial. The other six are oriented above and below the approximate plane
of the ring (three in each location), and are termed axial because they are aligned parallel to the symmetry
axis of the ring. In the stick model shown on the left below, the equatorial hydrogens are colored blue, and the
axial hydrogens are red. Since there are two equivalent chair conformations of cyclohexane in rapid
equilibrium, all twelve hydrogens have 50% equatorial and 50% axial character.
O-180
Symmetry axis
Cyclohexane chair confirmations

Axial hydrogens Axial hydrogens
Equatorial hydrogens Equatorial hydrogens
Fig. 16: Location of axial and equatorial hydrogens
Because axial bonds are parallel to each other, substituents larger than hydrogen generally suffer greater
steric crowding when they are oriented axial rather than equatorial. Consequently, substituted cyclohexanes
will preferentially adopt conformations in which large substituents assume equatorial orientation. In the two
methylcyclohexane conformers shown below, the methyl carbon is colored blue.
1 3
5
Methyl cyclohexane Methyl cyclohexane

Equatorial conformer Axial conformer
Sever hydrogen crowding
Fig. 17: Preferential location of methyl group in equatorial position
When the methyl group occupies an axial position it suffers steric crowding by the two axial hydrogens
located on the same side of the ring. This crowding or steric hindrance is associated with the red-colored
hydrogens in the structure. A careful examination of the axial conformer shows that this steric hindrance is
due to two gauche-like orientations of the methyl group with ring carbons number 3 and number 5.
The relative steric hindrance experienced by different substituent groups oriented in an axial versus
equatorial location on cyclohexane may be determined by the conformational equilibrium of the compound.
The corresponding equilibrium constant is related to the energy difference between the conformers, and
collecting such data allows us to evaluate the relative tendency of substituents to exist in an equatorial or axial
location.
O-181
Example 7: Which of these chair conformations are the most stable and why?
Cl
Cl
Solution: Top one is more stable because it is in an equitorial conformation because the equitorial
formation is more spread out.
5.5 Conformational Isomerism in Disubstituted Cyclohexanes

It has been noted earlier that cycloalkanes having two or more substituents on different ring carbon atoms
generally exist as a pair of configurational stereoisomers giving rise to geometric or optical isomerism as well.
Now one must examine the way in which favorable ring conformations influence the properties of the
configurational isomers. Remember, configurational stereoisomers are stable and do not easily interconvert,
whereas, conformational isomers normally interconvert rapidly. In examining possible structures for
substituted cyclohexanes, it is useful to follow two principles.
1. Chair conformations are generally more stable than other possibilities.
2. Substituents on chair conformers prefer to occupy equatorial positions due to the increased steric
hindrance of axial locations.
The following equations and formulas illustrate how the presence of two or more substituents on a
cyclohexane ring perturbs the interconversion of the two chair conformers in ways that can be predicted.
1,1-disubstituted cyclohexanes
In the case of 1,1-disubstituted cyclohexanes, one of the substituents must necessarily be axial and the other
equatorial, regardless of which chair conformer is considered. Since the substituents are the same in
1,1-dimethylcyclohexane, the two conformers are identical and present in equal concentration. In
1-t-butyl-1-methylcyclohexane the t-butyl group is much larger than the methyl, and that chair conformer in
which the larger group is equatorial will be favored in the equilibrium(> 99%). Consequently, the methyl
group in this compound is almost exclusively axial in its orientation.
O-182
CH3
CH3
1
1 CH3 ≡ CH3 1 CH3
CH3
CH3
CH3
1 C(CH3)3 ≡ 1 C(CH3)3 1 CH3
C(CH3)3
Fig. 18: Conformors of 1,1–disubstituted cyclohexanes
1,2-, 1,3- and 1,4-disubstituted compounds

In the cases of 1,2-, 1,3- and 1,4-disubstituted compounds the analysis is a bit more complex. It is always
possible to have both groups equatorial, but whether this requires a cis-relationship or a trans-relationship
depends on the relative location of the substituents. As one counts around the ring from carbon number 1 to
number 6, the uppermost bond on each carbon changes its orientation from equatorial (or axial) to axial (or
equatorial) and back.
1,2 disubstitution
It is important to remember that the bonds on a given side of a chair ring-conformation always alternate in
this fashion. Therefore, it should be clear that for cis-1,2-disubstitution, one of the substituents must be
equatorial and the other axial; in the trans-isomer both may be equatorial.
CH3 CH3 CH3
1
1
≡ 1 CH3
2 2
CH3
CH3 2
1 CH3 CH3
2 ≡ 1 CH3 1
CH3 2
CH3 2
CH3
The cis form (cis-1,2-dimethylcyclohexane) appears like below,

CH3 CH3 CH3
1
1
≡ 1 CH3
2 2
CH3
CH3 2
And, the trans form (trans-1,2-dimethylcyclohexane) is,

O-183
1 CH3 CH3
2 ≡ 1 CH3 1
CH3 2
CH3 2
CH3
1,3 disubstitution
Because of the alternating nature of equatorial and axial bonds, the opposite relationship is true for
1,3-disubstitution (cis is all equatorial, trans is equatorial/axial).
CH3
CH3
1 3
≡ CH3 1
CH3 3
1 3
CH3
CH3
CH3
≡ 1 3
1 3 CH3 3
1
CH3 CH3 CH3
CH3
The cisform(cis-1,3-dimethylcyclohexane) like below,

CH3
CH3
1 3
≡ CH 1
3 CH3 3
1 3
CH3
CH3
And the trans form(trans-1,3-dimethylcyclohexane) is,

CH3
≡ 1 3
1 3 CH3 3
1
CH3 CH3 CH3
CH3
1,4 disubstitution
Finally, 1,4-disubstitution reverts to the 1,2-pattern.
CH3 CH3
CH3 1 4
1 ≡ CH
3 1 CH
4 3
4
CH3 CH3
CH3 1 4
1 ≡
4 CH3 CH3 1
4
CH3 CH3
O-184
The cisform(cis-1,4-dimethylcyclohexane) appears like below,

CH3 CH3
CH3 1 4
1 ≡ CH 1 CH
4 3 3
4
CH3
And the trans form(trans-1,4-dimethylcyclohexane) is,
CH3 CH3
1 4
1 ≡
4 CH3 CH3 1
4
CH3 CH3
5.6 Difference Between Conformational and Configurational Isomers

1. Conformational isomers: Conformational isomers have the same molecular formula and group
connectivity but a different spatial arrangement due to the rotation of a single bond. Conformational
isomers are one single compound and deal with the orientations within a molecule. The free rotation
around a single bond accounts for the different conformations that can exist. An example is butane
which can have the following conformations as discussed earlier also,
Me Me H Me Me
Me
H Me H H
H Me
HH H H H HH H H H
H Me
fully eclipsed gauche eclipsed anti
(eclipsed) (staggered) (eclipsed) (staggered)
θme/me=0° θme/me=60° θme/me=120° θme/me=180°
Fig. 22: Conformational isomers of butane
In each conformational isomer the position of the two CH3 group are at different angles to on another if one
looks along the rotating central carbon-carbon bond. This is called the dihedral angle. Even though some of
these conformers are more favoured than others for butane, it cannot be isolated as one single isomer. In
some cases, however, a molecule may exist in two conformers if rotation around the single bond is severely
hindered or in compounds containing non-planar rings of atoms.
2. Configurational isomer: An isomer which is related to a central atom about which bonded groups
may vary in their arrangement so that the molecules are not superimposable on each other or the
positions of groups are inter changeable around a double bond in alkenes, oximes etc.
3. Modern approach: As observed, the term conformer is used to explain isomers related to the rotation
about C-C single bond of ethane and butane derivatives, and the term configuration is used to define
some substituted methanes and ethylenes. At first glance it seems straightforward to distinguish
conformation and configuration. The stereoisomerism which is due to the rotation about a single bond
is referred to as conformation. Conformers are easily interconvertible and it is difficult to isolate the
isomer. To the contrary, when two compounds are different in their configuration these are termed as
O-185
configuration isomers. For example, a pair of enantiomers of bromofluoromethane, or a pair of

geometrical isomers, maleic acid and fumaric acid, these are distinguishable compounds, and their
isolation is possible. However, if maleic acid can be converted into fumaric acid by heat, there remains
some ambiguitiy to classify conformational isomers and configurational isomers by their possibility of
interconversion. It would be more practical to classify them by their facility of interconversion. A new
nomenclature was proposed where stereoisomers with lower energy barrier of conversion are
conformational isomers, while those with higher energy barrier are configurational isomers.
Quantitatively, if the barrier of interconversion is above 100 kJ mol-1, these are configurational isomer
while if it is lower than 100 kJ mol-1, these are conformers.
O-186
Exercise
(i) H
1. What are sequence rules? How are these used for
assigning R and S configuration? Discuss with HO
suitable examples. [Bund. 2009] COOH
COOH
2. Explain stereo isomerism. Describe the optical
isomerism with examples. [Meerut 2008] HO
3. Discuss optical isomerism in detail by taking
example of lactic acid and tartaric acid. H
[Meerut 2009,10,11] (ii) CH2NH2
4. What is conformation ? Explain the conformations
of ethane and butane. Cl Br
[Meerut 2008,09,10,11,12]
5. What do you understand by stereo-isomerism?
Describe geometrical isomerism in detail.
[Meerut 2012] CH2NH,Me
6. Explain D-L and R-S system of determining
(iii) NH2
configuration of optically active compounds. Give
examples. [Meerut 2012] H COOH
7. Explain the puckered conformation of cyclohexane

and the stability of chair and boat forms. COOEt
[Avadh 2008]
(iv) H
8. (i) What is optical isomerism? Discuss C
CH3 [Lko. 2009]
optical isomerism of tartaric acid. Cl
CF3
(ii) Discuss confirmation of cyclohexane.
[Kashi 2011]
10. (i) Differentiate between conformation
9. (i) Does configuration change in the given and configuration.
reaction ? (ii) What is torsional strain? Why staggered
Cl conformation is more stable than eclipsed?
Cl
Cl2 Explain with the help of torsional angle and
H3C–H2C CH3 H3C–H2C C CH3Cl
light
rotational energy barrier. [Lko. 2009]
H H
Designate the product by D, L & R. S and 11. (i) With the help of reaction only show
how racemic mixture of 2-butanol can
justify
be resolved by L-(+) Tartaric acid (R,
(ii) Assign configuration to the following
R).
compounds :
(ii) Designate the following as R or S and write
their IUPAC name :
O-187
(i) CN 2. Describe the isomerism shown by fumaric & maleic

acid (diagram only). [Bund. 2008]
H3C C2H5
COOH (i) Enantiomer (ii) Diastereomer
(ii) C6N5 [Bund. 2008; Meerut 2009,11,12]
4. Write short notes on any four of the followings :

H3C CH
(i) Enantiomer and diastereoisomer.
CHO (ii) Plane of symmetry.
(iii) CH3
(iii) Optical isomerism.
H CH2OH (iv) Geometrical isomerism

(v) D and L system of nomenclature.
CH2CH3
[Lko. 2011]
(vi) Boat and chair conformations of
12. (i) Assign E and Z nomenclature to the cyclohexane. [Bund. 2010]
following compounds and write their
5. Give the explanation of configuration in n-butane.
IUPAC name :
[Agra 2009]
(a) C6H5 CH2OH 6. Explain geometrical isomerism with the help of one
C=C example. [Agra 2009; Kanpur 2010]
H3C COOH
7. Explain optical isomerism. [Kanpur 2011]
(b) CH3 CH3
C=C 8. (i) What is chiral molecule?
Br CH2Br
(ii) A carboxylic acid having molecular formula
(ii) Differentiate between : C3H5O2 is optically active. Draw its R and S
configuration. [Avadh 2009]
(a) Enantiomers and diastereomers
9. What is a stereogeniccentre, explain with examples.
(b) Meso and racemic form. [Lko. 2011]
Discuss the optical isomerism of a compound
13. What is stereoisomerism? What do you mean be containing two dissimilar stereogeniccentres.
optical isomerism? Discuss the optical isomerism is [Avadh 2010]
lactic acid. [Hazaribagh 2008] 10. What is stereoisomerism? What do you mean by
14. What is the cause of geometrical isomerism? Discuss optical isomerism? Discuss the optical isomerism of
geometrical isomerism of maleic and fumaric acid. lactic acid. [Kashi 2008]
[Hazaribagh 2010]
11. (i) Draw the different conformation of
15. Explain conformational isomerism in cyclohexane.
n-butane in Newmann projection
16. Discuss conformation in n-butane. formula and show which one is most
[Avadh 2010, Lko. 2008]
stable.
Short Answer Type Questions (ii) What is the difference between enantiomers
1. Explain the following : and diastereomers? [Kashi 2010]
(i) Enantiomer
(ii) Racemisation
[Bund. 2008; Meerut 2010,12; Agra 2009]
O-188
12. (i) Assign R or S configuration to the (c)

following :
H Me H
(a)
HO CHO H Me [Lko. 2008]

CH3
(i) Threo-and Erythrodiastereomers.
(b) NH2
(ii) Differences between enantiomers and
H3C H diastereomers.
(iii) Meso compounds. [Lko. 2010]
COOH
14. Arrange the following groups according to
(ii) Identify the disteremers from the following
compounds : Cahn-Ingold-Prelog sequence rule (from highest to
lowest) :
(a) CH3
-COOH, -CH2OH, OH, -CHO, NH2, CN, C3H7.
H OH [Lko. 2011]
HO H 15. (i) What are conformations? Discuss the
conformation of n-butane.
CH3
(ii) What are reaction intermediates? Discuss
(b) CH3 formation, structure and stability of carbon
free radicals. [Rohd. 2012]
HO H
16. What is a plane of symmetry? Discuss optical
HO H
isomerism in lactic acid. [D.D.U. 2008,11]
CH3 17. Racemic tartaric acid and meso tartaric acid both
(c) CH3 are optically inactive. Justify.
[D.D.U. 2009]
HO H
18. The potential energy of conformations of
H HO n–CH3–CH2–CH2–CH3 decreases in order, Eclipsed
> gauche > anti. Explain. [D.D.U. 2009]
CH3
(iii) Choose optically inactive compound from 19. Discuss the optical isomerism of a compound
the following : having two asymmetric carbons. [D.D.U. 2009]
(a)
20. Write the configuration of following compounds :
Me Me
(i) Z-1-Iodo-2-hydroxypropene.
(ii) E-2-Nitro-3-bromobut-2-enoic acid.
H H [D.D.U. 2009]
(b)
21. Meso-tartaric acid is optically inactive though it has
H Me asymmetric carbon atom. [D.D.U. 2010]
Me H 22. Discuss the methods used for determination of

configuration in geometrical isomers.
[D.D.U. 2010]
23. Write the structure of isomeric amines having
molecular formula C3H9N. [D.D.U. 2011]
O-189
24. Explain the geometrical isomerism in maleic acid 6. Write notes of the following :
and fumaric acid. Assign their configurations. (i) Tauatomerism
[D.D.U. 2011]
(ii) Geometrical isomerism [Kanpur 2008]
25. Draw the potential energy diagram for the various
7. Explain asymmetric synthesis. [Kanpur 2010]
conformations of C2H6 and explain their relative
stability. [D.D.U. 2011] 8. Explain the following :
(i) Meso compound
26. Draw conformations of ethane.
[Hazaribagh 2008] (ii) Racemic mixture [Kanpur 2010]
27. What is stereoisomerism? Discuss geometrical 9. What is E and Z system of nomenclature? Explain
isomerism in alicyclic compounds. with examples. [Kanpur 2010]
[Hazaribagh 2009]
10. Draw conformations of ethane. [Kanpur 2008]
28. Write short notes on the following :
11. Define resolution. [Kashi 2008; Hazaribagh 2008]
(i) Resolution on enaniomorphs.
(ii) E and Z system of nomenclature. 12. Define racemic mixture.
[Hazaribagh 2009] [Kashi 2008; Hazaribagh 2008]
29. Distinguish between enantiomer and diastereomer. 13. Draw the structure of R(-)-2 butanol.
[Hazaribagh 2010] [Kashi 2010]
30. Write short note on chair and boat confirmation of 14. Homologues can never be isomer.Why?
[Lko. 2009]
cyclohexane. [Hazaribagh 2010]
15. In the given reaction, given the number of isolated
31. Draw all the stereoisomers of 1,2– and 1,3–
stereoisomers, their R, S configuration and optical
dimethylcyclopentanes.
activity.
32. Explain stereoisomerism in tartaric acid. CH3
33. Explain erythro and threo system of nomenclature Na
2ClCH2–CHCH2CH3
CH3 CH3
1. Represent the configuration of following H3C–CH2–CH–CH–CH2–CH–CH2–CH3
compounds by R and S system. [Lko. 2009]
I CHO 16. What are enantiomers of lactic acid? [Lko. 2010]
Br C F HO C H 17. Depict axial and equatorial bonds in cyclohexane
Cl CH2OH chair conformation. [Rohd. 2013]
[Bund. 2010]
18. What are enantiomorphs? Explain.
2. Write the name and structure of different [Hazaribagh 2009]
conformation of cyclobutane (only by Newman
19. What is an asymmetric carbon atom?
projection). [Bund. 2010] [Hazaribagh 2011]
3. Write a detail note on geometrical isomerism. 20. What is the condition to be satisfied for a compound
[Meerut 2009]
to be chiral? [Hazaribagh 2008]
4. Write a detail note on resolution.
[Meerut 2009,10,12]
5. Give the concept of conformation of ethane.

[Agra 2008]
O-190
7. The molecules represented by the above two

Objective Type Questions structures are
(a) Identical (b) Enantiomers
Multiple Choice Questions (c) Diastereomers (d) Epimers
1. The isomers related to each other as object and 8. Which of the following compound is incapable of
mirror image are exhibiting tautomerism.
(a) Enantiomer (b) Diastereomer (a)
(c) Rotamer (d) None of the above O
[Bund. 2008]
2. The compound which exhibits optical isomerism is : O
(a) (CH3 )2 CH − CH2Br
(b)
CH3 O
|
(b) (CH3 )2 − CH − CH2Br
C2H5 O
|
(c) (CH3 )2 − CH − CH2Br
(c)
(d) (CH3 )3 − C − Br [Agra 2008] —CH=CH—OH
3. How much chiral carbon atom in following structure

CH3
(d)
| O
H − C − OH O
|
COOH
(a) One (b) Two 9. Benzil on reduction with NaBH4 gives (A). The
(c) Three (d) No chiral atom number of optically active stereoisomers possible
[Agra 2009] for (A) are
4. R and S system used in which isomerism? (a) 1 (b) 2
(a) Conformational (c) 3 (d) 4
(b) Configuration
10. Which of the following compounds will exhibit
(c) Geometrical
(d) Optical cis-trans isomerism?
[Agra 2009]
(a) 2-butene (b) 2-butyne
5. What is IUPAC name of compound below,
CH2OH (c) 2-butanol (d) butanal
CH3CH2CH2CHCH2CH3 11. The number of isomers of C6H14 is:

(a) 4 (b) 5
(a) 3-Methaneol hexane
(b) 2-Ethyl pentanol (c) 6 (d) 7
(c) 5-Ethyl pentanol 12. The isomers which can be inter converted through
(d) None of these [Agra 2009] rotation around a single bond are:
6. Which of the following compounds is optically (a) Conformers
active ? (b) Diastereomers
(a) Bromochloromethene (c) Enantiomers
(b) 2-Bromo-2-Chloropropane (d) Positional isomers
(c) 1–Bromo–2–Chloropropane 13. An isomer of ethanol is:
(d) All of the above. [Rohd. 2013] (a) Methanol (b) Diethyl ether
(c) Acetone (d) Dimethyl ether
O-191
(b) CH3 CH3

14. How many optically active stereoisomers are
H OH HO H
possible for butane-2,3-diol? and
OH H OH H
(a) 1 (b) 2
(c) 3 (d) 4 CH3 CH3
15. The total number of isomeric alcohols with the (c) CH3 CH3
molecular formula C4H9OH is H OH H OH
and
(a) 5 (b) 4 OH H H OH
(c) 3 (d) 2
CH3 CH3
16. The total number of isomeric trimethylbenzene is
(d) CH3 CH3
(a) 3 (b) 4
(c) 5 (d) 6 OH H HO H
and
H OH HO H
17. C6H5CHO + HCN → C6H5CH(OH)CN
CH3 CH3
The product would be
(a) Optically active 22. Which of the following Fischer's projection formula
(b) A meso compound is identical to D-glyceraldehyde?
(c) A racemate (a) CH2OH
(d) A mixture of diastereomers HO C CHO
18. The number of geometrical isomers of
H
CH3CH = CH - CH = CH - CH = CHCl is (b) CH2OH
(a) 4 (b) 6
H C OH
(c) 8 (d) 10
CHO
19. Tautomerism will be exhibited by
(a) R3CNO2 (b) RCH2NO2 (c) CHO
(c) (CH3)2NH (d) (CH3)3CNO HO C CH2OH
20. A similarity between optical and geometrical H
isomerism is that
(d) CHO
(a) If in a compound, one is present then so is
the other. H C CH2OH
(b) Each forms equal number of isomers for a
HO
given compound.
23. The name of the following compound is
(c) Both are included in stereo isomerism.
(d) They have no similarity.
21. Which of the following pairs of compounds are
(a) (2Z, 4Z)-2, 4-hexadiene
enantiomers?
(b) (2Z, 4E)-2, 4-hexadiene
(a) CH3 CH3
(b) (2E, 4Z)-2, 4-hexadiene
H OH HO H
and (d) (2E, 4E)-2, 4-hexadiene
OH H H OH
24. Number of structural isomers of C6H14 are
CH3 CH3
(a) 4 (b) 5
(c) 6 (d) 7
O-192
25. The enolic form of acetone contains 30. The number of enantiomers of the compound
(a) 9 σ bonds, 1 π bond and 2 lone pairs CH3CHBrCHBrCOOH is
(b) 8 σ bonds, 2 π bonds and 2 lone pairs (a) 0 (b) 1
(c) 9 σ bonds, 2 π bond and1 lone pair (c) 3 (d) 4
(d) 10 σ bonds, 1 π bond and1 lone pair 31. Isomerism between CH3CH2CH2OH and
CH3OC2H5 is
26. The compound which is not isomeric with diethyl
(a) Chain (b) Positional
ether is
(c) Functional (d) Structural
(a) Methylpropyl ether
(b) Butanol 32. The optical isomers which are not mirror images of
each other
(c) 2 methyl 2 propanol
(a) Enantiomers (b) Diastereoisomers
(d) Butanone
(c) Tautomers (d) Metamers
27. The compound
H3C H 33. Which has a symmetric carbon atom
C=C Cl Br H Cl
H
H3C C (b)
(a) H–C–C–H H–C–C–Cl
H3C COOH
H H H H
will exhibit
H Cl H H
(a) Geometrical isomerism
(b) Optical isomerism (c) H–C–C–D (d) H–C–C–H
(c) Geometrical and optical isomerism H H Br OH
(d) Tautomerism
34. Which one of the following has the smallest heat of
28. In following hydrogenation per mole ?
COOH COOR (a) 1–butene (b) trans–2–butene
H OH H OH
(c) cis–2–butene (d) 1, 3–butadiene
H OH H OH 35. Which of the following compounds will show

COOR COOH geometrical isomerism ?
(A) (B) (a) 2–butene
COOH (b) propene
H OH
(c) 1–phenylpropene
HO H (d) 2– methyl–2–butene
COOR 36. The number of isomers for the compound with
(C) molecular formula C2BrClFI is
(a) A and B are identical (a) 3 (b) 4

(b) A and B are enantiomers (c) 5 (d) 6
(c) A and B are diastereoisomers
37. Isomers which can be interconverted through
(d) A and C are enantiomers rotation around a single bond are
29. How many optically active stereoisomers are
(a) Conformers (b) Diastereoisomers
possible for 2,3– butanediol ?
(c) Enantiomers (d) Positional isomers
(a) 1 (b) 2
(c) 3 (d) 4
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38. Of the following compounds, which will have a zero

dipole moment ? True/False
(a) 1,1 - dichloroethylene 1. Geometric isomers are diastereomeric to each
(b) cis - 1,2 dichloroethylene other.
2. Maleic acid is more stable than fumaric acid.
(c) trans - 1,2 - dichloroethylene
(d) none of these compounds
3. Oximes are optically active around the double
39. The compounds :
bond.
H3C CH3 H3C H
4. All allenes are optically active.
C=C and C=C
CH3 5. A racemic mixture is optically inactive.
H H H
6. Chair form of cyclohexane is equally stable to its
are examples of : boat conformation.
(a) Enantiomers
(b) Geometrical isomers 7. Butane has infinite rotamors.
(c) Metamers 8. Methanol can show conformational isomerism.
(d) Optical isomers
9. All the rotamors are rapidly interconvertible.
Fill in the Blank 10. 1,3-dimethyl cyclobutane can show geometric

1. Lactic acid is an optically ……… compound. isomerism.
2. Meso form of tartaric acid contains a/an ………
plane of symmetry.
3. The compound which rotates the plane of plane
polarized light in clockwise direction is ……….
4. Glucose molecule has ……… optical isomers.
5. Tartaric acid has……… chiral carbon atoms.
6. The absolute method of configuring optically active
compound is referred as……….
7. The reference molecule for D,L configuration is
……….
8. The angle of rotation caused by an optically active
substance is……… proportional to the length of
polarimetric tube.
9. Threo and erythro isomers are……… to each other.
10. 1,2-Dimethylcyclopentane consists of ………
stereoisomers.
O-194
Answers

1. (a) 2. (c) 3. (a) 4. (d) 5. (b)
6. (c) 7. (c) 8. (c) 9. (b) 10. (a)
11. (b) 12. (a) 13. (d) 14. (b) 15. (b)
16. (a) 17. (c) 18. (c) 19. (b) 20. (c)
21. (a) 22. (c) 23. (d) 24. (c) 25. (a)
26. (d) 27. (b) 28. (b) 29. (b) 30. (d)
31. (c) 32. (b) 33. (c) 34. (d) 35. (a)
36. (d) 37. (a) 38. (c) 39. (b)
Fill in the Blank

1. active 2. internal 3. dextrorotatory
4. 16 5. 2 6. R,S nomenclature
7. glyceraldehyde 8. directly 9. diastereomeric
10. 3
True/False
1. True 2. False 3. False
4. False 5. True 6. False
10. True
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Hints and Solutions

15. There are two ways to draw cyclohexane because it can be in a hexagon shape or in a different
conformational form called the chair conformation and the boat conformation. The chair
conformation drawing is more favored than the boat because of H H
the energy, the steric hindrance, and a new strain called the H H
transannular strain. Here is what the boat conformation looks
like.
The boat conformation isn't the favored conformation because
H
it is less stable and has a steric repulsion between the two H's, H H
H
shown with the pink curve. This is known as the transannular
strain, which means that the strain results from steric H H H

H
crowding of two groups across a ring. The boat is less stable
than the chair by 6.9 kcal/mol. The boat conformation, H
however, is flexible, and when we twist one of the C-C
bonds, it reduces the transannular strain. When we twist the H
H
C-C bond in a boat, it becomes a twisted boat as drawn
H H
below. H H H
Although there are multiple ways to draw cyclohexane, the most stable and major conformer is the
chair because it has a lower activation barrier from the energy diagram.
Half–Chair
Half
E
Boat
Twist–boat Twist–boat
Chair Chair
Reaction coordinate to conformations of cyclohexane
The transition state structure is called a half chair. This energy diagram shows that the chair
conformation is lower in energy; therefore, it is more stable. The chair conformation is more stable
because it does not have any steric hindrance or steric repulsion between the hydrogen bonds. By
drawing cyclohexane in a chair conformation, we can see how the H's are positioned. There are two
positions for the H's in the chair conformation, which are in an axial or an equitorial formation.
O-196
H
H
H H
H H
H
H H
H
H H
This is how a chair conformation looks, but you're probably wondering which H's are in the equitorial
and axial form. Here are more pictures to help.
H
H
H
H H
These are hydrogens in the axial form.
H
H H
H H H
These hydrogens are in an equitorial form. Of these two positions of the H's, the equitorial form will be
the most stable because the hydrogen atoms, or perhaps the other substituents, will not be touching
each other. This is the best time to build a chair conformation in an equitorial and an axial form to
demonstrate the stability of the equitorial form.
16. The study of the relative energies of conformational isomers can be done nicely taking butane.Let us
have a Newmann projection by looking down the C(2)–C(3) bond of butane.
H
H CH3
1 2 3 4
CH3–CH2–CH2–CH3 C C
CH3 H
H
Let us assume that relatively large methyl groups will best be kept as far from CH3
each other as possible then we have the conformation called the anti-form H
H
shown in fig. (A). 120° clockwise rotation passes over a transition state to a
new minimum energy conformation of butane shown in fig. (B).
H H
CH3
Fig (A)
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Conformation (B) will be less stable than (A) because in (B) the two CH3
methyl groups are closer than they are in (A). Conformation (2) is called
H3C H
'gauche' form. Gauche form of butane (B) is about 0.6 kcal mol–1 higher in
energy than the anti form (A). There was an eclipsed transition state for
the interconversion of (A) to (B) which lies about 3.4 kcal mol–1 higher
than (A). H H
H
Fig (B)
Another 120° clockwise rotation brings us to a second gauche form of CH3
butane (B). The transition state for the conversion of (B) to (B') involves an H CH3
eclipsed state of two
H H
H
Fig (B')
C–CH3 bonds shown in fig. (C) and lies 3.8 kcal mol–1 above (B) and (B'), a H3C
CH3
total of about 4.4 kcal mol–1 above (A). Final 120° clockwise rotation return
us to (A).
H
H H
H
Fig (C)
The angle versus energy plot for butane can be shown as.
H3C
CH3
H3C H H H H3C H
H C H
H3C H H
Potential energy
CH3 H H
H 3.8 kcal H
H H H3C
mol–1
H H 3.4 kcal 3.4 kcal

mol–1 –1
CH3 B B' mol
CH3 CH3
A H CH3 A
H3C H
H H H H
H H
0° 60° 120° 180° 240° 300° 360°

Rotation about the central C2–C3bond
O-198

31. Cyclopentane is best considered as a flat ring. All trans–isomers exist as a pair of enantiomers. All cis
isomers are meso.
Me Me
Me
Me Me Me
racemate meso
trans–1,2–Dimethylcyclopentane trans–1,2–Dimethylcyclopentane
Me Me Me Me
Me Me
racemate meso
trans–1,3–Dimethylcyclopentane trans–1,3–Dimethylcyclopentane
32. Tartaric acid contains two asymmetric centers, but two of the "isomers" are equivalent and together are
called a meso compound. This configuration is not optically active, while the remaining two isomers
are D- and L- mirror images, i.e., enantiomers. The meso form is a diastereomer of the other forms.
COOH COOH COOH
H OH HO H
H OH
HO H H OH
H OH
COOH COOH
HO COOH COOH
HO COOH
Meso tartaric acid

HO COOH
HO COOH
(Natural) tartaric acid

L–(+)–tartaric acid D–(–)–tartaric acid
dextrotartaric acid levotartaric acid
(1:1)
DL–Tartaric acid
"racemic acid"
33. This nomenclature is used only in those compounds which have

(a) Only two chiral carbons and
(b) The following structure, R' - Cab - Cbc - R"
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i.e., out of six substituents on two asymmetric carbons, at least two should be same. When two like
groups 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 H C H
R" C6H5 C6H5

Brythroform Brythroform Thero form
6. CH3 CH3
H OH HO H
Br H Br H
C2H5 C2H5
7. Since the two stereoisomers are not mirror image, they are diastereomers.
8. Benzoquinone is very stable as it is highly conjugated system so it does not get enolized.
9. NaBH4 * *
Ph–C–C–Ph Ph–CH–CH–Ph
O O OH OH
The reduction product will have 3 stereoisomers of which only 2 would be optically active. The third
isomer (meso) will be optically inactive.
10. Logic:
The compounds with each doubly bonded carbon attached to two different groups (like Cab=Cab,
Cab=Ccd) exhibit geometrical isomerism i.e., cis and trans forms. The geometrical isomerism arises
due to restricted rotation of double bond.
However, even though there is restricted rotation for triple bond, alkynes do not exhibit geometrical
isomerism, since the triply bonded carbons are attached to one group each only.
11. C6H14 indicates saturated hydrocarbon i.e., an alkane. There are 5 chain isomers possible with this
formula i.e., one linear, two monosubstituted, two distubstituted.
O-200
Linear
H3C–CH2–CH2–CH2–CH3
hexane
Mono substituted Disubstituted

CH3 CH3
H3C–CH2–CH2–CH2–CH3 H3C–C–CH2–CH3
2–methylpentane CH3
H3C–CH2–CH2–CH2–CH3 2,2–dimethylbutane
CH3 H3C–CH–CH–CH3
3–methylpentane
CH3 CH3
2,3–dimethylbutane
12. Logic:
Isomers have same molecular formula but differ in their structures or in spatial arrangement.
Solution:
Compound Structural formula Molecular formula
Ethanol C2H5OH C2 H6 O
Methanol CH3OH CH4O
Diethyl ether C2H5OC2H5 C4H10O
Dimethyl ether CH3OCH3 C2 H6 O
Only dimethyl ether has same molecular formula as that of ethanol.

14. Logic:
Theoretically, the total number of enantiomers possible for a molecule is equal to 2n, where n =
number of chiral centers.
However, to show optical activity, the molecule must be asymmetric. Hence some of the configurations
may be optically inactive due to symmetry.
Solution: Butane-2,3-diol, CH3-CH(OH)-CH(OH)-CH3 has two chiral centers. Hence, theoretically, there
must be 2n = 22 = 4 enantiomers possible. However, one of the configuration has plane of symmetry and
hence is optically inactive. It is called meso isomer. It has no enantiomer. Therefore only three stereoisomers
are possible among which only are two optically active.
❍❍❍
UnitO-201
-III
C HAPTER 5
Alkenes, Cycloalkenes, Dienes
and Alkynes
1. Alkenes
Alkenes are hydrocarbons whose molecules contain the carbon–carbon double bond. They are also called
olefins. Alkenes or olefins contain the structural unit C = C and have the general formula CnH2n. These
unsaturated hydrocarbons are isomeric with the saturated cycloalkanes, so it can be said that one ring is
equivalent to a double bond.
CH3CH=CH2 H2C—CH2
Propylene
CH2
Cyclopropane
This can be further explained by the example C4H8. It has a number of isomers as shown below,
3
1 2 3 4 1 2 CH3
–CH3 H2C=CH–CH2–CH3 H2C=C
1-butene CH3
Cyclobutane Methylcyclopropane 2–methylopropene
1.1 Nomenclature and Isomerism
There are certain rules which have to be followed to write the IUPAC name of a compound containing a
double bond or more than one double bonds.
Rule number 1-Name the longest chain with the double bond. However, it is not always the longest chain of
carbons. End the name of longest chain carbon with "-ene".
C 2 H4 H H ethene
C=C
H H
C3 H6 HH propene
H
C = C–C–H
H
H
O-202
Rule number 2- When necessary, use the lowest number to give the location of double bond in the longest
chain. Some of the demonstrative examples are shown below,
C 4 H8 HHH 1-butene
H
C = C–C–C–H
H
HH
C 4 H8 HH HH 2-butene
H C–C = C–C–H
H H
C 4 H8 HH HH 2-butene
H C–C = C–C–H
H H
C5H10 HHH H 1-pentene

H
C=C–C–C–C–H
H
HH H
C5H10 HH HH H 2-pentene
H–C–C=C–C–C–H
H HH
C5H10 H 3-methyl-1-butene
H C H
H H
H
C=C–C–C–H
H
H H
H C H
HH
H
C=C–C–C–H
H
H H
H C H
H HH
H–C–C=C–C–H
H H
O-203
C5H11 H 2,2-dimethyl propene

H C H
H H
C=C–C–H
H
H
H C H
H
Alkenes normally show cis - trans or in general geometric isomerism, apart from other types of isomerism,
which has been discussed in detail in the chapter 4. Some of these geometric isomers in alkenes are shown
below,
CH2CH3 H3C H H
H3C H
C C C C
H H H CH2CH3 H
Cis–2–pentene Trans–2–pentene Cis–cyclooctene H
Trans–cyclooctene
1.2 Bonding in Alkenes

Like a single covalent bond, double bonds can be described in terms of overlapping atomic orbitals, except
that, unlike a single bond which comprises of a single sigma bond, a carbon-carbon double bond consists of
one σ and one π bond. This double bond is stronger than a single
covalent bond(611 kJ/mol for C=C vs. 347 kJ/mol for C-C) and also
shorter with an average bond length of 1.33 Angstroms (133 pm).
Each carbon of the double bond uses its three sp² hybrid orbitals to
form sigma (σ) bonds to three atoms. As predicted by the VSEPR
model of electron pair repulsion, the molecular geometry of alkenes
includes bond angles about each carbon in a double bond of about
120°. The angle may vary because of steric strain introduced by non
bonded interactions created by functional groups attached to the
Fig. 1: π bond in the perpendicular
carbons of the double bond. For example, the C-C-C bond angle in plane of ethene
propylene is 123.9°.
The unhybridized 2p atomic orbitals, which lie perpendicular to the plane created by the axes of the three sp²
hybrid orbitals, combine to form the pi (π) bond. This bond lies outside the main C-C axis, with half of the
bond on one side and half on the other. Rotation about the carbon-carbon double bond is restricted because
it involves breaking the π bond, which requires a large amount of energy (264 kJ/mol in ethylene). As a
consequence, substituted alkenes may exist as one of two isomers, called cis or trans isomers. More complex
alkenes may be named using the E-Z notation, used to describe molecules having three or four different
substituents or the side groups. If one considers but-2-ene, it has two geometric isomers. These two isomers of
butene are slightly different in their chemical and physical properties.
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1.3 Methods of Preparation of Alkenes

A good number of methods are available for the preparation of alkenes. Some of the more important
methods are being discussed below,
1.3.1 Partial Hydrogenation of Alkynes

Alkynes can be partially reduced to alkenes by the use of reagents like Lindlar's catalyst, Na in liquid NH3 etc.
An alternate to Lindlar's catalyst is P–2 catalyst with H2.
1. Lindlar's catalyst: Specially designed catalysts can be used to prepare cis–alkenes from disubstituted
alkynes. Metallic palladium deposited on calcium carbonate can be used in this way after it has been
conditioned with lead acetate and quinoline. This special catalyst is known as Lindlar's catalyst.
2. P-2 catalyst: Another catalyst that permits the hydrogenation of an alkyne to an alkene is nickel
boride called P–2 catalyst. This catalyst can be prepared by the reduction of nickel acetate with sodium
borohydride.
NaBh
4 → Ni B (P–2)
(CH3COO)2Ni    2
EtOH
Hydrogenation of alkynes in the presence of P–2 catalyst causes syn addition of hydrogen to take
place, and the alkene that is formed from an alkyne with an internal triple bond has the (Z) or cis
configuration.
Reduction with Lindlar's catalyst or P-2 catalyst

R R
H2,Pd/CaCO3
R–C ≡ C – R C=C
quinoline
(syn addition) H H
The alkene obtained in case of catalytic reduction is essentially cis.

3. Reduction with lithium or sodium metal in ammonia: When alkynes are reduced with lithium
or sodium metal in ammonia or ethylamine at low temperatures, the addition of hydrogen atom occurs
in anti–fashion. This reaction is called as dissolving metal reduction which produces trans–alkene.
R H
(i) Li,C2H5NH2
R–C ≡ C – R C=C
(ii) NH4Cl
(anti addition) H R
Mechanism
The mechanism for this reaction involves successive electron transfer from Li or Na atom and proton transfers
from NH3 or RNH2. In the first step, lithium atom transfers an electron to the alkyne to produce an
intermediate that bears a negative charge and has an unpaired electron, called as radical anion. In the second
step, the amine transfers a proton to produce a vinylic radical. Then, transfer of another electron gives a
vinylic anion. It is this step that determines the stereochemistry of the reaction. The trans–vinylic anion is
formed preferentially because it is more stable as the bulky alkyl groups are farther apart. Protonation of the
trans–vinylic anion leads to the formation of trans–alkene.
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R •• – •• R H R H
H–NHEt
Li• +R–C≡C–R C=C C=C C=C
Li•
• R • R – •• R
Vinylic radical Trans–vinylic
Radical anion
anion
•• R H
H–NHEt
C=C
H R
Trans–alkene
1.3.2 Cracking of Petroleum

Cracking of petroleum hydrocarbons is the source of commercial alkenes. Rather, it is an industrial method of
preparation of alkenes. The reaction scheme is.
1.3.3 Dehydrohalogenation of Alkyl Halides (1, 2-Elimination)

When an alkyl halide is subjected to elimination in the presence of a strong base, it loses a molecule of
hydrogen halide and yields an alkene. As an example, when isopropyl bromide is treated with hot
concentrated alcoholic solution of a strong base like potassium hydroxide, propylene is obtained.
C H OH
CH3–CHBrCH3 + KOH  2 5 → CH3CH = CH2 + KBr + H2O
heat
This is an example of dehydrohalogenation also known as 1,2-elimination. Dehydrohalogenation involves

elimination of the halogen atom and the hydrogen atom from adjacent carbons in this case. This is called
1,2-elimination. For the double bond to form, the hydrogen must come from a carbon that is adjacent to the
carbon holding the halogen. Now the carbon holding the halogen is commonly the α-carbon. Any carbon
adjacent to the α-carbon is a β-carbon, and its hydrogens are β-hydrogens. Elimination, thus involves loss of
a β-hydrogen, so it is very frequently termed as β–elimination. So, the general scheme of the reaction is,
–C–C– KOH +KX+H2O

C=C
alcohol
H X
In some cases, dehydrohalogenation, yields a single alkene and in other cases a mixture as shown below,
alc.
CH3CH2Cl + KOH  → CH2 = CH2
alc.
CH3CH2CH–CH3+KOH CH3CH2CH=CH2+CH3CH=CH–CH3
1-butene 2–butene
Cl (minor) (major)
In case of competing products, the formation of an alkene by dehydrohalogenation of alkyl halide is
governed by Saytzeff's rule which states that "The more substituted alkene is formed in greater amount during
an elimination process." All 1,2–elimination reactions are characterized by the following common traits:
O-206
(i) The substrate contains a leaving group (an atom or group that leaves the molecule) takes its
electron pair along with it.
(ii) In a position β–to the leaving group, the substrate contains an atom or group nearly always
hydrogen that can be abstracted by a base, leaving its electron pair behind.
(iii) Reaction is brought about by the action of a base. Typically, the base is a strongly basic anion
like, an alkoxide, derived from an alcohol and KOH. For example, ethoxide, C2H5O − ,
tert-butoxide, (CH3)3CO − etc. Heterolytic bond dissociation energies show that strength of
carbon-halogen bonds follow the sequence, Bulky bases like text–butoxide salts give to anti
Saytzeff or Hoffmann elimination product.
Heterolytic bond (Dissociation energy) R–F > R – Cl > R – Br > R – I
In these elimination reactions the reactivity of alkyl halides follows the sequence,
Reactivity towards (E2 elimination) R–I > R – Br > R – Cl > R – F

Some of the examples are,
(a)
(b) CH3 CH3 CH3
CH3–C–CH2CH2CH3 CH2=C–CH2CH2CH3+CH3–C=CHCH2CH3
(minor) (major)
Br
(c) CH3CH3 CH3
CH3–C – CHCH3 (CH3)2C=C(CH3)2+CH2=C–CH(CH3)2

(major) (minor)
Br
E2 Mechanism
This reaction involves a single step in which base pulls a proton away from the carbon and simultaneously a
halide ion departs, thus a double bond is formed. Halogen takes an electron pair with it while hydrogen
leaves its electron pair behind to form the double bond. What characterizes this particular mechanism is that
all the steps are taking place simultaneously, in a single step, via a single transition state. So, it is a concerted
mechanism.
X Xδ– #
–C–C– –C C– • –
•X +C=C+B–H
+ –
H Hδ Bδ
• –
•B
In this transition state two bonds are being broken that is C – H and C – X. The energy required for bond
breaking comes from the bond formation of the bond between the proton and the base, and the formation of
π bond. As the base begins to pull proton away from the molecule, the β-carbon, armed with the electron
pair begin to form a π bond with another carbon atom. As the π bond starts to form, the carbon-halogen
bond starts to break. Thus the π bond making helps to supply energy for the carbon-halogen bond breaking.
O-207
The rate-determining step involves reaction between a molecule of alkyl halide and a molecule of base, and
its rate is proportional to the concentration of both the reactants. This mechanism is named E2, as
molecularity is 2.
Rate = k[RX][:B–] E2 reaction (Bimolecular elimination)
Moreover, the order of reaction is also two because the rate of reaction depends upon the concentration of
alkyl halide and base. The best stereospecific conformation for E2 elimination is an anti-coplanar
conformation with H and X being 180° apart which permits the approaching electron-rich base to be at a
maximum distance from the electron-rich leaving group.
B•• –
H anti –coplanar
L L=Electron rich
leaving group
In certain cases, exception to Saytzeff's rule have also been observed. If one carries out dehydrohalogenation
with a strong and bulky base such as potassium tert butoxide in tert butyl alcohol, it leads to the formation of
the less substituted alkene in higher amount. Such kind of product formation is governed by Hoffmann's
elimination rule, so it is termed as Hoffmann's product. The dehydrohalogenation follows Hoffmann's rule in
two cases, either
1. When the base employed is very bulky like potassium tertiary butoxide and the leaving group is any
halide (Cl, Br, I) or
2. When the base employed is ethoxide and the leaving group is a poor one like fluoride ion.
1.3.4 Acid Catalysed Dehydration of Alcohols

Heating an alcohol with a strong acid like H2SO4 causes elimination of water and form an alkene. Elimination
of water is called dehydration.
+
H
–C–C– C=C + H2O
heat
H OH
The reaction is an elimination process and is favoured at higher temperatures. The most commonly used
acids in the laboratory are Bronsted acids which act as proton donors such as sulphuric acid and phosphoric
acid.
Mechanism
The mechanism of acid catalyzed dehydration is E1 (unimolecular elimination). In this case, the substrate is a
protonated alcohol also termed as an alkyl oxonium ion. It gives rise to the formation of carbocation
intermediate by the loss of weaker base, H2O. The carbocation formed may undergo rearrangement (if
O-208
possible) and it finally loses a proton to give an alkene. A catalytic role is assigned to the acid H2SO4 as it is
regenerated at the end of the reaction.
Step 1: Protonation of alcohol
Step 2: Formation of a carbocation
slow +
CH3CH–CH3 CH3CHCH3+H2O [rate determining step]
Isopropyl
+
H2O carbocation
Step 3: Deprotonation
+ fast CH CH=CH +H SO
CH3CH–CH2+HSO4– 3 2 2 4
It is important to note that the formation of the more stable alkene is the general rule as suggested by Saytzeff's
or Zaitsev rule in the acid-catalyzed dehydration of alcohols. However, Saytezeff's rule could predict the
formation of product only when the generated carbocation does not undergo rearrangement. In case of
carbocation undergoing rearrangement, dehydration does not follow Saytzeff's rule. Dehydration reactions
of alcohols show several important characteristics which are as follows,
1. The experimental conditions like temperature and acid concentration that are required to bring about
dehydration are closely related to the structure of the individual alcohol. Alcohols in which the
hydroxyl group is attached to a primary carbon (in case of primary alcohols) are the most difficult to
dehydrate. For example, dehydration of ethanol requires concentrated sulphuric acid and a high
temperature of 180°C.
Conc. H SO
CH3 – CH2 – OH    2
4 → CH = CH + H O
2 2 2
180 ° C
Secondary alcohols usually dehydrate under milder conditions. For example, cyclohexanol, which is a
secondary alcohol, dehydrates in 85% phosphoric acid at 165-170°C.
OH
85% H3PO4
+H2O
165–170°C
Tertiary alcohols are usually so easily dehydrated that extremely mild conditions is be used. For
example, tert butyl alcohol dehydrates in 25% H2SO4 at a temperature of 85°C only.
CH3 CH3
25%H2SO4
CH3–C–OH CH3–C=CH2+H2O
85°C
CH3
Thus, overall, the relative ease with which alcohols undergo dehydration is in the following order 3°
alcohol > 2° alcohol > 1° alcohol
O-209
2. Some primary and secondary alcohols also undergo rearrangements of their carbon skeleton during
dehydration since the intermediate involved is a carbocation which readily undergoes rearrangement.
Reactions involving carbocations undergo rearrangements wherever possible. They occur almost
invariably when the migration of an alkanide ion or hydride ion can lead to a more stable carbocation.
For example,
CH3 CH3
+ methanide +
CH3–C–CH2 migration
CH3–C–CH2
CH3 CH3
H
+ hydride +
CH3–C–CH–CH3 migration CH3–C–CH2–CH3
CH3 CH3
Rearrangements of carbocations can also lead to the change in ring size, as the following example
shows ring expansion.
CH3 OH CH3
+
CH–CH3
CH3 H+,heat
(–H2O)
2°Carbocation
In order to predict that a given ring size would undergo ring expansion or contraction, the following
points can be used as guiding principle.
(i) Formation of cyclic compounds by intramolecular cyclizations depends on two factors.
(a) Thermal stability which is determined by ring strain.
(b) The entropy factor (probability of bringing together the terminal carbons) that decreases with
chain length, making it successively more difficult to synthesize rings of increasing size.
(ii) Using the above two factors, we will summarize the ease of ring closure for cyclic compounds.
(a) Thermal stability: 6 > 7, 5 > 8, 9 >> 4 > 3
(b) Entropy (probability) of ring closure: 3>4>5>6>7>8>9

Ease of synthesis (net effect of 1 and 2) : 5 > 3,6 > 4, 7, 8, 9
O-210
(iii) In 3–membered ring synthesis, the entropy factor is more important than the thermal stability, so
their formation is readily attained despite greatest ring strain. For rings larger than six carbons,
ring stability is outweighed by the highly unfavorable entropy factor, so larger rings with more
than six carbons are stable but difficult to prepare.
Table1: Comparative details of E1 And E2 Reactions
E1 reaction E2 reaction
(a) Steps (i)

H–C–C–X H–C–C++ B••–+H–C–C–X B•• H+C=C+×
(ii) +
H–C–C+ –H C=C
(b) Transition state (i) δ– –

H–C–Cδ
+ –
Xδ B•• H C C Xδ
(ii) δ+
Hsδ H C C
(c) Kinetics First order, unimolecular. Second order, bimolecular.
Rate = k1[RX] Rate = k2[RX][:B − ]
−
(d) Driving force Ionization of R–X Attack by B: on H
(e) Stereo specificity Non–stereospecific Anti elimination
+
(f) Effect of R Stability of R Alkene stability (Saytzeff Rule)
3° > 2° > 1° RX
(g) Rearrangement Common None
(h) Regio-selectivity Saytzeff Usually, Saytzeff but Hoffmann elimination

taken place with bulky bases like (Me3CO − )
(i) Alkyl group 3° > 2° > 1° 3° > 2° > 1°
(j) Base strength Weak Strong
(k) Leaving group Weak base favours reaction Weak base favoures reaction
− −
I − > Br >Cl − > F − I − > Br >Cl − > F −
(l) Catalyst Ag+, AlCl3 No specific catalyst

O-211
Solved Examples
Example1: Compare the mechanisms of E1 and E2 reactions.
Solution: Concerted (One-step) mechanism–bimolecular elimination –E2

HO
H
H CH3 CH3 H
C=C +H2O+NaI
CH3 Na+
I C2H5 CH3
CH3CH2
Unconcerted (Two–step) mechanism–unimolecular elimination–E1

O
H H
C
H – CH3
H CH3 O CH3 CH3 H
CH3 CH3CH2
(CH3–CH2) C=C
CH3 Na+ or
I C2H5 CH3
CH3CH2 +
H CH3
+
CH3 CH3
CH3 H C=C
CH3CH2 H
C2H5
1.3.5. Debromination of Vicinal Dibromides

Vicinal or vic dibromides are dibromo compounds in which the bromine are placed on adjacent carbon
atoms. The name geminal or gem dibromide is used for those dibromides when both bromine atoms are
attached to the same carbon atom. Vic-dibromides undergo debromination when they are treated with a
solution of sodium iodide in acetone or a mixture of Zn dust in acetic acid or ethanol.
acetone
–C–C– +2NaI C=C + I2+2NaBr
Br Br
Zn in CH3CO2H
–C–C– C=C + ZnBr2
or CH3CH2OH
Br Br
Neither method is used for preparing alkenes since the necessary dibromo compounds are not readily
accessible, in fact they are prepared by the reaction of alkenes with Br2.
O-212
Mechanism
A possible mechanism of debromination with NaI in acetone is

Br
C—C– fast Br –+ C—C slow C=C + IBr

+
I– Br Br
Probable mechanism of debromination with Zn in acetic acid is
Zn → Zn2+ + 2e–
Br Br
2e–+ —C – C– Br –+ –C—C– C=C + Br–
Br
1.3.6 Wittig Reaction
This reaction involves a special class of compounds called alkylidene phosphoranes also known as
phosphorus ylides which have a carbanionic site. This carbanion attacks the carbonyl carbon giving an
intermediate called betaine which undergoes ring closure and then undergoes fission to give alkenes.
δ+ +
O PPh3 O– PPh3 O PPh3
–
δ Ph3P=O
C C C C C C
R1 H H R2 R1 H H R2 R1 H H R2
Betaine H +
H
C=C
R1 R2
Alkene
If one sees the reaction closely in terms of reactants, it can be concluded that the alkene can be generated by
putting the two reactants in such a manner that >C = O and Ph3P = C< part faces each other and then
removing O and PPh3 and joining the two carbon atoms.
C=O+Ph3P=C C=C+Ph3P=O
For example, the product formation of the reaction below is predicted on the basis of Wittig reaction.
O-213
+Ph3P=CH–CH3 X; now we have to identify x
Going with the mechanism of Wittig reaction, the product 'X' can be easily written as
CH–CH3
Some more examples of Wittig reaction are,
•• –
O
••
–
•• + •• +
O + CH2—Ph3P PPh3
••
••
CH2
••
+ •• –
O
••
CH2+ Ph3P— O
••
•• PPh3
CH2
H3C CH3 CH3

H3C
Br
Ph3P+-CH3
91% yield
KOBu
100°C,2h
H3C O H3C CH2
Camphor
1.3.7 Heating Quaternary or Tetra Alkylated Ammonium Hydroxides

Alkenes can also be formed by heating tetra alkyl ammonium hydroxides with the simultaneous elimination
of trialkyl amine. This reaction involves Hoffmann's elimination and product will be governed by Hoffmann's
rule.
H OH–
C2H5
⊕ ∆
CH2–CH2–N–C2H5 CH2=CH2+(C2H5)3N+H2O
β α C2H5
OH–
β α ⊕
CH3
∆
CH3–CH2–CH–N–CH3 CH3CH2CH=CH2+(CH3)3N+H2O
CH3 (major)
CH2–H
+
CH3CH=CH–CH3
(minor)
In those cases, when the two alkyl groups bear β −hydrogen atoms, the elimination occurs from that alkyl part
which has more number of β −hydrogens.
O-214
β
OH– α
β CH2–CH2CH3
α ⊕ ∆
CH3–CH2–CH–N–CH3 CH3CH2CH=CH2+N(Me)2n–Pr+H2O
(major)
CH2–H CH3 CH3CH=CH–CH3
β (minor)
Physical properties of alkenes

The first three members are gases, the next fourteen members are liquids and the higher ones are solids. They
are colourless and odourless except ethylene which has a faint sweet smell. These are practically insoluble in
water but fairly soluble in non–polar solvents like benzene, petroleum ether, etc. They show a regular
gradation in physical properties, such as boiling points, with increasing carbon content. The boiling points of
two successive members of the homologous alkene series differ by about 20–30°C, except for very small
homologues. The branched chain alkenes have lower boiling points than the corresponding straight chain
alkenes. Like alkanes, alkenes are generally non–polar, but certain alkenes are weakly polar. For example,
dipole moment of propene and 1–butene is about 0.35D due to their unsymmetrical geometry. Cis–alkenes,
in contrast to trans–alkenes, also have a small dipole moment. Therefore cis–alkenes, boil at somewhat
higher temperature than the trans–alkene. Cis–alkenes have poor symmetry and as such do not fit into the
crystalline lattice, with respect to the trans–isomers. Consequently, cis–alkenes have generally lower melting
points.
Chemical properties of alkenes

Alkenes commonly participate in electrophilic addition reaction due to presence of π electron cloud, which
makes them an electron abundant system inviting attack from electrophile. Out of alkenes and alkynes,
alkenes are more reactive than alkynes towards electrophilic addition reaction. It is definitely important to
remember that hydrogenation of alkene is not an electrophilic addition reaction. Moreover, towards
hydrogenation, out of alkenes and alkynes, alkynes are more reactive than alkenes.
1.5 Hydrogenation
Generally, the addition of hydrogen to unsaturated compounds like alkenes or alkynes is among the most
common and almost certainly the most useful of all their addition reactions. Direct addition of hydrogen
always involves heterogeneous catalysis by finely divided metals such as Ni, Pt, Pd, Ru, Rh etc. It is significant
in this context that both alkenes and hydrogen react exothermically and reversibly with the catalytic metals.
With the alkene this presumably involves its π electrons as alkanes are not similarly adsorbed. No π electrons
are available in the hydrogen molecule either and its adsorption must involve considerable weakening of its
σ bond, though not necessarily complete fission to yield H • atoms. The actual spacings of the metal atoms in
the surface will clearly be of importance in making one face of a metal crystal catalytically effective and
another not, depending on how closely the actual atom spacings approximate to the bond distances in alkene
and hydrogen molecules. In actual practice, only a relatively small proportion of the total metal surface is
found to be catalytically effective, so called 'active sites'. These adsorb alkene strongly, and then desorb the
resultant alkane molecule immediately, thus becoming free for further alkene absorption. In agreement with
this 'lining up' of alkene molecules on the catalyst surface and the probable approach of activated hydrogen
molecules from the body of the metal, it might be expected that hydrogenation would proceed
stereoselectively syn. For example,
O-215
Me H
Ni/H2
H Me
Me Me
Cis isomer
H2 H H H CMe3
Me3CC≡CCMe3 C=C not C=C
Lindlar's catalyst
Me3C CMe3 Me3C H
(1) (2)
Alkynes can often be reduced selectively to the alkene by use of the Lindlar's catalyst (Pd supported on
CaCO3 partialy poisoned with Pb(OAc)2). Here again syn stereoselectivity is observed despite the fact that
this will lead to the more crowded, thermodynamically less stable cis–alkene (1) rather than trans alkene(2). It
has also been demonstrated that cis alkenes are hydrogenated much more rapidly than trans alkenes. In any
case, the rate of hydrogenation falls with increasing substitution in the alkene.
More recently homogeneous hydrogenation catalysts, such as RhCl(Ph3P)3, (Wilkinson's catalyst) have been
developed which are soluble in the reaction medium. These are believed to transfer hydrogen to an alkene
via a metal hydride intermediate. Hydrogenation with Wilkinson's catalyst too leads to a considerable degree
of syn stereoselectivity in hydrogen addition.
Example 2: (i) Complete the following reactions

Pd,Pt, or Ni
(a) CH3CH = CH2 + H2     → ?
[RhCl(Ph 3 P)3 ]
(b) CH3CH = CH2 + H2      → ?
The catalyst in (ii) is Wilkinson's catalyst.
(ii) In terms of the catalysts used, classify these two reactions.
(iii) Show the steps in the mechanism of reaction (ii) involving the Wilkinson's catalyst.
Solution : (i) (a) and (b) CH3CH2CH3.
(ii) Both reactions are catalytic hydrogenations (addition of H2). (i) Heterogeneous catalytic
hydrogenation in which the solid catalyst is in a different phase from the reactants. (ii)
Homogeneous catalytic hydrogenation because reactants and catalyst are in the same phase. (c)
In step 1, an H2 adds to the rhodium complex and one Ph3P ligand (L) is lost, resulting in a
five–coordinate rhodium complex, (A) (L = Ph3P). In this oxidative addition, the Rh changes
oxidation state from +1 to +3. In step 2, the alkene reacts with (A) to form a π complex, (B)
which undergoes rearrangement (step 3) of an hydrogen atom to one of the carbons of the
double bond, the other carbon forming a σ bond to the Rh (C).
O-216
H H H
L Cl R2 L Cl C=C L Cl L Cl
Rh –L
Rh Rh Rh
L L L L L L L C–C–H
C=C
(A) (B) (C)
In the last step, a second hydrogen atom is transferred to the other carbon, and the alkane is lost with
simultaneous regeneration of the metal catalyst.
+L
(C) [RhCl(Ph3P)3]+HCH2CH2H.
The catalysis depends on the ability of rhodium (a transition metal), to form a π complex with alkene.
1.5.1 Addition of Hydrogen Halides
Hydrogen halides (HCl, HBr and HI) add to the double bond of alkenes.
R
R
C = C+HX –C–C–
X H
Mechanism for addition of hydrogen halide to an alkene is a normal electrophilic addition mechanism. It
involves the following two steps,
Step 1: Formation of carbocation

R H
R
slow
C = C+H–X (RDS) –C–C–+X–
⊕
RDS is rate determining step.
Step 2 : Attack on carbocation

–
R R X
– fast
–C–C–+X –C–C–
⊕
H X H
The addition of HBr to some alkenes gives a mixture of the expected alkyl bromide. If there is a possibility of
rearrangement, then some more isomers are also formed.
O-217
CH3 CH3 CH3

H+ Br–
CH2=CH CH–CH3 CH3–CH–C–CH3 CH3–CHBr–CH–CH3
⊕ ∼H– 2–Bromo–2–methylbutane
H CH3 CH3
–
Br
CH3CH2–C–CH3 CH3CH2–C–CH3
⊕
3° Br
2–Bromo–2–methylbutane
In the ionic addition of an unsymmetrical reagent to a double bond, the positive portion of the reagent
attaches itself to a carbon atom of the double bond so as to yield the more stable carbocation as intermediate.
Because this is the step that occurs first, it is the step that determines the overall orientation of the reaction. In
those cases where rearrangement does not occur, the addition of HX to alkenes follow Markovnikov's rule.
The rule states that during the addition of an unsymmetrical reagent to an unsymmetrical alkene "the
negative part of the unsymmetrical reagent goes to that carbon atom which bears lesser number of hydrogen
atoms". But in those cases, where rearrangement occurs, the overall addition of HX to alkenes does not
follow Markovnikov's rule. For example, when HI is added to 1-butene the reaction leads to the formation
2-iodobutane. 2-iodobutane contains a stereocenter as shown here with asterisked carbon,
*
CH3CH2CH=CH2+HI CH3CH2–CH–CH3
The product, therefore, can exist as a pair of enantiomers. The carbocation that is formed in this first step of
the addition is trigonal planar (sp2 hybridized) and is achiral. When the iodide ion reacts with this flat
carbocation, reaction is equally likely at either face. Thus reaction leads to the formation of two enantiomers
and both the enantiomers are produced in equal amounts. Thus, product of the reaction is a racemic mixture.
Example 3: Explain the regioselectivity of the products when HBr reacts with (a) CF3CH =
CH2, (b) BrCH = CH2 and (c) CH3–O–CH = CHCH3.
Solution: An electron–withdrawing group attached to the carbon that has lesser number of hydrogens will
tend to destabilize a positive charge on this carbon and cause the addition to be anti–Markovnikov in nature.
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 π delocalization of an unshared electron pair from Br to C+,
•• +
+
thereby stabilizing the R+,[•• Br − C H – CH3 ↔[•• B R = CH − CH3 ] .Thus, the Markovnikov product,
•• ••
Br2CHCH3, is formed. (c) Protonation of either C of the C = C gives a 2° R+. However, O atom behaves just
+ +
like Br in delocalizing a pair of electrons to the adjacent C , stabilizing the positive charge and H bonds to
the carbon β to the O as follows
•• + +
[CH3– O − C H–CH2CH3 ↔ CH3 – O = CH – CH2CH3]
•• ••
O-218
The product is CH3 – O – CHBrCH2CH3. In general when the electron withdrawing group attached to the
doubly–bonded carbon has an unshared pair of electrons, Markovnikov addition is observed.
1.5.2 Addition of Hydrogen Bromide in Presence of Peroxides

The addition of HBr to propene, MeCH = CH2(1), under polar conditions ( in absence of peroxide) yields
2–bromopropane. However, in the presence of peroxides like benzoyl peroxide or under other conditions
that promote radical formation the addition yields 1–bromopropane. This addition of HBr in presence of
peroxide is generally referred to as the peroxide effect leading to Anti Markvnikov addition. It is also
referred as Kharasch effect. This difference in orientation of HBr addition is due to the fact that in the first
case, the reaction is initiated by H+ and proceeds via the more stable secondary carbocation while in the
second case, it is initiated by Br • and proceeds via the more stable secondary carbon free radical.
Mechanism
Anti– Markvnikov addition is a free radical mechanism and it is normally comprised of 3 steps.
Step 1:Chain initiation step
R–O–O–R → 2RO • (–O–O–bond is weak)
RO • + H–Br → RO – H + Br •
Step 2:Chain propagation step

• •
MeCH=CH2+Br• MeCH–CH2Br+MeCH–CH2
(1) H–Br (2) (4)
• Br
Br +MeCH2–CH2Br
(3)
The initiation is by Br • , as hydrogen abstraction by RO • from HBr is energetically much more favourable
than the alternative of bromine abstraction to form ROBr + H • . The alternative addition of Br • to (1) to form
•
MeCH(Br)CH2 • (4) does not occur, as secondary radical MeCHCH2Br (2) is more stable than primary radical
(4).
It is very important to note that anti –Markovnikov addition is applicable only for HBr and that too in the
presence of a peroxide.The reason for this is reflected in the ∆H values (kJ mol–1) for the two steps of the
chain reaction for addition of HX to CH2 = CH2, as shown by data below,
(1) X • + CH2 = CH2 (2) XCH2CH2 • + HX
H–F –188 +155
H – Cl –109 + 21
H – Br –21 –46
H–I +29 –113

O-219
Only for HBr, both the chain steps are exothermic while for HF the second step is highly endothermic,
reflecting the strength of the H–F bond and the difficulty of breaking it. For HCl, it is again the second step that
is endothermic (though not to such a great extent) while for HI it is the first step that is endothermic, reflecting
the fact that the energy gained in forming the weak I–C bond is not compensatory to the energy being lost in
breaking the C = C double bond. Thus only a few radical additions of HCl are known, but the reactions are
not very rapid and the reaction chains are short at ordinary temperatures.
Even with HBr addition, the reaction chains tend to be rather short, much shorter than those in halogen
addition and more than a trace of peroxide is thus needed to provide sufficient initiator radicals. For
preparative purposes up to 0.01 mol peroxide per mol of alkene is required. Once inititated, reaction by this
pathway is very much faster than any competing addition via the polar pathway and the Anti–Markovnikov
product like (3) will thus predominate. If the Markovnikov product, e.g. MeCH(Br)CH3 from propene, is
required it is necessary either to purify the alkene rigorously before use or to add inhibitors (good radical
acceptors such as phenols, quinones, etc) to mop up any radicals formed in the reaction. Essentially
complete control of orientation of HBr addition, in either direction, can thus be achieved, under preparative
conditions, by incorporating either peroxides (radical initiators) or radical inhibitors in the reaction mixture.
This is particularly useful as such control is not confined purely to alkenes themselves.
Example 4 : (i) Rule out the following mechanism for the peroxide induced addition of HBr to
a symmetrically R–substituted alkene such as RCH = CHR.
Initiation step: RO • + HBr → ROBr + H •

•
Propagation step 1: RCH = CHR + H • → R C HCH 2R
•
Propagation step 2: R C HCH 2R + HBr → RCHBrCH 2R + H •
Bond energies of H – Br and C – Br bond are 88 and 69 kcal mol–1 respectively.
Example: (ii) Why is this mechanism inappropriate for an unsymmetrically R–substituted

alkene such as R2C = CH2 ?
Solution : (i) The actual initiation step, RO • + HBr → ROH + Br • , is thermodynamically more favorable
because O–H has a much greater bond energy than the very weak O–Br. Also, step 2 is endothermic, ∆H =
(bond energy of H–Br)–(bond energy of C–Br) = 88–69 = +19 kcal/mol.
Solution: (ii) This mechanism would lead to the unobserved Markovnikov addition.
1.5.3 Addition of Bromine and Chlorine

Alkenes react rapidly with bromine at room temperature and in the absence of light. If bromine in CCl4 is
added to an alkene, the reddish-brown colour of bromine disappears almost instantly as long as the alkene is
present in excess. This serves as a classical test for detection of unsaturation in alkenes or alkynes.
O-220
(a)
CCl4
C=C + Br2 –C–C– rapid decolorization of Br 2/CCl4 is
r.t.
a test for alkenes and alkynes
Br Br
vicinal–dibromide
(b) CH3CH=CH3+Cl2 –9°C CH3–CH–CH–CH3
Cl Cl
Mechanism
The mechanism proposed for halogen addition is an ionic mechanism proceeding via cyclic halonium ion in
general. In the first step the exposed electrons of the π bond of the alkene attack the halogen in the following
way.
Br
R R R R
Br2 in + – –Br– Br
C C C C C C C C
2 CCl4 1 2
1
Br Br
– +
Br Br Cyclic bromonium ion Vicinal dibromide
In this reaction, when the attacking reagent (bromine) approaches alkene, the temporary polarization
develops on the alkene with C2 atom gaining a negative charge and C1 atom acquiring positive charge as it
can be compensated by the +I effect of R group. The alkenes, being electron rich compounds due to the
presence of π–electron cloud, are attacked by the electrophile (Br+) to give a cyclic bromonium ion. Here, the
formation of cyclic bromonium ion as intermediate is possible because bromine is of considerably large size
having lone pairs to be bonded to both the carbons simultaneously. The cyclic bromonium ion is then
attacked by Br– from the top as lower side is already blocked. Now, the three membered ring is cleaved by
trans opening giving vicinal dibromide as the product. Thus, the overall addition of Br2 to alkene follows trans
stereoselectivity. For example, when cyclopentene reacts with bromine in CCl4, anti-addition occurs and a
mixture of two enantiomeric molecules of trans-1,2-dibromocyclopentane are obtained giving rise to a
racemic modification as shown below,
Br2 +
Br H H Br
CCl4
H Br Br H
Similarly, 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 it is observed 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.
1.5.4 Addition of Water

Conversion of an alkene into alcohol can be achieved by hydration of alkene. Couple of more methods like
hydroboration - oxidation and oxymercuration -demercuration also convert an alkene into alcohal.
O-221
1. Acid catalyzed hydration: The acid catalyzed addition of water to the double bond of an alkene is a
method of preparation of low molecular mass alcohols. The addition of water to the double bond follows
Markovnikov's rule in those case where rearrangement is not involved.
CH3 CH3
H+
CH3–C=CH2+HOH CH3–C–CH3
25°C
OH
Mechanism
As the reactions follow Markovnikov's rule, acid catalyzed hydration of alkenes do not yield primary alcohols
except in the special case of the hydration of ethene. The occurance of carbocation rearrangements limits the
utility of alkene hydrations as a laboratory method for preparing alcohols.
+
OH2 OH
H⊕ ⊕ H2O –H⊕
MeCH=CH2 MeCH –CH2 MeCH–CH2 MeCH–CH2
H H H
(1)
The formation of the carbocationic intermediate (1), either directly or via an initial π complex, appears to be
rate limiting and the overall orientation of addition is Markovnikov. Acids that have weakly nucleophilic
anions (like HSO −4 from dilute aqueous H2SO4) are chosen as catalysts, so that their anions will offer little
competition to the actual nucleophile H2O. In case, if any ROSO3H is formed, it will be hydrolysed to ROH
under the conditions of the reaction.
2. Hydroboration-oxidation (HBO): Whenever an alkene is allowed to react with diborane followed by

hydrogen peroxide an alcohol is obtained as shown below,
BH3. ET2O
diglyme B
91%
H2O2 / NaOH / H2O
OH
So, as observed, in the overall hydroboration-oxidation reaction, H2O is added to the double bond. This is
reiterated with the examples below,
(i) CH3 CH3
(BH3)2 H2O2 / OH–
CH3–C=CH2 CH3–CH–CH2OH
(ii) CH3 CH3
(BH3)2 H2O2 / OH–
CH3–CH=C–CH3 CH3–CH–CH–CH3
OH
O-222
The reaction is free from rearrangment because the reaction mechanism does not involve carbocation
intermediate. Moreover, the reaction involves syn addition of the two groups - H and OH.
The reaction scheme can be presented as below,
R' R'
R' H Hydroboration H2O2/OH–
C=C+H–B –C–C– –C–C–
Oxidation
H H
H B H OH
H
Mechanism
Step1:Hydroboration
With the reagent diborane, (BH3)2 alkenes undergo hydroboration to yield trialkylboranes, R3B.
(BH3)2
CH3–CH=CH2 CH3–CH–CH2 CH3-CH2-CH2
BH2
H BH2
(CH3–CH2–CH2+3B)
Step2: Oxidation
Trialkylboranes, R3B on oxidation gives alcohols. The oxidation step involves conversion of the C – B bond
into C – OH without inversion. The probable mechanism involves the following steps,
R H R R
H
O–O
B R–B–O–O R–B–O–R + OH
R R HOO–
R
H R R R
O–O–B–O–R B–O–R R–B–O–R
O HOO– O O
O
R R + H O
H
R–O–B–O–R
H–O O–H H
O H2O B
+ R–O
OH + R O
H
Interestingly, it can be said that hydroboration–oxidation process gives products corresponding to
anti-Markovnikov addition of water to the carbon–carbon double bond. Some more examples are,
O-223
OH
1. B2H6
+
2. H2O2 OH
85% 15%
H BH3 H OH
H3C
BH3 H2O2
C CH2 H3C—C—CH2 H3C—C—CH2
THF OH–
H3C CH3 CH3
3. Oxymercuration-Demercuration: In the overall oxymercuration-demercuration reaction, H2O is

added to the double bond. The reaction is again free from rearrangment like hydroboration-oxidation. It is
because the reaction does not involve carbocation intermediate.Moreover the reaction involves syn addition
using Markovnikov's rule. Alkenes react with mercuric acetate in the presence of water to give
hydroxymercurial compounds which on reduction yield alcohols.
H HgOAc HH
R H
Oxymercuration NaBH4
C = C+H2O+Hg(OAc)2 R–C–C–H R–C–C–H
Demercuration
R H
OH H OH H
OAc is CH3–COO– group
The first stage, oxymercuration involves addition to the carbon–carbon double bond of -OH and Hg(OAc)2.
The electrophile of Hg(OAc)2 is AcOHg+ that adds 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 carbon.
+HgOAc HgOAc
•• OAc–
H2O [RCH–CH2] RCH–CH2+HOAc
••
OH
Mercurinium ion
Then, in demercuration, HgOAc is replaced by H. The reaction sequence amounts to hydration of the
alkene, but is much more widely applicable than direct acid catalysed hydration due to the distinct advantage
of yielding non rearranged products. Oxymercuration-demercuration gives alcohols corresponding to
Markovnikov addition of water to the carbon-carbon double bond. For example,
O-224
(i) Hg(OAc)2,H2O
CH3(CH2)3CH=CH2 CH3(CH2)3CH–CH2
OH HgOAc
NaBH4
CH3(CH2)3CH–CH3
OH
(ii) CH3 CH3

Hg(OAc)2,H2O NaBH4
CH3–C–CH=CH2 CH3–C–CH–CH3
CH3 CH3 OH
1.5.5 Halohydrin Formation

If the halogenation of an alkene is carried out in aqueous solution rather than in CCl4, the major product of
the reaction is a halohydrin molecule. In this case, the molecules of the solvent become reactants.
C=C+X2+H2O –C–C–+–C–C–+HX
X OH X X
X2=Cl2 or Br2
Mechanism
Halohydrin formation can be explained by the following mechanism
C=C+X–X –C–C–+X–
X+
+OH OH
2
–C–C–+H2O –H+
–C–C– –C–C–
X+ X X
The addition of X and OH occurs in the trans manner, as the reaction proceeds by the formation of halonium
ion intermediate. If the alkene is unsymmetrical, the halogen adds up on the carbon atom with greater
number of hydrogen atoms so that the overall addition follows Markovnikov's rule.
H3C CH3
Br2,H2O
C = CH2 C–CH2Br
or HOBr
H3C CH3
OH
1.5.6 Hydroxylation
There are a number of reagents that overall add two OH groups to alkenes. The two OH groups can be either
added from the same side known as syn hydroxylation or from the opposite side which is generally termed as
anti hydroxylation.
O-225
1. Syn hydroxylation: Syn hydroxylation can be achieved by the use of osmium tetroxide (OsO4) or by
the use of Baeyer's reagent Baeyer's reagent is cold, alkaline KMn O 4 .
Addition of OsO4
OsO 4 adds to yield cyclic osmic esters (2) which can be made to undergo ready hydrolytic cleavage of their
Os–O bonds to yield the1,2–diol (3).
Me O
O
OsO4 Os
Me H HO
O
H2O
O H HO H
H Me Me
+(HO)2OsO2
Me H Me H
(1) (2) (meso compound)(3)
Cis 2–butene (1) thus yields the meso 1,2 diol–(3), i.e., the overall hydroxylation is stereoselectively syn, as
would be expected from Os–O cleavage in a necessarily cis cyclic ester (2). The disadvantage of this reaction
as a preparative method is the expense and toxicity of OsO4. However, this disadvantage can be nullified by
using it only in catalytic quantities in association with H2O2 which re–oxidises the osmic acid, (HO)2OsO2,
formed to OsO4.
Addition of Baeyer's reagent (cold, alkaline permanganate, Mn O −4 )
Alkaline permanganate, MnO −4 (a reagent used classically to test for unsaturation), will also effect
stereoselective syn addition and this by analogy with the above, is thought to proceed via cyclic (cis)
permanganic esters. It has not proved possible actually to isolate such species but use of Mn18O −4 , was found
to lead to a 1,2–diol in which both oxygen atoms were O18 labeled. Thus both were derived from MnO −4 , and
neither from the solvent H2O, which provides support for a permanganic analogue of (2) as an intermediate,
provided that Mn18O −4 undergoes no O18 exchange with the solvent H2O under these conditions. The
disadvantage of MnO −4 for hydroxylation is that the resultant 1,2 –diol is very much susceptible to further
oxidation by it.
2. Anti hydroxylation and epoxidation: Peroxyacids, RCOOOH will also oxidize alkenes, e.g. trans
2–butene (4), by adding an oxygen atom across the double bond to form an epoxide (5).
O O
C C
R Oδ
– R O H
H
– O O
H–Oδ
Me Me H H +RCO2H
Me Me
Me Me
H
H H
(4) (5)
O-226
Epoxides though uncharged have a formal resemblance to cyclic bromonium ion intermediates, but unlike
them are stable and may readily be isolated. However, they undergo nucleophilic attack under either acid or
base catalysed conditions to yield the 1,2–diol. In either case attack by the nucleophile on carbon atom will
be from the opposite side of the oxygen bridge in (5). Such attack on the epoxide will involve inversion of
configuration.
O H Me H Me
O– HO
H OH H2O OH
OH–
Me
Me Me Me
H H
H (7)
(5)
H⊕
H
O OH OH
⊕ H2O
H Me H Me Me H Me
H H
Me Me –H+
⊕
OH2 OH
H (6) (7)
Attack has been shown on only one of the two possible carbon atoms in (5) and (6), though on different ones
in the two cases. In each case, attack on the other carbon will lead to the same product, the meso 1,2–diol (7).
By comparing the configuration of (7) with that of the original alkene (4), it can be seen that in overall terms
setereoselective anti hydroxylation has been effected.Thus by suitable choice of reagent, the hydroxylation of
alkenes can be made stereoselectively syn or anti. For example,
3CH2=CH2+2KMnO4+4H2O 3CH2–CH2+2MnO2+2KOH (Syn addition)
OH OH
(Ethylene glycol)
(1) OsO4
CH3CH=CH2 CH3–CH–CH2 (Syn addition)
(2) NaHSO3/H2O
OH OH
(Propylene glycol) (Anti addition)
OH H
CH3 CH3
RCO3H
C=C H+, H2O
CH3–C–C–CH3+enantimer
H H
H OH
Cis–2–butene (Trans–,2–diol)
O-227
Example 5: Write the products formed when cis and trans - 2 -butene are treated with peroxy
acetic acid.
Solution : CH3 CH3 O
CH3CO3H
C=C C–C
CH3 CH3
H H
H H
Cis–2-butene
H CH3 O O
CH3CO3H
C=C C–C + C–C
CH3 H H CH3 CH3 H
Trans–2–butene CH3 H H CH3
Example 6 : Write the products formed when 1-butene is treated with mcpba.
Solution : O
O
O–OH CHCl3
H2C–CH2–CH=CH2 + H3C–CH2–CH–CH2 +
1,2–epoxybutane
O
Cl
mcpba OH
Cl
1.5.7 Oxidation by Hot Alkaline KMNO4

Alkenes are oxidatively cleaved by hot alkaline permanganate solution. The terminal CH2 group of 1-alkene
is completely oxidized to CO2 and water. A disubstituted carbon atom of a double bond becomes \/ C = O
group of a ketone. A monosubstituted carbon atom of a double bond becomes aldehyde group which is
further oxidised to salts of carboxylic acids. For example,
(i) KMnO4,OH– O
H+
CH3CH=CHCH3 2CH3–C 2CH3CO2H
heat
O–
(cis or trans) Acetate ion
(ii) CH3 CH3

KMnO4, OH–
CH3–CH2–C=CH2 CH3CH2–C=O +CO2+H2O
H+
(c)
O-228
(d) CH3 CH3

KMnO4, OH–
CH3–CH2–CH2HC=CH–CH CH3CH2CH2CO2H + CH–CO2H
H+ CH3
CH3
1.5.8 Ozonolysis
A more widely used method for locating the position of double bond in an alkene involves the use of ozone,
O3. Ozone reacts vigorously with alkenes to form unstable compounds called molozonides, which rearranges
spontaneously to form compounds known as ozonides. Ozonides, themselves are highly unstable so these
are reduced directly with Zn and water. The reductive ozonolysis produces carbonyl compounds - aldehydes
and ketones, that can be isolated and identified.
O
–C–C– C C 2 C = O + Zn(OH)2
O3
–C=C– O O O O
O Ozonide Aldehydes and /or Ketones
Ozonolysis can be of either of reductive type or of oxidative type. The difference lies in the fact that products
of reductive ozonolysis are aldehydes and/or ketones while in oxidative ozonolysis, the products are
carboxylic acids and/or ketones. This is because H2O2 formed would oxidize aldehdyes to carboxylic acids,
however ketones are not oxidized. In reductive ozonolysis, we add zinc which reduces H2O2 to H2O and thus
H2O2 is not present at all to oxidize any aldehyde formed.
Zn + H2O2 → ZnO + H2O
For example,
3 (i)O ,CH Cl ,
(CH3)2CH – CH = CH2     2 
2
→ (CH3)2CHCHO + HCHO
(ii)Zn / H2 O
3 (i)O ,CH Cl ,
(CH3)2C = CH – CH3     2 
2
→ (CH3)2C = O + CH3CHO
(ii)Zn / H2 O
Example 7: Write structural formula for the compounds which yield the following products on
reductive ozonolysis.
(i) Two moles of O = C(CH3)CH2CH3
(ii) (C2H5)2C = O + O = CHCH = O + O = CHCH2CH3
(iii) H2C = O + O = CHCH(CH3)CH(CH3)2
(iv) Two moles of O = CHCH2CH = O
(v) O = CHCH2CH2CH2CH = O
Solution : (i) 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.
O-229
CH3 CH3 H3C H3C
CH3CH2C=O O=CCH 2CH3 CH3CH2C=CCH2CH3(cis or trans)

(ii) 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
(iii) Two different carbonyl compounds means the alkene is unsymmetrical.
H2C = O+O = CHCH(CH3)CH(CH3)2 ← H2C = CHCH(CH3)CH(CH3)2
(iv) Two moles of a dicarbonyl compound signals a symmetrical cycloalkadiene.
HC=O O=CH
H2C CH2
HC=O O=CH
(v) 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
1.5.9 Substitution Reactions at Allylic Position

high
Cl2 + H2C = CHCH3  → H2C = CHCH2Cl + HCl
temperature
low concentration
Br2 + H2C = CH – CH3       → CH2 = CH – CH2Br + HBr
of Br2
These halogenations are like free radical substitution of alkanes. The order of reactivity of H-abstraction is
allyl>3 >2 >1 >vinyl. Allylic substitution by chlorine is carried out using Cl2 at high temperature and alkene
with α −carbon in gaseous phase. Allylic bromination can be carried out using N–bromosuccinimide.
Propene undergoes allylic bromination when it is treated with N–bromosuccinimide (NBS) in CCl4 in the
presence of peroxides or light.
O O
light or ROOR
CH2=CH–CH3 + N–Br CH2=CH–CH2–Br+ N–H
CCl4
O O
N–Bromosuccinimide 3–Bromopropene
(allyl bromide) Succinimide
(NBS)
O-230
Mechanism
The reaction is initiated by the formation of a small amount of Br • (possibly formed by dissociation of Br2
molecule). The chain propagation steps for this reaction are the same as for chlorination.
CH2=CH–CH2–H+Br CH2=CH–CH2+HBr
CH2=CH–CH2–Br–Br CH2=CH–CH2Br+Br
N–Bromosuccinimide is nearly insoluble in CCl4 and provides a constant but very low concentration of
bromine in the reaction mixture. It does this by reacting very rapidly with the HBr formed by the reaction of
NBS with traces of H2O present in it. Each molecule of HBr is replaced by one molecule of Br2.
O O
N–Br+HBr N–H+Br2
O O
Under these conditions, that is, in a non–polar solvent and with a very low concentration of bromine, very
little bromine adds to the double bond, instead it undergoes substitution and replaces an allylic hydrogen
atom.
To understand why high temperature favours allylic substitution over addition requires a consideration of the
effect of entropy changes on equilibria. The addition reactions has a substantial negative entropy change
because it combines two molecules into one. At low temperatures, the T∆S term in ∆G = ∆H –T∆S, is not
large enough to offset the favorable ∆H term. But as the temperature is increased, the T∆S term becomes
more significant, ∆G becomes more positive, and the equilibrium becomes more unfavorable for addition
and subsequently favours allylic substitution.
1.6 Polymerisation of Alkenes

Polymerisation of alkenes to produce polymers like polythene, polypropene, PVC, PTFE etc. the general
method of preparation is shown below,
O-231
Some of the common polymers of alkenes are
(a) Notice that the principle
is the same for each
addition polymerisation
H H
H H
n C C * C C *
H H
H H n
ethene Poly(ethene)
(b) Each of the polymer

structures shows the
repeat unit in brackets.
This is repeated thousands
of times in each polymer
molecule.
H H
H H
n C C * C C *
H Cl
H Cl n
chloroethene Poly(choloroethene)
(c) It is important to show

the repeat unit with
'side–links' to indicate
that both sides are attached
also to other repeat units.
H H
H H
n C C * C C *
H C6H5 C6H5 n
H
phenylethene Poly(phenylethene)
Most frequently encountered polymers of alkenes are generally addition polymers. Some of these types are
described below.
1.6.1 Poly(ethene) or Polythene or Polyethylene

It is generally of two types;
1. LDPE (low density polythene)
2. HDPE (high density polythene)
1. Low density poly(Ethene), LDPE: Formation of LDPE is an example of addition polymerisation. An

addition polymerisation reaction is one in which two or more molecules join together to give a single product.
During the polymerisation of ethene, thousands of ethene molecules join together to make poly(ethene) -
commonly called polythene.
O-232
nCH2=CH2 [–CH2–CH2]n
The number of molecules joining up is variable, but it is in the region of 2000 to 20000. Reaction conditions
are drastic and the temperature required is 200°C, pressure is high and a small amount of oxygen as an
impurity is required to initiate.
Properties and uses

Low density poly(ethene) has quite a lot of branching along the hydrocarbon chains, and this prevents the
chains from lying tidily close to each other. Those regions of the poly(ethene) where the chains lie close to
each other and are regularly packed are said to be crystalline. Where the chains are a random jumble, it is
said to be amorphous. Low density poly(ethene) has a significant proportion of amorphous regions. One
chain is held to its neighbours in the structure by Van der Waals dispersion forces. Those attractions will be
greater if the chains are close to each other. The amorphous regions where the chains are inefficiently packed
lower the effectiveness of the Van der Waals attractions and so lower the melting point and strength of the
polymer. They also lower the density of the polymer hence, "low density poly(ethene)". Low density
poly(ethene) is used for familiar things like plastic carrier bags and other similar low strength and flexible sheet
materials.
2. High density poly (Ethene), HDPE: This is made under quite different conditions from low density
poly(ethene). Conditions required are temperature is kept at about 60°C, pressure is low - a few atmospheres
and the reaction is catalysed by Ziegler-Natta catalysts or other metal compounds.
Ziegler-Natta catalyst
Ziegler-Natta catalysts are mixtures of titanium compounds like titanium(III) chloride, TiCl3, or titanium(IV)
chloride, TiCl4, and compounds of aluminium like aluminium triethyl, Al(C2H5)3. There are all sorts of other
catalysts constantly being developed. These catalysts work by totally different mechanisms from the high
pressure process used to make low density poly(ethene). The chains grow in a much more controlled - much
less random - way.
Properties and uses of HDPE

High density poly(ethene) has very little branching along the hydrocarbon chains - the crystallinity is 95% or
better. This better packing implies that van der Waals attractions between the chains are greater and so the
plastic is stronger and has a higher melting point. Its density is also higher because of the better packing and
smaller amount of wasted space in the structure. High density poly(ethene) is used to make things like plastic
milk bottles and similar containers, washing up bowls, plastic pipes and so on. Look for the letters HDPE near
the recycling symbol.
1.6.2 Polyvinyl Chloride,PVC

Poly(chloroethene) or poly vinyl chloride is commonly known by the initials of its old name, PVC.
Poly(chloroethene) is made by polymerising chloroethene, CH2=CHCl.
O-233
The equation is usually written:
Cl H Cl H
nC C —C–C—
H H HH n
It doesn't matter which carbon is attached to chlorine in the original molecule. The polymerisation process
produces mainly atactic polymer molecules - with the chlorines orientated randomly along the chain.
2. Cycloalkene (or Cycloolefin)

A cycloalkene is a type of alkene hydrocarbon which contains a closed ring of carbon atoms, but has no
aromatic character. Some cycloalkenes, such as cyclobutene and cyclopentene, can be used as monomers to
produce polymer chains. In IUPAC nomenclature cyclic alkenes named as cycloalkenes. The general formula
of cyclic alkene is CnH2n-2. Due to geometrical considerations, smaller cycloalkenes are almost always the cis
isomers, and the term cis tends to be omitted from the names. Some of the cyclic compounds containing
double bonds is shown below,
6
5 1
4 2
3
Cyclobutene Cyclopentene Cyclohexene 1, 4–Cyclohexadiene
Some frequently observed examples of cyclic alkenes are cyclobutene and cyclopentene. Cycloalkenes have
wide applications in synthesis of different polymers.
2.1 Conformation in Cycloalkene

Conformation is a spatial arrangement of a molecule of a given constitution and configuration. In the case of
a four atom molecule linked in a chain manner, rotation of atom A or D about the inner B-C bond by an angle
ω leads to a different mutual relation of atom A and D and results in population of a set of different rotational
isomers or "conformations".
O-234
D
rotation C D
through ω C A B
A B
The single parameter differentiating such conformers is an angle between two planes that contain atoms ABC
and BCD in themselves. This dihedral angle ω is called a "torsion" angle and is most frequently used for
specification of the type of conformations.
Fig. 3. Torsional angle
Just like aliphatic alkenes, cycloalkenes can show geometrical isomerism. Generally cis-form of cyclic alkene
is more common compare to trans-form. In larger rings containing around 8 atoms, cis-trans isomerism
around the double bond is observed as shown below,
H H
H
H
cis–form
H H
from–form
Moreover, the non planar or trans form shows chirality as shown below,
O-235
mirror
plane
H H
H H H
H
H Nonplanar trans cyclooctene

Planar cis–cyclooctene (Chiral forms)
(Achiral)
(a) (b)
2.2 Methods of Preparation of Cycloalkenes

Just like aliphatic alkenes, cycloalkenes can be synthesized by following methods.
1. By dehydration of cyclic alcohols: Cyclohexanol undergoes dehydration in the presence of

concentrated acids like phosphoric acid forms to form cyclohexene. The reaction scheme is shown
below,
OH
Heat
+ H2O
conc. H3PO4
Cyclohexanol Cyclohexene
Mechanism
Dehydration of cyclic alcohol involves the formation of cyclohexyl carbocation which further loses a proton
to form cyclic alkene.
H+ ⊕ H2O
OH OH2 ⊕
⊕ –H+
2. By Diels-Alder cycloaddition: Diels-Alder cycloaddition is a-cycloaddition of a conjugated diene

and an alkene or alkyne also termed as dienophile to form cyclic alkenes. It is a type of pericyclic or an
electrocyclic reaction which involves the 4 π-electrons of the diene and 2 π–electrons of the dienophile
to form cycloalkenes. Reaction involves the cleavage of less stable π bond to more stable σ bonds.
O-236
diene
4 electron
dienophile
2 electrons
The most common example of Diels-Alder cycloaddition is additional reaction of 1,3-butadiene and ethene
to form cyclohexene.
700°C
+
Chemical properties of cycloalkenes: These compounds go through the electrophilic addition reactions
that are characteristic of alkenes, when the ring remains intact. Cycloalkenes decolourise the purple colour of
dilute cold KMnO 4 or red colour of bromine in carbon tetrachloride.
1. Addition of proton acids to cycloalkenes: It has been observed that electrophiles like protic acid
can react with alkenes to form carbon-halogen bonds by donating positive halogen, Br ⊕ , Cl ⊕ , or I ⊕ .In
a similar manner these reagents can add to cycloalkenes as well to yield similar products. Likewise,
carbon-hydrogen bonds can be formed by the use of typically strong proton acids. These acids are
more effective in the absence of large amounts of water because water can compete with the alkene as
a proton acceptor. Hydrogen chloride addition to a cycloalkene occurs by way of a proton-transfer step
to give the carbocation and a chloride ion followed by a step in which the nucleophilic chloride ion
combines with the carbocation:
H
slow ⊕
CH2=CH2+H—Cl CH2–CH2+Cl
fast
⊕
CH3–CH2+Cl CH3–CH2 –Cl
All of the hydrogen halides (HF, HCl, HBr, and HI) will add to alkenes. Addition of hydrogen fluoride, while
facile, is easily reversible. However, a solution of 70% anhydrous hydrogen fluoride and 30% of the weak
organic base, pyridine, which is about 1/10,000 times as strong as ammonia, works better, and with
cyclohexene gives fluorocyclohexane. With hydrogen iodide, care must be taken to prevent I2 addition
products resulting from iodine formed by oxidation reactions such as 4HI + O2 -> 2I2 + 2H2O. With
hydrogen bromide, radical-chain addition may intervene unless the reaction conditions are controlled
carefully later. The stereochemistry of addition depends largely on the structure of the alkene, but for simple
O-237
alkenes and cycloalkenes, addition occurs predominantly in an antarafacial manner. For example, hydrogen
bromide reacts with 1,2-dimethylcyclohexene to give the trans addition product as shown below,
+ HBr H H3C
CH3 CH3 CH3 Br

. 1,2–dimethylcyclohexene trans–1–bromo–1,–dimethyl–cyclohexane
2. Hydroxylation and oxidation of alkenes hydroxylation reaction: Several oxidizing reagents

react with cycloalkenes just like alkenes under mild conditions to give, as the overall result, addition of
hydrogen peroxide as HO—OH. Of particular importance are alkaline permanganate (MnO4-) and
osmium tetroxide (OsO4), both of which react in an initial step by a suprafacial cycloaddition
mechanism like that postulated for ozone. Both the addition mechanisms are shown below, with
acyclic isomers.
C C C C
C C
H2O
O O O +MnO3
O HO OH
Mn Mn
O O O O
Unstable
C C C C
C C +Os(0)
mild reduction
O O O O (Na2SO3) HO OH
Os O Os
O O O
Stable osmate ester
Each of these reagents produces cis-1,2-dihydroxy compounds (diols) with cycloalkenes:

1. OsO4, 25°
2. Na2SO3
(Or KMnO4, OH, H2O) H H
Cyclopentene
HO OH
Cis–1,2–cyclopentanediol
3. Hydrogenation of cycloalkenes: Cycloalkenes upon reduction with dihydrogen in the presence of

a metallic catalyst produce cycloalkanes. As an example, cyclohexene is subjected to reduction giving
rise to cyclohexane as shown below,
Pd/C
+ H2
Cyclohexene Cyclohexane
O-238
3. Dienes
Systems with more than one C=C is referred to as polyenes. The simplest types of polyenes are those in
which there are two double bonds, known as dienes. A diene is a molecule that has two double bonds. If
the molecule is also a hydrocarbon, it is called an alkadiene. The relative arrangement of the double bonds
defines the characteristic reactions of the systems.
3.1 Types of Dienes

There are three possible arrangements for double bonds in the order of from most to least stable;
1. Conjugated diene
2. Isolated diene
3. Cumulated diene
3.1.1 Conjugated Diene

The double bond units occur consecutively giving a continuous π system. Here, all the adjacent "p" orbitals
can overlap with each other. The result is that conjugated diene reactivity differs to that of simple alkenes.
This extra bonding interaction between the adjacent π systems makes the conjugated dienes the most
stable type of diene. Conjugated dienes are about 15kJ/mol or 3.6 kcal/mol more stable than simple
alkenes. The simplest conjugated diene is 1,3–butadiene as shown here, H2C=CH–CH=CH2
The extended conjugation in 1,3–butadiene can be shown below,
3.1.2 Isolated Diene

The double bond units occur separately. The π systems are isolated from each other by sp3 hybridised
centers. The result is that isolated dienes have reactivity that is characteristic of simple alkenes. One of the
simpler isolated diene is ,
H2C=CH–CH2–CH=CH2
1,4–pentadiene
3.1.3 Cumulated Diene

The double bond units share a common sp hybridised C atom. The result is that cumulated dienes have
reactivity more like simple alkynes. It is important to note the relative spatial positions of the two CH2 units at
the ends of the cumulated system. The simplest of such compounds are allenes. The structural arrangement
of allene is shown below,
O-239
H H
C=C=C
H
H
Bonding in allene
The bonding arrangement of allenes is interesting and shown as,
H 1s
1s H py py
sp2
sp2 sp C sp sp2
C C
sp2 pz pz
sp2
1s H
H 1s
Fig. 5. Bonding arrangement in allene
The two carbon atoms on the left and right are supposed to have sp2 hybridization. This leaves the two
extreme carbon atoms, left and right, with one un-hybridised p-orbital each. The carbon on the left hand side
is rotated such that the unhybridized p orbital is py. The carbon on the right is rotated such that the
unhybridized p orbital is pz. The central carbon atom is supposed to be sp hybridised. The p orbital used for sp
hybridization is px. Expectedly, the central carbon is left with two un-hybrid p-orbital. One is pz and another is
py. The middle carbon atom forms one π bond due to pz - pz overlap and another π bond due to py - py overlap
as shown in the above diagram. Due to this reason the two extreme carbon atoms belong to different planes
causing asymmetry. This asymmetry further results into chirality in properly substituted allenes. The relative
instability of allenes probably reflects extra strain as a result of one carbon atom forming two double bonds.
1,2-Propadiene is slightly more strained than propyne, its heat of hydrogenation being about 2 kcal mol-1
greater than that of propyne.
3.2 Methods of Preparation of Dienes

Dienes are prepared from the same reactions that form ordinary alkenes. The two most common methods are
the dehydration of diols also known as dihydroxy alkanes and the dehydrohalogenation of dihalides. The
generation of either an isolated or conjugated system depends on the structure of the original reactants.
Vicinal diols, which have two hydroxyl groups on adjacent carbon atoms, and vicinal dihalides, which have
halogen substituents on adjacent carbons, always become conjugated systems in elimination reactions.
Other reactant configurations can lead to products that include both conjugated and isolated systems.
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Dehydration of diols:
H–
HOCH2CH2CH2CH2OH H2C=CH–CH=CH2
butane–1,4–diol 1,3–butadiene
+
HOCH2CH2CH2CH2CH2OH H H2C=CH–CH2–CH=CH2
pentane–1,5–diol 1,4–pentadiene
Dehydrohalogenation of dihalides:
KOH
XCH2CH2CH2CH2X alcohol H2C=CH–CH=CH3
1,4–dihalobutane 1,3–butadiene
KOH
XCH2CH2CH2CH2CH2X alcohol H2C=CH–CH2–CH=CH3
1,5–dihalobutane 1,4–pentadiene
Chemical properties of dienes

1. Diels alder reaction: In the Diels Alder reaction a double bond adds to a 1,3–conjugated diene to give a
6-membered ring. This reaction is known as 4+2 cycloaddition. The diene is labelled as dienophile. The
simplest example is reaction between a 1,3-butadiene and ethene to yield a cyclohexene as shown below,
The dienes show some interesting chemical reactivities. Some important ones are discussed below,
The analogous reaction of 1,3-butadiene with ethyne to form 1,4-cyclohexadiene is also known and the
reaction scheme is shown below,
heat
Since the reaction forms a cyclic product, via a cyclic transition state, it can also be described as a
"cycloaddition".
Mechanism
The reaction normally is a concerted or one step process:
The reaction is widely used in synthetic organic chemistry due to high degree of regio– and stereoselectivity
which is attributed to the concerted mechanism. The reaction usually is thermodynamically favourable due to
the conversion of 2 π–bonds into 2 new stronger σ-bonds.
The two reactions shown above require drastic reaction conditions, but the normal Diels-Alder reaction is
favoured by electron withdrawing groups on the electrophilic dienophile and by electron donating groups on
the nucleophilic diene. e.g..
O-241
O O
+ O O
O O
maleic anhydride
Some common examples of dienes and dienophiles are shown below:
Dienes
O CO2Me O
O
CN CO2Me CO2Me
Dienophiles
O
MeO2C CO2Me O
O CO2Me
Benzene does not undergo a Diels Alder reaction, despite the fact that one can 'locate' a diene fragment in its
structure. It is definitely because of the aromaticity of benzene ring. If it participates in cycloaddition reaction,
aromaticity is lost.
O
+ O No reaction
O
But interestingly anthracene responds to the reaction as shown below,
O
O
O
+ O
O
RE=350kj/mol RE=2×150= 300kj/mol
Therefore loss of RE=50kj/mol
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Why anthracene exhibits diene behaviour is definitely because the product still has 2 benzenoid rings left. In
the heteroaromatic systems like furan or thiophene the Diels Alder reaction is given by furan but not by
thiophene. It is being shown below,
O
O
easy
O O
O O
O
O O
S O No Reaction
Why thiophene does not respond is due to the fact that thiophene has more aromatic character than furan.
Stereoselectivity in Diels Alder reaction

The Diels Alder reaction is stereospecific with respect to both the diene and the dienophile. Addition is syn on
both components as bonds formed from same species at the same time.
2. Electrophilic addition to a diene: The addition of an electrophile to a diene yields various
products depending upon the nature of diene -whether it is conjugated or isolated, temperature etc. It
is discussed below one by one.
Kinetic and thermodynamic control and effect of temperature

A very interesting and significant discussion arises from the fact that while the pathway to the 1,4 product
occurs with greatest free energy decrease, the pathway to the 1,2 product is achieved with less activation
energy as shown below in the energy profile,
Energy
Thermodynamic
control
Kinetic
control
R
A
B
Reaction
Fig. 6: Energy profile of different product formation paths
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This means that formation of 1,4 product is favoured thermodynamically, but 1,2 product is favoured
kinetically. Higher temperatures, 'thermodynamic conditions', promote the formation of 1,4 product, ecause
if a larger fraction of the molecules possess activation energy for either pathway, as would occur at higher
temperature, a large portion of diene concentration continuously moves down the 1,4 pathway and forms
the more stable 1,4 product. Lower temperatures, however, are 'kinetic conditions'. At lower temperatures,
fewer reagent diene particles have enough energy to get over the activated complex energy hump to form the
1,4 product, so 1,2 addition predominates.
Case1: Addition to Conjugated Diene
The addition of halogen to 1,3–butadiene at temperatures below zero leads mainly to the 1,2–addition
product, while addition reactions run at temperatures above 50°C with these chemicals produces mainly the
1,4–addition product.
Br Br
H2C=CH–CH–CH2 (low temp.)

1,2 product
Br2
H2C=CH–CH=CH2 +
Br Br
Conjugated diene
H2C–CH=CH–CH2 (high temp.)
1,4 product
If the reaction is initially run at 0°C and then warmed to 50°C or higher and held there for a period of time, the
major product will be a 1,4 addition. These results indicate that the reaction proceeds along two distinct
pathways. At high temperatures, the reaction is thermodynamically controlled, while at low temperatures, the
reaction is kinetically controlled.
Mechanism
Br Br
+ +
H2C=CH–CH=CH2 + Br–Br H2C=CH–CH–CH2 H2C–CH=CH–CH2+Br–
Conjugated diene
Allylic corbocation
intermediate
Br + Br Br Br Br
Br Br Br
+ + H2C=CH–CH–CH2 + H2C–CH=CH–CH2
H2C=CH–CH–CH2 or H2C–CH=CH–CH2 1,2 product 1,4 product
Instead of forming the triangular halonium ion which is typical of electrophilic addition of halogen to alkene,
this reaction follows the standard carbocation mechanism for addition across a double bond. So, halogen
adds to a conjugated diene to form a resonance stabilized allylic carbocation intermediate. The two
resonance forms of the resonance stabilized allylic carbocation lead respectively to two different possible
products, the 1,2 and 1,4 products of addition. The energy diagram of the reaction of 1,3–butadiene with
hydrogen bromide shows the pathways of the two products generated from the intermediate.
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Addition of other electrophiles

When other electrophiles are added to conjugated dienes, 1,4 addition also occurs. Many reactants, such as
halogens, halogen acids, and water, can form 1,4–addition products with conjugated dienes. Like the
addition of hydrogen halides to conjugated dienes, halogens add to dienes via direct and conjugate addition
pathways:
1 2 1 3
X X
X–X + X 2 4
X
Direct or 1,2–addition Conjugate or 1,4–addition
Addition in isolated dienes

Both isolated and conjugated dienes undergo electrophilic addition reactions. In the case of isolated dienes,
the reaction proceeds in a manner identical to alkene electrophilic addition. The addition of hydrogen
bromide to 1,4–pentadiene leads to two products.
Br
H2C=CHCH2CH=CH2+HBr H2CCHCH2CH=CH2+BrH2CCH2CH2CH=CH2
4–bromo–1–pentene 5–bromo–1–pentene
(Markovnikov product) (anti–Markovnikov product)
3. Isomerisation: As propadiene is less stable than propyne, so, 1,2-propadiene naturally isomerizes to
propyne. This isomerization occurs under the influence of strongly basic substances such as sodium
amide in liquid ammonia or potassium hydroxide in ethyl alcohol:
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NaNH2, NH3
CH2=C=CH2 CH3C≡CH
∆G°(g)=–2 kcal
KOH,C2H5OH
(CH3)2C=C=CH2 (CH3)2CHC≡CH
3–methyl–1,2–butadiene
∆G°(g)=–2.5 kcal
4. Alkynes
The alkynes are unsaturated hydrocarbons that contain one triple bond. They have the general formula
CnH2n–2 and the triple bond is known as the 'acetylenic bond'. Many alkynes have been found in nature. Some
of the commonest alkynes are shown below,
H
|
H−C ≡C −H H – C ≡ C – C– H
|
H
ethyne propyne
H H H
| | |
H − C− C ≡ C – C− H H − C– C ≡ C – C – C – H
| | |
H H H
2 butyne 2,4 pentayne
Alkynes are isomeric to alkadienes, cycloalkenes and bicycloalkanes. An example of C5H8 is shown below,
2 1
1 2 3 4 5 1 2 3 4 5
5
H3C–C≡C–CH2CH3 H2C=CH–CH2–CH=CH2
2–pentyne 1,4–pentadiene 3 4
Cyclopentene Bicyclo[2,1,0]pentane
4.1 IUPAC Rules for Nomenclature of Alkyne

1. The yne suffix (ending) indicates an alkyne or cycloalkyne.
2. The longest chain chosen for the root name must include both carbon atoms of the triple bond.
3. The root chain must be numbered from the end nearest a triple bond carbon atom. If the triple bond is
in the center of the chain, the nearest substituent rule is used to determine the end where numbering
starts.
4. The smaller of the two numbers designating the carbon atoms of the triple bond is used as the triple
bond locator.
5. If several multiple bonds are present, each must be assigned a locator number. Double bonds precede
triple bonds in the IUPAC name, but the chain is numbered from the end nearest a multiple bond,
regardless of its nature.
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6. Because the triple bond is linear, it can only be accommodated in rings larger than ten carbons. In
simple cycloalkynes the triple bond carbons are assigned ring locations 1 and 2. Which of the two is 1
may be determined by the nearest substituent rule.
7. Substituent groups containing triple bonds are:
HC ≡ C (Ethynyl group) HC ≡ CH-CH2 (Propargyl group)
4.2 Bonding in Alkynes

In acetylene, the H-C ≡ C bond angles are 180°. By virtue of this bond angle, alkynes tend to be rod-like.
Correspondingly, cyclic alkynes are rare. Benzyne is highly unstable. The C ≡ C bond distance of 121
picometers is much shorter than the C=C distance in alkenes (134 pm) or the C-C bond in alkanes (153 pm).
The triple bond is very strong with a bond strength of 839 kJ/mol. The sigma bond contributes 369 kJ/mol,
the first pi bond contributes 268 kJ/mol and the second pi-bond of 202 kJ/mol bond strength. Bonding
usually discussed in the context of molecular orbital theory, which recognizes the triple bond as arising from
overlap of s and p orbitals. In the language of valence bond theory, the carbon atoms in an alkyne bond are
sp hybridized: they each have two unhybridized p orbitals and two sp hybrid orbitals. Overlap of an sp orbital
from each atom forms one sp-sp sigma bond. Each p orbital on one atom overlaps one on the other atom,
forming two pi bonds, giving a total of three bonds. The remaining sp orbital on each atom can form a sigma
bond to another atom, for example to hydrogen atoms in the parent acetylene. The two sp orbitals project on
opposite sides of the carbon atom.
pz–Orbital
py–Orbital
σ–bond
C C H
H
π–bond
π–bond
Fig. 8: Molecular orbital diagram of ethyne
Terminal and non terminal or internal alkynes

Internal alkynes feature carbon substituents on each acetylenic carbon. Symmetrical examples include
diphenylacetylene and 3-hexyne. Terminal alkynes have the formula RC2H. An example is propyne.
Terminal alkynes, like acetylene itself, are mildly acidic, with pKa values of around 25. They are far more
acidic than alkenes and alkanes, which have pKa values of around 40 and 50, respectively. The acidic
hydrogen on terminal alkynes can be replaced by a variety of groups resulting in halo-, silyl-, and
alkoxoalkynes. The carbanions generated by deprotonation of terminal alkynes are called acetylides.
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4.3 Methods of Preparation of Alkynes

There are a number of methods available for the synthesis of alkynes. Some of these are discussed below in detail.
1. From calcium carbide: Calcium carbide is the compound CaC2, which consists of calcium ions
(Ca2+) and acetylide ions, C 2−
2 . It is synthesized from lime and coke in the following reaction:
CaO + 3C → CaC2 + CO
This reaction is very endothermic and requires a temperature of 2000°C. For this reason it is produced
in an electrical arc furnace. As a matter of fact, calcium carbide may formally be considered a
derivative of acetylene which is an extremely weak acid though not as weak as ammonia. The double
deprotonation means that the carbide ion has very high energy. Instant hydrolysis occurs when water is
added to calcium carbide, yielding acetylene gas, the hydrolysis reaction taking place is shown below,
CaC2 + 2H2O → Ca(OH)2 + C2H2
2. Dehydrohalogenation of vic-dihalides or gem-dihalides: A geminal (1,1) or vicinal (1,2)

dihalide upon dehydrohalogenation with alc. KOH and eventually with NaNH2 yields an alkyne as
shown below,
H X H H H
NaNH2
–C–C– or –C–C– alc. KOH KX+H2O+–C=C NaX+NH3+–C≡C–
Alkyne
H X X X X
A gem-dihalide A vic-dihalide A vinyl halide
The vinyl halide requires the stronger base, sodamide (NaNH2) to carryout elimination process of
dehydrohalogenation.
3. Dehalogenation of vic-tetrahalogen compounds: Even tetrahalogenated alkanes can also give

rise to alkynes using strong base in high concentration as shown below,
EtOH
CH3-CBr2-CBr2-CH3 + 2Zn   
→ CH3-C ≡ C-CH3 + 2ZnBr2
heat
2,2,3,3-tetrabromobutane 2-butyne
This reaction has the drawback that the halogen compound is itself prepared by halogen addition to
alkynes. The mechanism for dehalogenation has been taken up in the topic "alkenes".
4. From Kolbe's electrolytic process: The starting compound is a salt already containing a
carbon-carbon double bond. One such compound is maleic acid. Mechanism is similar to that of
formation of ethane using Kolbe's electrolysis.
CH–COONa
||
CH − COONa sodium maleate is a sodium salt of maleic acid. It is subjected to electrolysis using inert
electrodes and the products at respective electrodes are analysed.
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At Anode:
CH-COO- -2e →
||
CH-COO*
CH-COO* CH* CH
|| -2CO2 → || → |||
CH-COO* CH* CH
(free radical formation)

At cathode:
2Na+ + 2e– → 2Na
2Na + H20 → 2NaOH + H2

In this manner, alkyne is obtained at anode, while NaOH is formed at cathode and hydrogen gas is
liberated.
5. Alkyl substitution in acetylene or 1-alkynes: In this reaction lower alkynes are used to synthesise
higher alkynes or alkynes of higher molecular mass.
NaNH2 NH3
or →R—C ≡ C: Na + or +
R— C ≡ C—H +
1
Na 2 H2
–
R —C: + R'— CH2 – X → R—C C— CH2— R' + X (SN2 mechanism)
1° alkyl holide
There is wide variety possible using this method. Acetylene itself may be alkylated either once to make a
terminal alkyne or twice to make an internal alkyne. The basis of the reaction is that acetylene or 1–alkyne has
the terminal hydrogen which is weakly acidic as discussed earlier, so it is easily removed either by an amide
base or an electropositive metal.
3 liq.NH 4 
9 n-C H Br
HC ≡ CH + NaNH2     → HC ≡ C– Na+    → CH3(CH2)3C ≡ CH
−33 ° C
1-hexyne
+
2NaNH
2 → Na–C≡C–Na +    3 2 n − C H Br
HC≡CH    
  7→ CH3CH2CH2C≡CCH2CH2CH3
liq.NH3
−33 ° C 4-octyne
Since acetylide ions are highly basic, competing elimination is a common side reaction. The products of such an
elimination reaction are an alkene from the alkyl halide alongwith an alkyne by substitution reaction pathway.
Br
R–C≡C+H–CH2–CHR CH2=CHR+Br–+RC≡C–H
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Limitation of the reaction

So, in order to get good yield of alkynes, the reaction should take the course of substitution, for which primary
alkyl halides would be the right reagent. In practice, the alkylation of acetylene or another terminal alkyne is
only a good method for the synthesis of higher alkynes when reacted to primary halides that do not have
branches close to the reaction centre. With secondary halides, and even with primary halides that have
branches close to the reaction centre, elimination is usually competing or major reaction.
6.From chloroform: When two moles of chloroform is condensed with silver metal, acetylene is produced
as shown below,
Ag, Heat
HCCl3 HC≡CH
Chloroform Ethyene
Example 8: Outline a synthesis of propyne from isopropyl or n–propyl bromide. The needed
vic-dihalide is formed from propene, which is prepared from the alkyl halides.
Solution :
CH3CH2CH2Br
n–Propylbromide Br
alc. alc.
or CH3–CH=CH2 2 CH3CHBrCH2Br KOH CH3CH=CHBr
CH3CHBrCH3 KOH
Isopropylbromide NaNH2
CH3C=CH
Example 9: Synthesize the following compounds from HC ≡ CH and any other organic and
inorganic reagents (do not repeat steps):
(a) 1-pentyne, (b) 2-hexyne.
Solution :
NaNH
2 →H–C ≡ C• − Na+   
3 2  CH CH CH I
2→ H– C ≡ C– CH CH CH
(a) H–C ≡ C–H     • 2 2 3
CH I NaNH
2 → CH –C ≡ C − Na+
3→ CH –C ≡ C–H    
(b) Na+ :C– ≡ C–H    3 3
CH CH CH I
3 2 
2→ CH –C ≡ C–CH CH CH
 3 2 2 3
Physical properties of alkynes

The physical properties of alkynes are similar to those of the corresponding alkenes. The lower members are
expectedly gases with boiling points somewhat higher than those of the corresponding alkenes. Terminal
alkynes have lower boiling points than isomeric internal alkynes and can be separated by careful fractional
distillation. The CH3-C bond in propyne is formed by overlap of a sp3 hybrid orbital from the methyl carbon
with a sp hybrid orbital from the acetylenic carbon. The bond is sp3–sp type. Since one orbital has more
s-character than the other and is thereby more electronegative, the electron density in the resulting bond is
not symmetrical. The unsymmetrical electron distribution results in a dipole moment larger than that
observed for an alkene, but still relatively small.
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CH3CH2C≡ CH CH3CH2CH=CH2 CH3C≡CCH3

µ= 0.80 D µ= 0.30 D µ= 0.0 D
Symmetrically disubstituted acetylenes, of course, have no net dipole moment.
4.4 Acidity of Terminal Alkynes

The acidic nature of hydrogen in acetylene is characteristic of hydrogen in the group ≡ CH, and it has been
suggested that this is because the C ≡ H bond has considerable ionic character due to resonance.
There is, however, evidence to show that the electronegativity of a carbon atom depends on the number of
bonds by which it is joined to its neighbouring carbon atom. Since π − electrons are more weakly bound than
σ − electrons, the electron density round a carbon atom with π bonds is less than that when only σ– bonds are
present. Thus a carbon atom having one π −bond has a slight positive charge compared with a carbon atom
which has only σ – bonds. Hence, the electronegativity of an sp2 hybridised carbon atom is greater than that
of an sp3 hybridised carbon atom. Similarly, a carbon atom which has two π −bonds carries a small positive
charge which is greater than that carried by a carbon atom with only one π −bond. Thus the electronegativity
of an sp hybridized carbon atom is greater than that of an sp2 hybridised carbon atom. Thus more the's'
character a bond has, the more electronegative is that carbon atom. Therefore the attraction for electrons by
hybridized carbon will be sp > sp2 > sp3.
Therefore the hydrogens in terminal alkynes are relatively acidic. Acetylene itself has a p K a of about 25. It is a
far weaker acid that water ( p K a 15.7) or the alcohols ( p K a 16-19), but it is much more acidic than ammonia
( p K a 34). A solution of sodium amide in liquid ammonia readily converts acetylene and other terminal
alkynes into the corresponding carbanions.
RC ≡ CH + NH −2 → RC ≡ C– + NH3
This reaction does not occur with alkenes or alkanes. Ethylene has a p K a of about 44 and methane has a p K a
of about 50, which means that they are weaker acid than NH3.
From the foregoing p K a 's one can see that there is a vast difference in the basic character of the carbanions
RC ≡ C − , CH2 = CH − , and CH −3 . This difference may readily be explained in terms of the character of the
orbital occupied by the lone-pair electrons in the three anions. Methyl anion has a pyramidal structure with
the lone-pair electrons in an orbital that is approximately sp3. In vinyl anion, the lone-pair electrons are in an
sp2 orbital. In acetylide ion, the lone pair is in an sp orbital.
sp3 sp2
H sp
H ••
C ••
C=C H–C≡C
••
H
H H H
Methyl anion Vinyl anion Acetylide ion
Electrons in s-orbitals are held closer to the nucleus than they are in p-orbitals. This increased electrostatic
attraction means that s-electrons have lower energy and greater stability than p-electrons. In general, the
greater the amount of s-character in a hybrid orbital containing a pair of electrons, the less basic is that pair of
electrons, and the more acidic is the corresponding conjugate acid. Alternatively, since the greater the
electronegativity of an atom, the more readily it can accommodate a negative charge and hence less basic the
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−
species would be. Basicities of the following carbanions follow the order: CH≡ C − < CH2=CH <CH −3 and
hence the order of acidic strength would be HC≡ CH > CH2 = CH2 > CH4.
Of course, the foregoing argument applies to hydrogen cyanide as well. In this case, the conjugate base, N ≡
C − , is further stabilized by the presence of the electronegative nitrogen. Consequently, HCN is sufficiently
acidic ( p K a 9.2) that it is converted to its salt with hydroxide ion in water.
HCN + OH − → CN − + H2O
Chemical properties of alkynes

Alkynes frequently undergo electrophilic addition reactions like alkenes. Owing to the presence of a triple
bond, acetylene is more unsaturated than ethylene, and forms addition products with two or four univalent
atoms or groups. A triple bond consists of one σ bond and two π bonds which produces a linear molecule.
When two univalent atoms add on to a triple bond, the diagonal arrangement sp hybridized lobes of atomic
orbitals changes into the trigonal lobes due to sp2 hybridization, and the further addition of two univalent
atoms changes the trigonal arrangement into the tetrahedral arrangement due to sp3 hybridization. Under
suitable conditions, it is possible to isolate the intermediate alkene.
Arguments based on bond strengths would lead to the conclusion that acetylene should be more reactive
than ethylene:
C ≡ C (808.3) → C=C (606.7), ∆H = +196.6 kJ mol–1 ;
C=C (606.7) → C–C (347.3), ∆H = +259.4 kJ mol–1.
This order of reactivity is observed for catalytic hydrogenation. The mechanism of this reaction, however,
does not involve electrophiles. However, the reactivity of alkynes towards general electrophilic addition
reaction is lesser than that of alkenes. This is unexpected in view of the fact that the π electron density in a
triple bond is higher than that in a double bond. A possible contributing factor for decreased reactivity of a
triple bond to electrophiles may be the fact that the bridged carbonium ion from acetylene (assuming its
formation) is more strained than the bridged carbonium ion from ethylene.
Br+
Br2
–C≡C– –C C–+Br–,
Br+
Br2
C C C C+Br–,
Justification for the assumption of these intermediate bridged ions being involved in addition to acetylene by
the polar mechanism lies in the fact that the additions are stereoselectively trans.
1. Hydrogenation: Acetylene adds on hydrogen in the presence of a catalyst, the reaction proceeding in
two stages.
H / Ni H / Ni
C2H2  2 → C2H4  2 → C2H6
O-252
Most catalysts like Ni, Pt, Pd, Rh, etc. cause hydrogenation of a triple bond. As such the reaction is so fast that
alkene is not isolated, rather the reaction stops after the formation of alkane. However, it is possible to isolate
the intermediate alkene by using suitable conditions. One such method uses Lindlar's catalyst, which consists
of a Pd supported on CaCO3 catalyst partially poisoned with lead acetate. A better catalyst is Pd supported on
BaSO4 partially poisoned with quinoline. Dialkylacetylenes can be catalytically reduced by Lindlar's catalyst
to a mixture of cis– and trans–alkenes, the former predominating while reduction with sodium in liquid
ammonia produces predominantly the trans–alkene, which is also produced by reduction with lithium
aluminium hydride. These mechanism have been dealt in the topic on alkenes. cis–reduction can also be
carried out with diborane or with di–isobutylaluminium hydride.
2. Addition of halogen: Halogens are added to alkynes just like alkenes with a slight difference that the
product formed is a tetrahalogenated alkane as shown in the scheme below,
X X X X
X2 X
R–C≡C–H R–C=C–H CCl2 R–C–C–H
CCl4 4
X X
The electrophilic addition mechanism for this reaction has been already taken up in the topic "alkenes".
This reaction is used for detecting unsaturation of the type C = C or C ≡ C as the reddish–brown colour
of Br2 disappears due to the formation of colourless vicinal tetrabromo alkane.
3. Addition of HX: Alkynes can also add on the halogen acids, their order of reactivity being HI > HBr
> HCl > HF. HF addition requires high pressure. The addition of the halogen acids can take place in
the dark but is catalysed by light or metallic halides. The addition is in accordance with Markovnikov's
rule. For example, acetylene combines with hydrogen bromide to form vinyl bromide first and then
ethylidene dibromide in the following manner,
HBr
CH ≡ CH + HBr → CH2=CHBr  → CH3CHBr2
Peroxides have the same effect on the addition of hydrogen bromide to acetylene as they have on
alkenes. The mechanism of the addition of halogen acids is the same as that for the alkenes.
+
CH≡CH+H–Br Br–+CH=CH2 CH2=CHBr
Addition of another molecule of hydrogen bromide could give either the intermediate carbonium ion,
+
CH3C HBr (a stable carbocation due to the stabilization imparted through pπ–dπ bonding with
+
bromine), or C H2CH2Br (a primary carbocation). Since the former is more stable than the later, the
reaction proceeds via the former to form ethylidene dibromide. Thus,
+
Br–H+CH2=CHBr CH3–CHBr+Br– CH3CHBr2
O-253
Example 10: Give the equation for the reaction of one equivalent of HBr with 1–
pentene–4–yne.
Solution : The reaction proceeds through a carbocation. Since the alkyl cabocation from the alkene group
is more stable than the vinyl carbocation from the alkyne group, the ∆H# for its formation is less and alkenes
react at a faster rate than alkynes toward electrophilic addition.
H+ + Br–
H2C=CHCH2C≡CH H3C–C HCH2C≡CH H3CCHBrCH2C≡CH
4. Addition of H2O (Nucleophilic addition reaction): When passed into dilute sulphuric acid at
60°C in the presence of mercuric sulphate as catalyst, acetylene adds on a molecule of water to form
acetaldehyde. The mechanism of this hydration probably takes place via the formation of vinyl alcohol
as an intermediate.
H2SO4 tautomerize
CH ≡ CH + H2O [CH2=CHOH] CH3CHO
Hg2+
Mechanism
The function of the mercuric ion imparhing nucleophilic addition character. A possible explanation is that the
mercuric ion, because of its large size, can readily form a bridged ion or a π complex. Moreover, mercuric ion
provides electro–philicity to alkyne thereby inviting attack from water as a nucleophile. So, this becomes an
example of nucleophilic addition reaction.
2+ H2O +
HC≡CH+Hg HC CH HC=CHOH2
Hg2+ Hg+
–H
+ H3O+ tautomerize
HC=CH–OH Hg2++[CH2=CHOH] CH3CHO
Hg+
The homologues of acetylene form ketone when hydrated using this method. For example, propyne gives
acetone in the following manner,
OH O
H2SO4
CH3–C≡C–H+H2O HgSO CH3–C=C–H CH3–C–CH3 (Markovnikov addition)
4
H Acetone
A vinyl alcohol
(unstable)
O-254
Phenyl acetylene yields acetophenone as shown below,

C≡C–H O=C–CH3
2 H SO
4
+H2O HgSO
4
Acetophenone
5. Addition of Boron Hydride: Monoalkylacetylene on treatment with R2BH gives vinyl adduct which
on hydrolysis gives alkene but on alkaline oxidation yields aldehyde.
R' H
CH3COOH
R'—C≡C–H+R2BH C=C R'CH=CH2
hydrolysis
H BR2
Oxidation H2O2NaOH
R'CH2CHO
With dialkylacetylenes, the products of hydrolysis and oxidation are cis-alkenes and ketones,
depending upon the choice of reagent as shown below,
CH3 CH3
BH3 H2O2
3CH3–C≡C–CH3 C=C B CH3–CH2–CO–CH3
NaOH
H 2–butanone
3
a vinylborane
CH3COOH
CH3 CH3
C=C
H H
Cis–2–butene
6. Dimerization: Acetylene upon dimerization with Cu+ salt yields vinylacetylene as shown,
Cu(NH3 )+ Cl −
2 
2 H – C ≡ C – H  → H2C=CH–C ≡ C–H
H2 O
Vinylacetylene
7. Oxidation to carboxylic acids: Oxidation with hot potassium permanganate yields smaller
carboxylic acids. The site of triple bond is the site of cleavage,
3 CH3C ≡ CH + 8KMnO4 + KOH → 3CH3COOK + 3K2CO3 + 8MnO2 + 2H2O
CH3CH2C ≡ C–CH3 + 2KMnO4 + KOH → CH3CH2COOK + CH3COOK + 2MnO2 + 2H2O

O-255
CH3 CH3
oxidation
CH3–CH–C≡CCH2CH2CH3 CH3CH–CO2H + CH3–CH2CH2COOH
(Two isomeric acids each having M.F. C4H8O2)
8. Ozonolysis: Even alkynes undergo ozonolysis like alkenes to yield a variety of products,
1.O
3 → CH COOH + HOOCCH CH
CH3C ≡ CCH2CH3   3 2 3
2.hydrolysis
2–pentyne Acetic acid Propanoic acid
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.
C
1 2 1 2 H2O 1 2 1 2 1 2
R C≡CR +O3→R C C–R R –C–C–R +H2O2 R –C–C–R +H2O2→R CO2H+R CO2H
O O
O O
Acetylene is exceptional in that it gives glyoxal as well as formic acid.

(i)O
3 → OCHCHO + HCO H
CH ≡ CH    2
(ii)H2 O
Example 11: List the alkynes needed to synthesize the following ketones in the best possible
yields
(i) (CH3 )2 CH C CH3 (ii) CH3CH2 C CH2CH2CH3

|| ||
O O
(iii)
CCH2
Solution : (i) Methyl ketones, CH3COR are best made from terminal alkynes. Use (CH3)2CHC ≡ CH to
prepare given ketone.
(ii) Use the symmetrical internal alkyne CH3CH2C ≡ CCH2CH3 rather than the unsymmetrical CH3C
≡ CCH2CH2CH3, which also gives CH3COCH2CH2CH2CH3.
(iii)
C≡C
O-256
9. Polymerization reactions: When acetylene is passed into dilute hydrochloric acid at 65°C in the
presence of mercuric ions as catalyst, vinyl chloride is formed.
Hg 2+
CH ≡ CH + HCl   
→ 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. When acetylene is passed into warm acetic acid in the presence of mercuric
ions as catalyst, vinyl acetate and ethylidene diacetate are formed.
Hg 2+
CH ≡ CH + CH3CO2H   
→ CH2=CHOOCCH3
Hg 2+
CH2=CHOOCCH3 + CH3CO2H   
→ CH3CH(OOCCH3)2
Vinyl acetate (liquid) is used in the plastics industry. Ethylidene diacetate (liquid), when heated rapidly
to 300-400°C, gives acetic anhydride and acetaldehyde. When passed through a heated Cu or Fe
tube, acetylene polymerises to a small extent to benzene as shown here,
3C2H2→
Homologues of acetylene behave in a similar manner. For example, propyne polymerises to

1,3,5-trimethylbenzene, and but-2-yne to hexamethylbenzene.
CH3 CH3
H3C CH3
3CH3C≡CH→ ; 3CH3C≡CCH3→
H3C CH3 H3C CH3
CH3
Under suitable conditions acetylene polymerises to cyclooctatetraene (COT) as well in the following
manner,
4C2H2→
COT
10. Reaction with hypochlorous acid: When acetylene is passed into hypochlorous acid solution,
dichloroacetaldehyde is formed.
HOCl
CH ≡ CH + HOCl → CHCl=CHOH   
→ Cl2CHCH(OH)2 → Cl2CHCHO +H2O
Dichloroacetic acid, Cl 2CHCO2H, is also formed by the oxidation of dichloroacetaldehyde in the
presence of hypochlorous acid.
O-257
11. Reaction due to acidic nature: Due to their acidic nature, alkynes are quantitatively deprotonated
by alkyllithium compounds, which may be viewed as the conjugate bases of alkanes.
CH3(CH2)3C ≡ CH + n–C4H −9 Li+ → CH3(CH2)3C ≡ C–Li++n-C4H10
The foregoing transformation is simply an acid-base reaction, with l-hexyne being the acid and
n-butyllithium being the base. Since the alkyne is a much stronger acid than the alkane (by over 20 pK
units!), equilibrium lies essentially completely to the right. Terminal alkynes give insoluble salts with a
number of heavy metal cations such as Ag+ and Cu+. The alkyne can be regenerated from the salt, and
the overall process serves as a method for purifying terminal alkynes. However, many of these salts are
explosively sensitive when dry and should always be kept moist.
–C ≡ C – H + M+ → –C ≡ C – M + H +
For example, when a terminal alkyne like acetylene is treated with [Ag(NH3)2]+ white ppt. of silver
acetylide is formed. So, this reaction can be used for identification of acetylene or any terminal alkyne
through formation of silver acetylide (white ppt.) or silver alkynide.
H – C ≡ C – H+2[Ag(NH3)2]+ → Ag – C ≡ C – Ag +2NH +4
Another characteristic reaction is shown below when a terminal alkyne is treated with [Cu(NH3)2]+ to
yield a red precipitate as shown below in the case of propyne,
CH3–C ≡ C – H + [Cu(NH3)2]+ → CH3–C ≡ C–Cu + NH +4 + NH3

Cuprous
methylacetylide (red ppt.)
Some more reactions pertaining to acidic nature of terminal alkynes are shown below like reaction with
sodium metal or with sodamide,
liq.NH
3 → H–C ≡ C: Na++ ½H
H–C ≡ C–H + Na     2
Sodium acetylide
ether
CH3–CH–C≡C–H+NaNH2 CH3–CH–C≡C:–Na++NH3
CH3 CH3
Sodium isoprophylacetylide
Example 12 : Dehydrohalogenation of 3-bromohexane gives a mixture of cis-2-hexene and

trans-2- hexene. How can this mixture be converted to pure
(i) cis-2-hexene? (ii) trans-2-hexene?
Solution : Relatively pure alkene geometric isomers are prepared by stereoselective reduction of alkynes.
(i) Hydrogenation of 2-hexyne with Lindlar's catalyst gives 98% cis-2-hexene.

O-258
Br2 2NaNH2
CH3CH=CHCH2CH2CH3 CH2CH–CHCH2CH2CH3
Br Br
H3C CH2CH2CH3
H2
CH3C≡CCH2CH2CH3 C=C
Lindlar's
2–hexyne catalyst H H
Cis–2–hexene
(ii) Reduction with Na in liquid NH3 gives the trans product.

H3C H
Na
CH3C≡CCH2CH2CH3 NH3
C=C
H CH2CH2CH3
Trans–2–hexene
Example 13 :
(i) Give the equations for the reactions of propyne with (a) Na (in hexane),
−
(b) Na+NH −2 (in liquid NH3), (c) Ag(NH3) +2OH − and (d) Cu( NH 3 )2OH − .
(ii) On which chemical property of propyne do these reactions depend?
Solution :
(i) (a) 2CH3 ≡ CH + 2Na → 2[CH3C ≡ C: Na+ ] (sodium propynide) + H2
an alkynide anion
liq.NH3
(b) CH3C ≡ CH + NaNH2    → CH3C ≡ C: − Na+ + NH3
(c) CH3C ≡ CH + Ag(NH3) +2 OH − → CH3C ≡ CAg(s) + 2NH3 + H2O

white ppt.
(d) CH3C ≡ CH + Cu(NH3) + OH − → CH3C ≡ CCu(s) + 2NH3 + H2O

2
red ppt.
(ii) The acidity of the terminal hydrogen of a terminal alkyne.
Example 14: Write down the structures of (A) and (B).

NaNH , MeI
2 Na / NH (I)
PhC ≡ CH     → (A)    3
→ (B)
Solution :
(A): Ph – C ≡ C – CH3 (B): Ph H
(Pure trans)
H CH3
O-259
Example 15: What would be the major product in each of the following reactions?
(i) CH3
C2H5OH
CH3 C CH2Br
∆
CH3
(ii)
H2
Lindlar catalyst
CH3
Solution :
(i) CH3
CH3 C CH2CH3
OC2H5
(ii) CH3
H H
Example 16: (i) Identify (A), (B) and (C) in the following schemes and write their structures:
Br2 / CCl4 NaNH2 HgSO4 / H2SO4

(A) (B) (C)
(ii) Identify (X), (Y) and (Z) in the following synthetic scheme and write their structures.
Explain the formation of labelled formaldehyde (H2C*O) as one of the products
when compound (Z) is treated with HBr and subsequently ozonolysed. Mark the C*
carbon in the entire scheme.
BaC*O3 + H2SO4 → (X) gas [C* denotes C14]
(i)Mg/ ether4 → (Z) LiAlH
CH2 = CH – Br     
→ (Y)    

(ii)X
(iii)H 3 O +
Solution:
(i) Br
Br2/CCl4 NaNH2
CH–CH2 (dehydrohalogenation) C≡CH
Br
(A) (B)
HgSO4 / H2SO4
C–CH3
O
(C)
O-260
* *
(ii) Ba C O 3 + H2SO4 → C O 2 (g) + BaSO4 + H2O
(x)
(i) Mg/ether * LiAlH4 * OH
CH2=CH–Br * CH2=CH–COOH CH2=CH–CH2
(ii) CO2
(iii) H3O+ (Y) (Z)
HBr * + *
(Z) CH2=CH–CH2 CH+2–CH=CH2
(Allyl carbocation) Br –
* =O O3 /H2O/Zn *
Br–CH2CHO+CH 2 CH2–CH=CH 2
Br
Example 17: The reactivity of hydrogen atoms in an alkane towards substitution by bromine
atom is:
(i) 1°H > 2°H > 3°H (ii) 1°H < 2°H < 3°H
(iii) 1°H > 2°H < 3°H (iv) 1°H < 2°H > 3°H
Solution: Homolytic bond dissociation energy is inversely related to the stability of free radicals. Thus the
order of reactivity is 3°H > 2°H > 1°H.
∴ (ii)
Example 18: The treatment of CH3OH with CH3MgI releases 1.04 ml of a gas at S.T.P. The mass
of CH3OH added is:
(i) 1.485 mg (ii) 2.98 mg
(iii) 3.71 mg (iv) 4.47 mg
Solution: CH3OH + CH3MgI → CH4 + MgI(OH)
1.04
Moles of CH4 = = 4.642 10 −5
22400
∴ No. of moles of CH3OH = 4.642 ×10–5
Mass of CH3OH = 4.642 10–5 ×32 = 1.485 mg
∴ (i)
Example 19: Anti Markovnikov addition of HBr is not observed in:
(i) Propene (ii) Butene
(iii) 2–butene (iv) 2–pentene
Solution: If double bond is attached to two similar groups, then anti–Markovnikov addition is not possible.
In 2–butene, double bond is attached to two similar alkyl (CH3) groups.
∴ (iii)
O-261
Example 20: Dipole moment is shown by:

(i) 1,4–dichlorobenzene (ii) cis –1,–2– dichloroethene
(iii) Trans –1,2– dichloroethene (iv) Trans –1,–2 dichloro–2–pentene
Solution: Symmetrical compounds will have zero dipole moment.

Cl
H Cl
& C=C
Cl H
Cl
Unsymmetrical compounds will show dipole moment.
H H H3C Cl
C=C C=C
Cl CH2CH3
Cl Cl
Cis–1,2–dichloroethene Trans–1,2–dichloro–2–pentene
∴ (ii), (iv)
Example 21: The dehydrohalogenation of 2–bromobutane with alcoholic KOH gives:

(i) Only 2–butene (ii) Only 1–butene
(iii) 2–butene as the major product (iv) 1–butene as the major product
Solution:
H Br H
alcoholic KOH
H3C–C–C–CH3 H3C–C=C–CH3 + H3C–C–C=CH2
H H H H H H
Major (more substituted alkene) Minor
∴ (iii)
Example 22: The addition of HCl in the presence of peroxide does not follow anti Markovnikov
rule because
(i) HCl bond is too strong to be broken homolytically
(ii) Cl atom is not reactive enough to add on to a double bond
(iii) Cl combines with H to give back HCl
(iv) HCl is a reducing agent
Solution: Peroxide effect involves free radical mechanism. HCl bond is too strong to be broken
homolytically, so addition of HCl in presence of peroxide does not follow anti Markovnikov's rule.
∴ (i)
O-262
Example 23: The ozonolysis of an olefin gives propanone. The olefin is:
(i) propene (ii) but –1– ene
(iii) but –2– ene (iv) 2,3–dimethyl but–2–ene
Solution: Terminal double bond on ozonolysis will produce only aldehyde. To form ketone it should not be
a terminal alkene. Olefin forms only one ketone so it is a symmetrical alkene.
O /H O
(CH3)2C = C(CH3)2  3 2
2 → 2CH COCH
3 3
∴ (iv)
Example 24: The ozonolysis of a triple bond produces
(i) A mixture of aldehydes/ketones and carboxylic acids
(ii) A mixture of aldehydes/ketones
(iii) A mixture of carboxylic acids
(iv) CO2 and H2O
Solution : Ozonolysis of a triple bond produces carboxylic acids.
O
O3
CH3CH2C≡CCH3 CH3CH2C–CCH3
O O
H2O
CH3CH2COOH+CH3COOH
Mixture of carboxylic acid
∴ (iii)
Example 25: The addition of water to propyne in the presence of HgSO4–H2SO4 produces:
(i) CH3COCH3 (ii) CH3 – C(OH) = CH2
(iii) CH3CH2CH2OH (iv) CH3CH2CHO
Solution: The homologues of acetylene form ketone when hydrated in presence of HgSO4 and H2SO4.
OH
H2SO4
CH3–C≡C–H+H2O HgSO CH3–C=C–H
4
H
Vinyl alcohol
(Markovnikov addition)
(Unstable)
tautomerize
CH3–C–CH3
O
∴ (i)
O-263
Example 26: The compounds 1–butyne and 2–butyne can be distinguished by using:
(i) Bromine water (ii) KMnO4 solution
(iii) Tollen's reagent (iv) Chlorine gas
Solution: Terminal and non terminal alkynes can be distinguished using ammonical Ag+ solution (Tollen's
reagent). The metal ion Ag+ reacts with acetylinic hydrogen to form insoluble acetylides. This reaction is
possible only for terminal alkynes.
∴ (iii)
Example 27: Propyne is produced during the hydrolysis of:
(i) CaC2 (ii) Al4C3
(iii) Mg2C3 (iv) SiC
Solution: On hydrolysis CaC2 gives acetylene where Mg2C3 gives propyne.
Mg2C3 + 4H2O → CH3C ≡ CH + 2Mg(OH)2
∴ (iii)
Example 28: Which of the following will produce C2H6 on reaction with C2H5MgBr in
significant amount?
(i) Toluene (ii) Benzyne
(iii) Phthalimide (iv) Cyclopropene
Solution: Any compound having active H–atom on reaction with RMgX evolves alkane.
∴ (iii)
Example 29: When isobutane is monochlorinated in the presence of ultra-violet light, the
product obtained in higher yield is:
(i) n-butyl chloride (ii) Isobutyl chloride
(iii) sec-butyl chloride (iv) Tert-butyl chloride
Solution: Cl
Cl2/hν
CH3–CH–CH3 CH3–CH–CH2Cl+CH3–C–CH3
CH3 CH3 CH3
isobutyl chloride no. of 1°H× reactivity of 1°H 9

∴ = = × 1
tert butyl chloride no. of 3°H× reactivity of 3°H 1 5
∴ (ii)
Example 30: An organic compound (A) contains only C, H and O atoms. On reaction with
excess of CH3MgI, (A) gives a gas (X) whose volume under STP conditions was found to be 67.2
litre. The number of hydroxyl groups in the compound (A) are:
O-264
(i) 1 (ii) 2
(iii) 3 (iv) 4
Solution:
67.2
= mole of gas(X) evolved = 3 mole of gas (X)
22.4
The number of active H–atom present in a molecule is equal to the number of moles of gas obtained i.e., no.
of –OH groups in compound (A)=3
∴ (iii)
Example 31: Ph3SnH can be used to reduce:

(i) Primary alkyl halide (ii) Secondary alkyl halide
(iii) Tertiary alkyl halide (iv) All of these
Solution: Ph3SnH is used to reduce all types of alkyl halides i.e., primary, secondary and tertiary alkyl
halides.
∴ (iv)
Example 32: Identify the correct order of boiling points of the following compounds:
CH3CH2CH2CH2OH, CH3CH2CH2CHO, CH3CH2CH2COOH
1 2 3
(i) 1>2>3 (ii) 3 > 1 > 2
(iii) 1 > 3 > 2 (iv) 3 > 2 > 1
Solution: Carboxylic acids are intermolecularly hydrogen bonded forming stable cyclic dimer, while
alcohols are associated with intermolecular hydrogen bonding to form associated molecules. Aldehydes are
unable to form H–bonds. Thus, boiling point should be highest for butanoic acid, followed by butanol and
then butanal.
∴ (ii)
Example 33: Identify the set of reagents/reaction conditions 'X' and 'Y' in the following set of
transformations:
X Y
CH3 – CH2 – CH2Br  → Product  → CH3 –C H – CH3
|
Br
(i) X = dilute aqueous NaOH, 20°C; Y = HBr/acetic acid, 20°C

(ii) X = concentrated alcoholic NaOH, 80°C; Y = HBr/acetic acid, 20°C
(iii) X = dilute aqueous NaOH, 20°C; Y = Br2/CHCl3, 0°C
(iv) X = concentrated alcoholic NaOH, 80°C; Y = Br2/CHCl3, 0°C
O-265
Solution: X can be either dilute aqueous NaOH or concentrated alcoholic NaOH giving 1 propanol or
propene respectively. 1–propanol on reaction with Y (HBr/acetic acid) would have given 2–bromopropane
as the major product through substitution while propene on reaction with Y would have given the same
product via addition. Since addition reactions are faster than substitution, so the most appropriate option is.
∴ (ii)
Example 34: Consider the following reaction:
•
H3C − CH − CH − CH3 + B R → ' X' +HBR
| |
D CH3
Identify the structure of the major product 'X'

(i) • •
H3C − C H − CH − C H2 (ii) H3C − C H − C − CH3
| | | |
D CH3 D CH3
(iii) • •
H3 C − C − CH − CH3 (iv) H3C − C H − C H − CH3
| | | |
D CH3 D CH3
Solution: Attack of Br • free radical on tertiary carbon is thermodynamically more favoured, leading to the
formation of tertiary free radical, which is stabilized by hyperconjugation.
∴ (ii)
Example 35: Identify a reagent from the following list which can easily distinguish between
1–butyne and 2–butyne:
(i) Bromine, CCl4 (ii) H2, Lindlar catalyst
(iii) Dilute H2SO4, HgSO4 (iv) Ammoniacal Cu2Cl2 solution
Solution: 1–butyne has acetylenic hydrogen; so it will react with ammoniacal Cu2Cl2 solution to give red
precipitate of copper butynide. 2–butyne does not respond to this test.
∴ (iv)
Example 36: Which one of the following alkenes will react fastest with H2 under catalytic
hydrogenation condition?
(i) R R (ii) R H
H H R H
(iii) R R (iv) R R
R H R R
Solution: Rate of Hydrogenation of an alkene decreases with increasing alkyl substitution on C = C.

Choices (C) and (D) are ruled out due to steric hindrance (as the number of R groups are more). Among (A)
and (B) two alkyl groups on the same carbon atom offer more steric hindrance than alkyl groups on two
separate carbon atoms.
∴ (i)
O-266
Exercise
Long Answer Type Questions 7. (i) Classify different types of dienes.
1. Write short notes on the following : Discuss 1, 2 and 1, 4 addition reactions
of conjugated dienes.
(i) Markovnikov's rule
(ii) Write a note on acidity of 1-alkynes.
(ii) Diel's Alder reaction [Bund. 2008; Agra 2009]
[Kashi 2011]
2. How is buta-1, 3-diene is prepared? Why is it more
8. (i) Separately ethylene and bromine
stable than non-conjugated dienes? Explain the
both are non-polar. How will you
formation of 1, 2- and 1,4-addition product when
explain that addition of bromine to
buta 1, 3-diene reacts with hydrobromic acid.
[Meerut 2009]
ethylene takes place by ionic
mechanism? Outline the mechanism.
3. What is ozonolysis? Explain with examples. Write
the structure and IUPAC name of alkene which give (ii) An olefine compound 'A' on ozonolysis gives
the following produced on ozonolysis: one molecule each of formaldehyde.
(i) Acetone only Acetaldehyde and methylglyoxal. Assign the

structure for A.
(ii) Acetone and formaldehyde
(iii) Compete the reaction. Outline the
(iii) Methyl ethyl ketone and acetone
mechanism of the given reaction:
[Kanpur 2010]
Peroxide
4. A compound (A) C5H12, on chlorination at 300°C H3C – C =CH =CH3 + HBr   → ?
gives a mixture of four different monochorinated [Lko. 2009]
derivatives (B), (C), (D) and (E). Two of these 9. (i) H–C ≡ C(–) is a waker base than H3C - CH2(–).
derivatives give the same stable alkane (F) of Explain.
dehydrohalogneation. (F) on oxidation with hot (ii) How will you synthesise the following:
alkaline KMnO4 followed by acidification, gives two (a) Methyl acetylene from isopropyl alcohol
products (G) and (H). Identify (A) to (H) and write (b) 1,4 dibromo –butene from acetylene
all reactions. [Kanpur 2011] (c) Chloroprene from acetylene. [Lko. 2009]
5. (i) How will you convert acetylene into the
10. How will you bring about the following
following compounds? conversions?
(a) 1-Butyne (b) Neoprene (i) Ethanol → Chloroform
(c) Vinyl acetone (ii) Acetylene → Ethylidene dibromide
(ii) How will you convert propene into the (iii) Chloral →DDT
following compounds? (iv) Acetylene → Cyclooctatetraene [Rohd. 2012]
(a) Allene (b) Ethene (c) n-propyl alcohol
11. (i) Explain Markovnikov's rule and its
[Kanpur 2011]
mechanism with example.
6. Complete the following reactions & write down the
mechanism of any one of them (ii) Discuss the stability and 1,4 addition
(i) BH / THF reactions in conjugated butadiene.
CH3 – CH =CH2  →
(ii) H2 O/ NaOH [Hazaribagh 2010]
HBr 12. Discuss the mechanism of 1,2 and 1,4 addition of

CH2 – CH – CF3   → [Avadh 2008] HBr to buta-1,3 diene with the relative yield of the
two products.
O-267
13. On ozonolysis followed by the hydrolysis of an

Short Answer Type Questions organic compound AC7H14 gave and aldehyde
1. (i) Acetylene is passed through red hot BC3H6O and a kentone CC4H6O Identify the
iron tube in presence of catalyst compounds A, B and C and give all chemical
dicarbonyle di (triphenyl phosphino) reactions . [Kanpur 2008]
nickel. 14. Give name and structure of such alkenes that yield
(ii) Calcium carbide reacts with water. Write on ozonolysis followed by the hydrolysis with
reactions only. [Bund. 2008] chemical reaction :
2. Arrange the following in decresing order of their
(i) CH3CHO and HCHO
acidity and explain. [Bund. 2008]
(ii) CH3COCH3 and HCHO [Kanpur 2008]
CH3 – CH3, – CH ≡ CH, CH2 = CH2
15. What is Diel's Alder reaction? Give its mechanism.
3. Explain ozonolysis. [Bund. 2008] [Kanpur 2009]
4. Describe the types of polymerisation in acetylene. 16. Give structure of alkenes from which on ozonolysis
[Bund. 2009] followed by hydrolysis the following are obtained :
5. Explain Markovnikov's rule with suitable example.
(i) CH3COCH3 and HCHO
[Bund. 2009]
6. Explain the following : (ii) Two molecules of CH3CHO [Kanpur 2009]
(i) Saytzeff rule 17. Write short notes on the following:

(ii) Markovnikov's rule. [Bund. 2010] (i) Hydroboration
7. What are dienes ? Classified the dienes. Give
(ii) Hydroxylation [Kanpur 2009]
methods of preparation, properties and structure
and stabillity of Butadiene - 1,3. 18. Write the reaction of HBr on propene. Give the
[Meerut 2008, 10, 11] mechanism in the presence of peroxide and in
8. Explain the mechanism of any two of the following : absence of peroxide. [Kanpur 2009]
(i) Elimination reactions 19. What is Markovnikov's rule? Explain with example
(ii) Addition reaction to C=C and give mechanism. [Kanpur 2010]
(iii) SN reactions [Meerut 2008] 20. Complete the following reactions :
9. Discuss Kharasch effect. Zn
[Meerut 2012] (a) CH3–CH=CH2+O3→?  → ? + ?
H2 O
10. Explain ozonolysis with mechanism. [Agra 2009]
11. Complete the following reactions. (b) CH ≡ CH +2CuCl +2NH4OH → ? +? +?
[Kanpur 2011]
(i) CH2 =CH2 +CS2Cl2 → ?
21. Complete the following reactions :
(ii) CH3 – CH =CH2 +HBr → ? (a) CCl
CH2 =CH2 +O3  4→
(iii) 1 Ag
CH2 =CH2 + O2  → ? (b) CH2 =CH2 +HOCl → ? [Kanpur 2011]
2 200 –400 ° C
[Kanpur 2008] 22. Discuss the mechanism of E1 reaction.
[Avadh 2008]
23. Complete the following reaction and give its
(i) CH ≡ CH +2CuCl +2NH4OH → ? mechanism. [Avadh 2010]
Ni
(ii) R – CH =CH2 +2H  → ? CH2 =CH2 – CH =CH2 +Br2 →
200 ° C
[Kanpur 2008]
O-268
24. Give the mechanism of the reaction: 32. Explain the following with suitable examples :
Conc. CH2SO4
CH3 – CH2 – OH  
→ (i) Dehydration of Alcohols.
∆
CH3 – CH =CH2 (ii) Saytzeff Rule
[Avadh 2010]
(iii) Dehydrohalogenation [Lko. 2008]
(i)BH / THF 33. Explain :
3
(i) CH3 – CH2 – C ≡ C – H  →
(ii)H2 O2 / NaOH (i) Unimolecular and biomolecular elimination
H O/ Hg++
reactions.
2
(ii) CH3 – CH2 – C ≡ CH  →
[Avadh 2009] (ii) Dehydration of alcohol with mechanism.
[Lko. 2010]
26. Explain:
34. Explain:
(i) Alkene is more reactive than alkyne for
(i) Oxymercuration Demercuration reaction.
electrophilic addition.
(ii) Antimarkovnikov's rule.
(ii) 1-Butyne is more acilic than 1-Butene.
(iii) Hydroboration-oxidation of propene.
[Avadh 2009]
[Lko. 2010]
27. Write note on:
35. In the presence of diethyl peroxide the addition of
(i) Hofmann elimination reaction. HBr to propene is against Markownikoff's rule. Give
(i) Hydration of alkyne. [Avadh 2009] mechanism also. [Rohd. 2009, 10]
28. Complete the following reactions and indicate the 36. Explain the addition of halogen acid on an
major product, unsymmetrical alkene. Give the mechanism of the
(i) 3 (i) BH / THF reaction. [Rohd. 2011]
CH3 – CH – CH2  →
(ii) H2 O2 / NaOH 37. Explain the mechanism of elimination (E1 and E2)
Cl2 /500 ° C reaction of alkyl halides.
(ii) CH3 – CH =CH2  → [Rohd. 2011]
[Avadh 2009] 38. Explain ozonolysis of benzene. [Rohd. 2012]
29. Discuss the structure of ethylene and acetylene 39. Delocalisation leads to stability.Why? [Rohd. 2012]
based on molecular orbital theory with the help of
40. How is 1,3-butadiene industrially prepared?
suitable diagram. [Kashi 2008] [Rohd. 2012]
30. (i) Explain why hydrogen atom of acetylene is 41. Complete the following reactions :
more acidic than that of ethane. (i) 2 O .Ag
H2C=CH2  →?
(ii) Write short notes on : 250 ° C
KMnO
(ii) H3C–CH=CH–CH3  4→
(a) Epoxidation (b) Ozonolysis
[D.D.U. 2009]
(c) Hydroxylation [Kashi 2010] 42. In butadiene, C– C bond length is 1.46 A° and C =
31. Complete the following reaction : C bond length is 1.39 A°, Why? [D.D.U. 2011]
(i) CH3
43. (i) Give the product and mechanism of
H3C–C–Br EtOH, ∆ ? their formation of the following :
Conc,
CH3 CH3 – CH2 – Cl   →
NaOH
(ii) CH2 = C ≡ CH2 + Br2 → ? (ii) Write the structure of alkene which on
(i) O3 / CH2 Cl2 ∆ ozonolysis gives acetone molecule only.
(iii) CH3 – C ≡ CH  →
(ii) ZnIH2 O [Lko. 2008] [D.D.U. 2011]
O-269
44. Discuss the structure of ethylene and acetylene 9. Indicate the type of hybridization on each carbon
based on molecular orbital theory with the help of atom in the following molecules.
suitable diagram. [Hazaribagh 2008] (i) CH3 − CH2 − C ≡ CH
45. What is Saytzaff rule? Explain it taking example of (ii) HC ≡ C − C ≡ CH [Agra 2008]
the mechanism of dehydration of alcohols? 10. Give the IUPAC names of the following compound :
[Hazaribagh 2008,10]
CH3 − CH2 = CH – CH ≡ CH [Agra 2008]
46. Write a note on peroxide effect.
11. Complete the following reactions:
[Hazaribagh 2008,10]
(i) CH2 = CH − CH =CH2 +CH2 =
47. What is Saytzeff rule? Explain it taking example of Heat
CH2  → ?
the mechanism of dehydration of Butanol-2.
[Hazaribagh 2009,11] (ii) CH2 = CH − CH =CH2 +
low temp
48. Explain polymerization of alkenes. HCl  → ?
[Hazaribagh 2009] [Kanpur 2009]
49. Explain the action of H2O on propyne in presence 12. Why acetylene is acidic while ethane is neutral ?
of HgSO4/H2SO4. [Hazaribagh 2009] [Kanpur 2009]
50. What are the conjugated diens? Discuss the relative 13. Show hybridization on each carbon atom in
stabilities of different dienes. [Hazaribagh 2011] CH3 − C ≡ H . What is the difference between
bonds ? [Kanpur 2009]
51. Alkynes undergo nucleophilic additions but alkenes
do not. Explain. [Hazaribagh 2011] 14. How will you distinguish between butyne-1 and
butyne-2? [Kanpur 2009]
Very Short Answer Type Questions 15. Convert: HC = CH → CHOCHO [Kanpur 2009]
1. Give reactions only: 16. (i) Ethyne into 1-Butyne
(i) Cyclohexane reacts with hydrogen in (ii) Methane into Carbon tetrachloride
presence of Ni at 80°C to 100°C. [Kanpur 2009]
(ii) Cyclobutane reacts with HBr. [Bund. 2008]
2. Explain why hydrogen of alkyne is acidic?
[Bund. 2009; Avadh 2009]
(a) CH2 = CH − CH =CH2 +CH2 =CH2 → ?
3. What is Diels-Alder reaction? CH3 − CH2 − CH(–OH) – CH3

(b) 60%H SO
[Bund. 2010; Avadh 2009] 2 4 → ? +?
 
100 ° C [Kanpur 2010]
4. Explain why acetylene is more acidic than ethylene.
[Bund. 2010] 18. Convert: Chloroform into acetylene.
[Kanpur 2010]
5. Write the I.U.P.A.C names of the following :
CH2 = CH − C ≡ CH 19. How will you convert the following ?
[Meerut 2008]
(i) CH ≡ CH to acetaldehyde
6. What happens when
dil H SO (ii) CH ≡ CH to chloroprene. [Kanpur 2011]
(a) 2
CH ≡ CH  4
→..............
HgSO4 20. Complete the following reactions :
(b) oxidation HOH
 → C3COOH [Meerut 2008] (i) CH3 – CH =CH – CH2Cl  →
[Avadh 2008]
7. Discuss Saytzeff's rule. [Meerut 2012]
21. Which one of the following alkenes is most stable?
Peroxide
(i) CH3 – CH2 – CH2 – CH =CH2
CH3 − CH = CH2 + HBr   → ? (ii) CH3 – CH =CH – CH2 – CH3
[Agra 2008] [Avadh 2010]
O-270
22. Write IUPAC name of CH2= CH–CH.=CH2. (i) CH2 = C = CH2

[Kashi 2008]
(ii) CH2 = CH – CH = CH2
23. Explain why hydrogen atom of acetylene is acidic.
(iii) CH3 – CH2 – CH2 – CH = CH2
[Kashi 2008]
(iv) CH2 = C(CH3) – CH = CH2. [Lko. 2011]
24. Complete the following reaction :
CH3 – CH =:CH2 – HO – Cl → [Kashi 2010] 35. Explain, why ethylene is more reactive than
acetylene towards electrophilic addition reaction.
25. Why alkynes are less reactive than alkenes towards
[Lko. 2011]
electrophilic reagent? [Kashi 2010]
36. Indicate the product and explain its formation
26. Complete the following reaction mechanistically in the equation given,
CH3 – CH =CH2 +HBr → [Kashi 2011] H+
CH2 =C =CH2  →
H2 O [Lko. 2011]
27. Write product of ozonolysis in the following
reaction: 37. Write mechanism of epoxidation.
CH3 CH3 38. Write IUPAC name of CH2 = CH – C = CH.
(I) O3
C=C ? [Hazaribagh 2008]
(I) Zn/H2O
CH3 H
[Kashi 2011] Objective Type Questions

28. Write IUPAC name of the following :
CH3
(i)
1. Alkenes have general formula:
CH3–C–CH2–CH3
(a) CnH2n (b) C2nH2n
CH3 (c) CnH2n+2 (d) CnH2n-2 [Bund. 2008]
CH3 2. Which one of the following alkenes will give acetone

(ii) [Kashi 2008]
on ozonolysis?
CH3–CH=CH–CH–CH3 (a) CH3–CH2–CH=CH2
(b) CH3–CH=CH–CH3
29. Ethylene is more reactive than acetylene towards
(c) CH3–CH=CH–CH3
electrophilic reagents. Explain. [Lko. 2009]
(d) none [Avadh 2010]
30. What happens when 2-methyl -1- butanol is
dehydrated with conc. H2SO4? 3. Reaction of cold alkaline KMnO4 solution with
[Lko. 2009]
alkene is called :
31. Give the peroxide effect on the given reaction:
(a) Hydration
CH3CH =CH2 +HBr → Product. [Lko. 2009]
(b) Hydroxylation
32. Write the product of ozonolysis of Butene-1. (c) Oxidative Cleavage
[Lko. 2009]
(d) Hydrogenation [Avadh 2010]
33. Name the product of reductive ozonolysis of the
4. Which of the following compounds forms a white
following :
ppt. with ammonical silver nitrate?
(i) CH3CH = CHCH3
(a) CH3CH2C ≡ CCH3
(ii) R2C = CHR [Lko. 2010]
(b) CH2 =CHCH2CH3
34. Which amongst the following has highest heat of (c) CH3CH2C ≡ CH
hydrogenation and why?
(d) CH3CH ≡ CHCH3 [Rohd. 2012,13]
O-271
10. When propyne is treated with aqueous H2SO4 in

5. The reaction of propene with HOCl proceeds via
the presence of HgSO4, the major product is:
the addition of:
(a) propanol
(a) H + in the first step
(b) propyl hydrogen sulphate
(b) Cl + in the first step (c) acetone
(c) −
OH in the first step (d) propanol
+ − 11. Water can be added across a triple bond in the
(d) Cl and OH in a single step
presence of:
6. Which of the following compound will be least
(a) Acidic medium
susceptible to elimination of hydrogen bromide ?
(b) Alkaline medium
(a) Br–CH2–CH2–NO2
(c) Neutral medium
(b) Br–CH2–CH2–CH3 (d) Acid and HgSO4
(c) Br–CH2–CH2–CN 12. The treatment of R'MgBr with RC≡CH produces an
alkane:
(d) Br–CH2–CH2–CO2Et
(a) RH (b) R'H
7. Me H Me
(c) R–R (d) R'–R
13. The ozonolysis of an olefin gives only propanone.
H
The olefin is:
Me
H (a) Propene
(b) but–1–ene
Hydrogenation of the above compound in the
(c) but–2–ene
presence of poisoned palladium catalyst gives:
(d) 2,3–dimethyl –but–2–ene
(a) An optically active compound 14. Anti–Markovnikov's addition of HBr is not observed
(b) An optically inactive compound in:
(a) propene (b) butene
(c) A racemic mixture
(c) 2–butene (d) 2–pentene
(d) A diastereomeric mixture
15. n–Propyl bromide on treating with ethanolic
8. The treatment of ethene with cold alkaline potassium hydroxide produces:
potassium permanganate produces: (a) propane (b) propene
(a) Ethylene glycol (c) propyne (d) propanol
16. 1–Chlorobutane on reaction with alcoholic potash
(b) Formaldehyde
gives
(c) Formic acid (a) 1–butene (b) 1–butanol
(d) Carbon dioxide and water (c) 2–butene (d) 2–butanol
9. Propyne and propene can be distinguished by: 17. Which of the following compounds gives the same
carbocation on ionization ?
(a) conc. H2SO4
Br
(b) Br2 in CCl4
(c) dil. KMnO4 Br
(d) AgNO3 in ammonia (1) (2)
O-272
Br
7. Isolated diene is ……… stable than cumulated
Br
diene.
(3) (4) 8. Ethyne is ……… acidic than ethane.
9. Properly substituted allenes are ………. .

(a) 1 and 3 (b) 2 and 4
10. Cyclooctene can show ……… isomerism around
(c) 1 and 2 (d) 1 and 4
double bond.
18. The addition of HBr to an alkene in the presence of
peroxide is an example of: True/False
(a) Electrophilic addition reaction
1. Cumulated diene is less stable than conjugated
(b) Nucleophilic addition reaction diene.
(c) Free radical addition reaction 2. Diels Alder reaction is a pericyclic reaction.
(d) The formation of carbocation as the
3. Bromine water test is confirmatory test for alkenes
intermediate
and alkynes.
19. The peroxide effect involves: 4. Reductive ozonolysis of but-2-ene yields 2 moles of
(a) Ionic mechanism acetone.
(b) Free–radical mechanism 5. Alkynes are more reactive than alkenes towards
electrophilic addition reaction.
(c) Heterolytic fission of double bond
6. Cyclohexa-triene is a conjugated triene.
(d) Homolytic fission of double bond
7. Ethene upon treatment with peroxyformic acid
20. The addition of HCl to 3,3,3–trichloropropene
yields an epoxide.
gives:
(a) Cl3CCH2CH2Cl 8. Out of cis 2-butene and trans 2-butene, trans isomer
is less stable.
(b) Cl3CCH(Cl)CH3
9. Dehydration of alcohols is an E1 mechanism.
(c) Cl2CHCH(Cl)CH2Cl
(d) Cl2CHCH2CHCl2 10. Dehydrohalogenation of 2-Bromobutane yields
2-butene as major product.
Fill in the Blank

1. Alkenes are ……… hydrocarbons.
2. Alkenes are ……… reactive than alkynes towards

catalytic hydrogenation.
3. Buta-1,3-diene undergo ……… addition at 273K.
4. Conversion of propyne into acetone is an example

of ……… .
5. Baeyer's reagent is ………. .
6. Cyclohexene and hexyne are ……… isomers.

O-273
Answers

1. (b) 2. (d) 3. (b) 4. (c) 5. (b)
6. (b) 7. (b) 8. (a) 9. (d) 10. (c)
11. (d) 12. (b) 13. (d) 14. (c) 15. (b)
16. (a) 17. (c) 18. (c) 19. (b) 20. (a)
Fill in the Blank

1. unsaturated 2. less 3. 1,2
4. nucleophilic addition 5. cold alkaline potassium 6. ring–chain

reaction. permanganate solution
7. more 8. more 9. chiral
10. cis–trans
True/False
4. False 5. False 6. True
7. True 8. False 9. True
10. True
Hints and Solutions

12. Conjugated dienes undergo addition reactions in a similar manner to simple alkenes, but two modes of
addition are possible.
These differ based on the relative positions of H and X in the products:
1 1 3
H–X 2 + X
H H
2 4
X
Direct or 1,2–addition Conjugate or 1,4–addition
O-274
Direct H-X adds "directly" across the ends of a C=C
Conjugate H-X adds across the ends of the conjugated system
The numbers 1,2- and 1,4- denote the relative positions of H and X in the products. The distribution of the
products depends on the reaction conditions as shown by the example below. The corresponding
mechanism is also given here with.
HBr 81% 19%

–30°C
Br Br
3–bromo –1–butene 1–bromo –2–butene

HBr 44% 56%
20°C
Br– Br–
mechanism
H+
H H
+ +
2° carbocation 1°carbocation
At low temperature, the reaction is under kinetic control and the major product is the one which is obtained
from fastest reaction. The fastest reaction is definitely the one in which the bromide ion reacts with the
secondary carbocation yielding 3-bromo-1-butene.
At higher temperature, the reaction is under thermodynamic control and the major product is the more stable
system. The more stable system refers to the more highly substituted alkene which is 1-bromo-2-butene.

38.
C=C C–C
O
O
O H
C H
C R O
R O
mmm
UnitO-275
-IV
C HAPTER 6
Arenes and Aromaticity
1. Arenes
There are hydrocarbons which consist of both aliphatic and aromatic groups and these compounds are
known as arenes. Toluene, ethyl benzene and isopropyl benzene are alkyl benzenes while vinyl benzene also
known as styrene is an alkenyl benzene. The aliphatic portion of these compounds is commonly called the
side chain.
CH3 C2H5 CH(CH3)2 CH=CH2
Methyl benzene Ethyl benzene Isoprophyl benzene Phenyl ethene
1.1 Methods of Preparation of Arenes

Preparation of Alkyl Benzenes
There are a number of methods available for the formation of arenes. Some of these are discussed below,
1. Friedel−Crafts alkylation: Substitution of hydrogen atom by alkyl group in aromatic compound is
known as Friedel–Crafts alkylation. Friedel–Crafts alkylation is initiated by the attack of alkyl
carbocation on aromatic ring. The carbocation can be generated either by R–X and AlX3, alcohol and
acid or by alkene and acid.
AlX
3 → R++Alx −
R – X  
 4
H+
R – OH  → R + + H2O
The Friedel–Crafts acylation involves following steps,
H+
Alkene  → Alkyl carbocation
O-276
H
R
K1 +
+R
+
+ R –H
K–1 K2
This reaction has the limitation that linear alkyl benzenes (LAB) cannot be prepared by this method as the
carbocations undergoes extensive rearrangements.
2. Friedel−Crafts acylation: Substitution of hydrogen by acyl group in aromatic compound is known
as Friedel Crafts acylation. The most commonly used catalyst is anhydrous AlCl3, although other
Lewis acids can also be used. The acylating reagents are normally an acid derivative like acid halides or
acid anhydrides.
The Friedel–Crafts acylation involves following steps,
(i) O
+ •• + –
R–C–Cl + AlCl3 R–C=O R–C≡O +AlCl4 or RCO+AlCl4–
••
••
(ii) H
Slow
+R–C+=O COR
RDS
⊕
(iii) H COR
AlCl4–
COR +HCl+AlCl3
fast
⊕
This reaction can be employed for preparing lab. In the first step, Friedel–Crafts acylation is done
which is followed by Clemmenson's reduction in the second step.
1.2 Preparation of Alkenyl Benzenes

1. Styrene (vinyl benzene) can be prepared as
CH(Br)CH3
CH2CH3
CH2=CH2 NBS
H+ in CCl4
alc. KOH
CH=CH2
(Styrene)
O-277
Alkenyl benzenes that have their side-chain double bond conjugated with the benzene ring are more stable
than those that do not have.
—C=C–C– is more stable than —C–C=C–
Conjugated Non conjugated

system system
Evidence is support of this comes from acid-catalyzed dehydration of alcohols, which are known to yield the
most stable alkene. For example, dehydration of the following alcohol yields exclusively the conjugated
system.
H H H
H+,heat
—C=C–C– —C=C–C–
(–H2O)
H OH H
As conjugation always lowers the energy of an unsaturated system by allowing the p electrons to be
delocalized, this behavior is just what we would expect.
2. Alkenyl benzenes can also be obtained by simple elimination process like the dehydrohalogenation of
haloalkyl groups attached to benzene ring. The elimination is generally governed by Saytzeff rule i.e.,
more substituted alkene is formed in greater amount. Couple of examples are given below,
CH2–CH–CH3 CH=CH–CH3 CH2–CH=CH2
alc. (major) (minor)
Br +
KOH
CH2CH2–CH–CH3 CH2CH=CHCH3 CH2CH2CH=CH2

(minor)
Br alc. (major)
+
KOH
Solved Examples
Example 1: Give the products and account for the major product of dehydrohalogenation of
(i) ArCH2CHBrCH2CH2CH3 (ii) CH3CBrArCH2CH2CH3
(iii) CH3CHArCHBrCH2CH3 (iv) BrCH2CHArCH2CH2CH3
Solution : (i) Conjugated ArCH = CHCH2CH2CH3 (major), unconjugated ArCH2CH = CHCH2CH3
(minor).
(ii) Conjugated, trisubstituted CH3CAr = CHCH2CH3 (major), conjugated disubstituted H2C =
CArCH2CH2CH3 (minor)
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(iii) Conjugated CH3CAr = CHCH2CH3(major) unconjugated CH3CHArCH = CHCH3 (minor).
(iv) H2C = CArCH2CH2CH3. A 1° Br can give only a single product.
In general the most substituted, least sterically–hindered alkene with its C = C conjugated with the ring is the
major product because of its greatest stability. This stability is a contributing factor towards faster rate of
formation.
2. Structure of Benzene
Benzene is formed from a six-membered ring constituted by carbon atoms with alternating single and double
bonds. Interestingly, this description fits well for a cyclohexatriene ring. This bonding arrangement was
developed by Kekule. According to Kekule model, benzene has two resonating structures as shown below,
H H
H C H C
H H
C C C C
C C C C
H C H H C H
H H
Fig. 1: Two resonating Kekule structures of benzene
These two resonating forms correspond to the double and single bonds superimposing to give rise to six
one-and-a-half bonds. As is standard for resonance diagrams, a double-headed arrow is used to indicate that
the two structures are not distinct entities, but merely hypothetical possibilities. Neither of the two structures is
an accurate representation of the actual compound. Rather the actual compound is the best represented by a
resonance hybrid or average of these two Kekule structures, and the whole phenomenon can be shown
below,
nb: not
Or, it can be compared to a real life situation below,
Unicorn Dragon ≡ Rhinoceros
Resonance structures Real structure
(hybrid)
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H
H H
H H
H is a far better representation of benzene molecule. Here, the circular π–bond also known as
Armstrong's inner cycle represents a delocalised π-bond above and below the ring. The
electron density is evenly distributed throughout the molecule. This model more correctly represents the
location of electron density within the aromatic ring.
2.1 σ and a π-bonding Arrangement

The single bonds are formed with electrons in line between the carbon nuclei–these are called σ-bonds.
Double bonds consist of a σ-bond and a π-bond. Following diagram shows the σ bonding arrangement
among only carbon atoms in the ring.
σ σ
σ σ
σ σ
Fig. 2: σ bonding arrangement in the hexagonal ring of benzene
However, the benzene ring contains two types of σ–bonds–type I involve C-C σ bonds which is being shown
in fig above and the type II involve C-H σ bonds. These are shown together in the diagram below,
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The π-bonds are formed from overlap of atomic p-orbitals above and below the plane of the ring. The
following diagram shows the positions of these p-orbitals:
Fig. 4: Position of p–orbitals in benzene ring
These p–orbitals are out of the plane or more precisely in the plane perpendicular to the molecular plane of
the carbon atoms. These p–orbitals can interact with each other freely, and give rise to delocalized π bonding.
This means that instead of being tied to one atom of carbon, each electron is shared among all six carbon
atoms in the ring. Thus, the "extra" electrons strengthen all of the bonds on the ring equally.
H H
H H H
H
H
H H H
H H
6 p–orbitals Delocalized
Fig. 5: Delocalized π – ring in the perpendicular plane
2.2 Bond length

Comparing the two contributing Kekule structures of benzene, it can be observed that all the single and
double C-C bonds are interchanged in the two canonical forms as observed in fig1.
Bond lengths can be measured using X-ray diffraction technique. The average length of a C-C single bond is
154 pm; that of a C=C double bond is 133 pm. In localized cyclohexatriene, the carbon-carbon bonds
should be alternating 154 and 133 pm. Instead, all carbon-carbon bonds in benzene are found to be about
139 pm, a bond length intermediate between single and double bond. This mixed single and double bond
character is typical for all molecules in which bonds have a different bond order in different contributing
structures. Bond lengths can be compared using bond orders. For example in cyclohexane the bond order is
1 while that in benzene is 1+(3/6)= 1.5 . Consequently, benzene has more double bond character and hence
has a shorter bond length than cyclohexane.
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2.3 Resonance Energy of Benzene

Every structure is associated with a certain quantity of energy, which determines the stability of the molecule
or ion. So, lower is the energy, the greater is its stability. A resonance hybrid has a structure that is
intermediate between the contributing structures; the total quantity of potential energy, however, is lower
than the intermediate. Hybrids are therefore always more stable than any of the contributing structures would
be and the same is true for benzene also. Delocalization of the π-electrons lowers the orbital energies,
imparting this stability. The difference between the potential energy of the actual structure (the resonance
hybrid) and that of the contributing structure with the lowest potential energy is called the "resonance
energy".
2.4 Measurement of Resonance Energy of Benzene

It is known that resonance or delocalization energy is the amount of energy needed to convert the true
delocalized structure into that of the most stable contributing structure. The empirical resonance energy can
be estimated by comparing the enthalpy change of hydrogenation of the real substance with that estimated
for the contributing structure.
The complete hydrogenation of benzene to cyclohexane via 1,3-cyclohexadiene and cyclohexene is

exothermic; 1 mole benzene delivers 208.4 kJ (49.8 kcal).
H2 H2 H2
1 mol
∆H=+23.4 kJ ∆H=–112.1 kJ ∆H=–119.7 kJ
(+5.6 kcal) (–26.8 kcal) (–28.6 kcal)
Benzene 1,3–Cyclohexadiene Cyclohexene Cyclohexane
Hydrogenation of one mole of double bonds delivers 119.7 kJ (28.6 kcal), as can be deduced from the last
step, the hydrogenation of cyclohexene. In benzene, however, 23.4 kJ (5.6 kcal) are needed to hydrogenate
one mole of double bonds. The difference, being 143.1 kJ (34.2 kcal), is the empirical resonance energy of
benzene. Because 1,3-cyclohexadiene also has a small delocalization energy (7.6 kJ or 1.8 kcal/mol) the net
resonance energy, relative to the localized cyclohexatriene, is a bit higher: 151 kJ or 36 kcal/mol. This
measured resonance energy is also the difference between the hydrogenation energy of three
'non-resonance' double bonds and the measured hydrogenation energy:
(3 × 119.7) – 208.4 = 150.7 kJ/mol (36 kcal).
2.5 Molecular Orbital Representation of Benzene

The bond angle of 120° in benzene suggests that C atoms are sp2 hybridised. An alternative representation
therefore starts with a planar framework and considers overlap of the p orbitals (π electrons).
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Unused p orbital
×6
sp2 hybridised C Delcocalised π system
According to simple MO rules, mixing n atomic orbitals yields the same number of molecular orbitals or stated
mathematically,
Mix n × π atomic orbitals → nπ molecular orbitals
If applied in the case of ethene, a predicted result is obtained. So, two 2p atomic orbitals are mixed together
to yield a pair of molecular orbitals labelled as bonding molecular orbitals and antibonding molecular
orbitals,
2p orbitals Bonding π–orbital Antibonding π–orbital (π*)
π∗
overlap
Energy
Similarly, in benzene ring, there are 6 overlapping pure atomic p orbitals, so there will be 6 molecular orbitals
formed as well. Out of these 6 molecular orbitals, 3 are bonding and 3 are antibonding. So, it can be
summarised as,
3 Higher energy π*
In benzene there are 6 x overlapping p–orbitals → 6 π MO's
3 Lower energy π
The exact calculation of their position as shown below is beyond the scope of this text book.
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π∗
Energy overlap
6 isolated p–orbitals
π
Each MO can accommodate 2 electrons, so for benzene, one can observe that all electrons are paired and
occupy low energy MO's or bonding MO's. All bonding MO's are filled. Benzene is therefore said to have a
closed bonding shell of delocalised π electrons and this accounts in part for the stability of benzene. There
is a simple "trick" for working out the orbital energies which is termed as Frost-Musulin diagrams. In this
diagram, a polygon is drawn in a circle. One has to draw the molecular framework of a cyclic system of
overlapping p-orbitals, making sure that an atom must be kept at the bottom. Atomic positions, in the present
case the positions of p-orbitals then map on to the energy level diagram as shown below,
3. Aromaticity and Huckel's Rule

3.1 Aromaticity
Historically, the earliest use of the term "aromatic" was in an article by August Wilhelm Hoffmann in 1855.
Hoffmann used the term as a class term for compounds of benzene, many of which do have odors unlike pure
saturated hydrocarbons. Today, there is no general relationship between aromaticity as a chemical property
and the odour or smell of such compounds. In terms of the electronic nature of the molecule, aromaticity
describes the way conjugated ring of unsaturated bonds, lone pairs of electrons, or empty molecular orbitals
exhibits a stabilization stronger than would be expected by the stabilization of conjugation alone. Huckel's
rule helps us to decide that a given compound would be aromatic or not by observing its structure.
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3.2 Huckel's Rule

Huckel's rule deals with the aromaticity of a compound. According to Huckel's rule, an aromatic compound
contains a set of covalently bonded atoms with specific characteristics. These characteristics are outlined
below,
1. A compound must contain a delocalized conjugated π system so that it can become aromatic. A
delocalized conjugated π system is most commonly an arrangement of alternating single and double
bonds in a compound. However, conjugation can be achieved in a number of other ways like a
negative charge is conjugated with a double bond or a lone pair is conjugated with a double bond etc.
2. The compound must have a coplanar structure, which means that all the contributing atoms must be in
the same plane.
3. Constituting atoms arranged in one or more than one rings must constitute a closed loop of electrons.
4. Most importantly, the species must have (4n + 2) π electrons, where n=0, 1, 2, 3, and so on.
Whereas benzene is aromatic due to the presence of 6 π electrons, from 3 double bonds, cyclobutadiene is
not. It is because the number of π delocalized electrons is 4 and does not confirm to the prerequisite of (4n +
2) π electrons. The cyclobutadienide (2–) ion, however, is aromatic because it has 6π electrons. Aromatic
molecules typically display enhanced chemical stability, compared to similar non-aromatic molecules. A
molecule that can be aromatic will tend to alter its electronic or conformational structure to be in this situation.
This extra stability changes the chemistry of the molecule. Aromatic compounds undergo electrophilic
aromatic substitution and nucleophilic aromatic substitution reactions very frequently. However, these
compounds do not show electrophilic addition reactions as happens with carbon-carbon double bonds. It is
definitely attributed to the fact that taking part in electrophilic addition reactions causes loss of aromatic
stability of the compound.
3.3 Aromaticity in Some Other Compounds

1. The cases of naphthalene (I) & anthracene (II) are considered to check for their aromaticity.
(I) (II)
These compounds are definitely planar due to the sp² hybridized carbon atoms. Both these
compounds have conjugation in carbocyclic ring leading to cyclic delocalization and the closed loop
formed would have 10 π and 14 π electrons respectively. So, both the compounds are aromatic as both
the conditions are fulfilled.
2. If four species are provided, which are shown as
• •
⊕ •
H H H
Cyclopropene Cyclopropenyl Cyclopropenyl Cyclopropenyl
(III) radical (IV) cation (V) anion (VI)
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Of these four species, (III), (IV) and (VI) are non-aromatic, due to the failure of first condition, second
condition and second condition respectively. While the species (V) is aromatic as it will have permitted
cyclic delocalization and closed π–orbital is having 2 π electrons corresponding to n = 0.
3. If following species are provided then the aromatic species has to be picked out.
H H H
• ⊕ ••
Cycloheptatriene Cycloheptatrienyl Cycloheptatrienyl Cycloheptatrienyl

(VII) radical (VIII) cation anion (X)
(Tropyliumion) (IX)
Of the given species, only species (IX) is aromatic since it satisfies both the conditions required by a
species to be aromatic, while (VII), (VIII) and (X) are non-aromatic. (VII) is non–aromatic since it does
not undergo cyclic delocalization as one of the carbon atoms of the ring is sp3 hybridized inhibiting
extended conjugation. (VIII) is non–aromatic since in the closed loop, it has 7 π electrons which is not a
Huckel number so it is not satisfying Huckel's rule. (X) is non–aromatic since in the closed loop; it has 8
π electrons which is also not a Huckel number.
4. Now, it has to be analysed whether pyrrole and pyridine are aromatic or not. It will be analysed one by
one.
N N
Pyridine Pyrrole
(XI) H (XII)
In pyridine, the nitrogen atom is sp2 hybridized with one of the sp2 hybrid orbital having a lone pair of
electrons. Thus, the sp2 hybrid lobe with lone pair is out of the plane with respect to the delocalized π
bond present in the ring. It is because the 6π electron ring is present in the Z plane as the ring is formed
by the overlap of pz orbital of adjacent carbon and the molecular plane is XY, so the lone pair of
nitrogen is not at all involved in delocalization. Thus pyridine is aromatic with no involvement of lone
pair in cyclic delocalization. While in pyrrole, the nitrogen atom is sp3 hybridized with one of the sp3
hybridized orbital having a lone pair of electrons. This sp3 lobe with lone pair is nearly planar with
respect to pz–orbital of the adjacent carbon, so the lone pair of nitrogen is involved in cyclic
delocalization and the closed loop will have 6 π–electrons. Thus, pyrrole is aromatic in nature.
5. Furan (IX) and thiophene(X) are aromatic as well due to the same line of explanation as applicable to
pyrrole.
O S
Furan Thiophene
(XIII) (XIV)
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Both furan and thiophene are typical in one aspect. These two compounds represent cases when an atom in
any aromatic system can have more than one lone pair of electrons and out of those lone pairs only one is the
part of aromatic sextet and the rest are not therefore ignored for the 4n + 2 rule. So, in furan, the oxygen
atom is sp² hybridized. One lone pair is in the π system and the other in the plane of the ring lying in one of the
sp² hybridized lobes. So, only one lone pair of electrons is considered as part of the aromatic ring of furan and
the other one which is lying in the molecular plane is excluded from the aromatic sextet. Since there are 6 π
electrons, so furan is aromatic with one lone pair of electrons available on oxygen atom which is not a part of
aromatic ring. The same explanation is applicable for thiophene.
NMR signal
The circulating π electrons in an aromatic molecule produce ring currents that oppose the applied magnetic
field in NMR. The NMR signal of protons in the plane of an aromatic ring are shifted substantially further
down-field than those on normal non-aromatic sp² carbon atoms. This is an important way of detecting
aromaticity. By the same mechanism, the signals of protons located near the ring axis are shifted up-field.
3.4 Antiaromaticity
Planar monocyclic molecules containing 4n π electrons are called antiaromatic and are, in general,
destabilized. Molecules that could be antiaromatic will tend to alter their electronic or conformational
structure to avoid this situation, thereby becoming non-aromatic. For example, cyclooctatetraene (COT)
distorts itself out of planarity, breaking π overlap between adjacent double bonds. Relatively recently,
cyclobutadiene was discovered to adopt an asymmetric, rectangular configuration in which single and
double bonds indeed alternate but there is no resonance and the single bonds are markedly longer than the
double bonds, reducing unfavorable p-orbital overlap. This reduction of symmetry lifts the degeneracy of the
two formerly non-bonding molecular orbitals, which by Hund's rule forces the two unpaired electrons into a
new, weakly bonding orbital and also creates a weakly antibonding orbital. Hence, cyclobutadiene is
non-aromatic; the strain of the asymmetric configuration outweighs the anti-aromatic destabilization that
would afflict the symmetric, square configuration.
Example 2: Which species is the smallest aromatic substance?

Solution : The cyclopropenyl cation is an aromatic substance because it has two π electrons (n = 0). It
forms a stable salt that can be stored in a bottle.
H–C=C–H
C+
H
Example 3: Which of the following species is/are aromatic
(i) (ii)
⊕
SbCl6
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(iii) Ph (iv)
⊕
⊕ •
H
Ph
Solution : For a compound to be aromatic, there must be cyclic delocalization with the closed loop formed
must have (4n + 2) π electrons. In the given case, (i), (ii) and (iii) qualify to be called as aromatic.
∴ (i), (ii) & (iii)
4. Electrophilic Aromatic Substitution Reactions

Most substitutions at an aliphatic carbon are nucleophilic. However, in aromatic systems the situation is
reversed, because the high electron density at the aromatic ring attracts positive species and negative ones
not so easily. In electrophilic substitutions, the attacking species is an electrophile-normally a positively
charged ion or sometimes a neutral species as well. The leaving group must necessarily depart without its
electron pair; therefore in electrophilic substitutions the most important leaving groups are those that can best
exist without the pair of electrons necessary to fill the outer shell, which is thereby the weakest Lewis acids.
The most common leaving group in electrophilic aromatic substitutions is a proton. These reactions in the
general form are shown below:
4.1 General Mechanism

Normally an electrophilic aromatic substitution reaction has some common steps like in the first step,
generation of electrophile takes place. In the second step, the electrophile attacks the benzene ring to give a
σ −complex and in the last step, retention of aromaticity takes place which leads to the eventual product
formation.These steps are discussed below one by one.
Step -1: Generation of electrophile

In this step, normally electrophiles like Cl + , nitronium ion , alkyl carbocation, acylium ion etc are produced as
per the reaction.
Step-2: Formation of σ – complex

The electrophile (E + ) attacks the ring, removing a pair of electrons from the sextet to give a carbocation which
is a resonance hybrid as shown in step–1. Ions of this type are called Wheland intermediate, σ
–complexes or arenium ions. Normally σ –complexes are highly resonance stabilized as shown below,
H H + H H
E E E E
+ Slow
+ E ≡ +
+ +
Arenium ion
( σ complex)
O-288
Step-3: Retention of aromaticity
The arenium ion loses a proton from the carbon atom that bears the electrophile. This step results into
retention of aromaticity and yield the eventual product.
+ E
H E
fast +
+H
The energy profile for general mechanism is shown as,
Some of the important electrophilic aromatic substitution reactions are halogenation, sulphonation, nitration,
Friedel Craft reactions-alkylation and acylation both etc.These are discussed one by one below,
4.2 Halogenation
Benzene does not react with bromine or chlorine unless a Lewis acid is present in the mixture. It is because of
this, benzene does not decolorize a solution of bromine in carbon tetrachloride despite having three double
bonds. When Lewis acids are present, however, benzene reacts readily with bromine or chlorine, and the
reaction yields bromobenzene and chlorobenzene in good percentage as shown,
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The Lewis acids most commonly used to effect chlorination and bromination reactions are FeCl3, FeBr3, and
AlCl3 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
Mechanism
The mechanism for aromatic bromination proceeds in the following manner.
Step–1: Generation of electrophile

Bromine combines with FeBr3 to form a complex that dissociates to form a positively charged bromine ion
and FeBr4– .
Step–2: Formation of σ − complex

The positive bromine ion attacks benzene to form an arenium ion also known as σ − complex.
H H + H
Br Br Br
+
Slow
+ Br
+ +
Arenium ion
Step–3: Retention of aromaticity

The arenium ion loses a proton to become bromobenzene.
–
H Br –FeBr3
Br Br
+H–Br +FeBr3
+
O-290
The general energy profile is,

Transition
state
⊕ Br
∆G# H
Energy
Br
∆G°
Reaction progress
Fig. 8: Energy profile for halogenation of benzene
Iodination
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 or iodic acid. The
oxidizing agent has an important role to play- it removes whatsoever HI formed in the reaction. As such HI is
strongly reducing in nature and it can reduce iodobenzene back to benzene.
I
HNO3
+ I2
4.3 Nitration
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.
Concentrated sulphuric acid increases the rate of the reaction by increasing the concentration of the
electrophile–the nitronium ion.

Nitric acid acts as a base and accepts a proton from the stronger acid, sulfuric acid as shown below,
O-291
The protonated nitric acid dissociates and produces a nitronium ion.
Step 2: Formation of σ − complex

The nitronium ion reacts with benzene by attacking the π cloud and forming an arenium ion.
Step 3: Retention of aromaticity

The arenium ion then transfers a proton to some base in the mixture such as HSO −4 and becomes
nitrobenzene.
+ NO2
H+HSO4– NO2
fast
+H2SO4
The general energy profile is,

≠
≠
NO2 H
Energy
NO2
+HNO3
+H2SO4
Reaction coordinate
Fig. 9: Energy profile for nitration of benzene
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4.4 Sulfonation
Benzene reacts with fuming sulfuric acid at room temperature to produce benzenesulfonic acid. Fuming
sulfuric acid is an equimolar mixture of sulfuric acid and sulfur trioxide (SO3). Sulfonation also takes place in
concentrated sulfuric acid alone, but the reaction rate is very slow.

In concentrated sulphuric acid, sulfur trioxide is produced in the following manner in which H2SO4 acts both
as an acid and a base.
2H2SO4 SO3+H3O++HSO4–
Step–2: Formation of σ −complex

The neutral SO3 molecule which is an electrophile reacts with benzene by attacking the π cloud and forming
an arenium ion.
O
H H + H
SO3– SO3– SO3–
Slow
+ S
+ +
O O
Sulfur trioxide
Arenium ion

The arenium ion thus formed then transfers a proton to the conjugate base of sulphuric acid, HSO −4 and
yields unprotonated benzene sulphonic acid.
–
+ SO3
H+HSO4– SO3–
fast
+H2SO4
Step– 4
Eventually the protonation of the compound takes place to yield benzene sulphonic acid.
–
SO3 SO3H
fast
+H3O+ +H2O
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All the steps in sulphonation are reversible, including step 1 in which sulfur trioxide is formed from sulfuric
acid. This means that the overall reaction is an equilibrium process as shown below,
SO3H
+H2SO4 +H2O
4.5 Friedel–Crafts Alkylation

A general schematic representation for a Friedel - Crafts alkylation reaction is expressed as:
R
AlCl3
+R—X +HX
Mechanism

Alkyl halide molecule in the presence of a Lewis acid catalyst gives rise to a carbocation as shown below. The
carbocation is the effective electrophile in the reaction.
(CH3)2CHCl+AlCl3 (CH3)2CH+ +AlCl4–
Isopropyl cholride Carbocation

Benzene ring attacks on the carbocation and yield the σ −complex also known as arenium ion as shown here,
H
CH3
CH3
CH
+ +CH + CH3
CH3
Arenium ion
The arenium ion thus formed then transfers a proton to the AlCl4 and yields alkylated benzene.
CH3
H
CH3 CH
CH CH3+HCl+AlCl3
+ CH3 +AlCl4–
Isopropylbenzene
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Some more examples are,

CH(CH3)2
+CH3CH=CH2 0°C
HF
Propene Isopropylbenzene
A mixture of an alcohol and an acid may also be used to yield a carbocation.

OH
60°C
+
BF3
Cyclohexanol Cyclohexylbenzene
4.6 Friedel Crafts Acylation

The RCO–group is called an acyl group, and a reaction where by an acyl group is introduced into a
compound is called acylation reaction. 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.
COCH3
AlCl3
+CH3COCl excess +HCl
benzene
80°C
Acetyl Acetophenone
Cholride
Acyl chlorides, also called acid chlorides, are easily prepared by treating carboxylic acids with thionyl
chloride (SOCl2) or phosphorus pentachloride (PCl5).
80 ° C
CH3CO2H + SOCl2   → CH3COCl + SO2 + HCl
PhCO2H + PCl5 → PhCOCl + POCl3 + HCl
Benzoic Phosphorus Benzoyl
acid pentachloride chloride
Friedel - Crafts acylations can also be carried out using carboxylic acid anhydrides. For example :
COCH3
AlCl3
+(CH3CO)2O excess +CH3COOH
benzene
80°C
Acetic anhydride Acetophenone
(a carboxylic acid
anhydride)
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Mechanism
In most Friedel - Crafts acylation the electrophile appears to be an acylium ion formed from an acyl halide in
the following way:
Step 1: Generation of electrophile
Acyl halide molecule in the presence of a Lewis acid catalyst gives rise to an acylium ion which is a highly
stable carbocation as shown below. As such, the carbocation-acylium ion is the effective electrophile in the
Friedel–Crafts acylation reaction.
O O
+
–
R – C – Cl + AlCl3 R – C – Cl – AlCl3
O
+ + +
–
R – C – Cl – AlCl3 R–C=O R – C ≡ O + AlCl4–
An acylium ion
(a resonance hybrid)
Benzene ring attacks the carbocation and yield the σ −complex also known as arenium ion as shown here,
H
R C–R
+ C + O
O+
Arenium ion
The arenium ion thus formed then transfers a proton to the AlCl4 and yields acylated benzene as shown below
H COR
+ COR +AlCl – +HCl+AlCl3

4
Step–4
In the last step aluminum chloride which is a Lewis acid as well forms a complex with the ketone (a Lewis
base). After the reaction is over, treating the complex with water liberates the ketone.
C–R C–R –
+AlCl3 AlCl3
O O
+
R R
C=O AlCl3+3H2O C=O +Al(OH)3+3HCl
C6H5 C6H5
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4.7 Limitations of Friedel-Crafts Reaction

1. The carbocation formed from an alkyl halide, alkene, or alcohol can rearrange to a more stable
carbocation and the major product obtained from the reaction is usually the one from the more stable
carbocation. When benzene is alkylated with butyl bromide, some of the developing 1° butyl
carbocation rearrange by a hydride shift -- to become more stable 2° carbocation. Then benzene reacts
with both kinds of carbocations to form both n–butylbenzene and sec-butyl-benzene.
δ+ δ +
CH3CH2CH2CH2Br AlCl3 CH3CH2CHCH2 BrAlCl3 CH3CH2CHCH3
(–BrAlCl–3)
(–AlCl3)
(–H+)
(–HBr)
CH3CH2CH2CH2 CH3CH2CHCH3
n–Butylbenzene sec–Butylbenzene
(32–36% of mixture) (64–68% of mixture)
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. This applies to both alkylation
and acylation.
O O
+ +
NO2 N(CH3)3 C–OH C–R CF3 SO3H NH3
It is always important to remember 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.
3. Friedel–Crafts reactions do not take place even in the case of the amino groups like -NH2, -NHR, and
-NR2 attached directly to benzene ring. It is because these groups are changed into powerful electron -
withdrawing groups by the Lewis acids used to catalyze Friedel - Crafts reaction. For example:
O-297
H H
H–N H–+N––AlCl3
+ AlCl3
Does not undergo

a Friedel–Crafts reaction
4. Aryl and vinylic halides cannot be used as the halide component because they do not form
carbocations readily.
Cl
no Friedel – Crafts reaction

AlCl3
no Friedel – Crafts reaction

–C=C–Cl
4.8 Birch Reduction

The Birch reduction is an organic reaction which is particularly useful in synthetic organic chemistry. The
reaction was reported in 1944 by the Arthur Birch. It converts aromatic compounds having a benzenoid ring
into a product, 1,4-cyclohexadienes, in which two hydrogen atoms have been attached on opposite ends of
the molecule. It is the organic reduction of aromatic rings like benzene or naphthalene or their derivatives in
liquid ammonia with sodium, lithium or potassium and an alcohol, such as ethanol and tert-butanol. Though
the original reaction reported by Arthur Birch in 1944 utilized sodium and ethanol.
H H
Na
NH3 ROH
H H
This reaction is quite dissimilar to the catalytic hydrogenation, which usually reduces the aromatic ring all the
way to a cyclohexane. Another example is the reduction of naphthalene,
Na, NH3,–78°C
EtOH, Et2O
78–80%
The Birch reduction also offers access to substituted 1,4-cyclohexadienes.

O-298
Mechanism
H H H
e– ROH e– ROH H
–RO– –RO–
H H H
H H H H
The question of why the 1,3-diene is not formed, even though it would be more stable through conjugation,
can be rationalized in valence bond terms. It is very important to observe that the electron-electron repulsions
in the radical anion will prefer to have the nonbonding electrons separated as much as possible, in a
1,4-relationship rather than 1,3-relationship.
Reactions of arenes with +I- and +M-substituents lead to the products with the most highly substituted
double bonds:
OMe OMe
Li, NH3
EtOH
Na,NH3
EtOH
On the other side for arenes with –I and –M substituents, the effect of electron-withdrawing substituents on
the Birch Reduction varies. For example, the reaction of benzoic acid leads to 2,5-cyclohexadienecarboxylic
acid. It can be rationalized on the basis of the carboxylic acid stabilizing an adjacent anion which is placed
alpha to it:
COOH COOH
Na,NH3 H3O+
EtOH
Alkene double bonds are only reduced if they are conjugated with the arene.
Na,NH3
EtOH
O-299
5. Disubstitution in Benzene Ring and Theory of Substituent Effect

It has been observed that certain groups activate the benzene ring toward electrophilic substitution, while
other groups deactivate the ring. When it is said that a group activates the ring, it means that the group
increases the relative rate of the reaction. So, an aromatic compound with an activating group reacts faster in
electrophilic substitutions than benzene. When it is said that a group deactivates the ring, it means that an
aromatic compound with a deactivating group reacts slower than benzene or the rate of reaction is retarded.
It is generally found that the relative rates of the reactions depend on whether the group S shown below
withdraws or releases electrons towards the benzene ring.
If S is an electron-releasing group (relative to hydrogen), the reaction occurs faster than the corresponding
reaction of benzene. If S is an electron-withdrawing group, the reaction occurs slower than that of benzene. It
appears, then, that the substituent (S) must affect the stability of the transition state relative to that of the
reactants. Electron-releasing groups apparently make the transition state more stable, while
electron-withdrawing groups make it less stable. This is fairly reasonable, because the transition state
resembles the arenium ion, and the arenium ion is a delocalized carbocation. On this basis of electron release
or withdrawal, groups attached to the ring can be put into two categories,
1. Ortho-para directing
2. Meta directing
O-300
The general energy profile for disubstitution of a benzene ring is,

Y H
Y
Ortho E
attack
⊕
+E
Y
Meta
⊕
Cl SO3H attack ⊕
Chlorination Sulfonation H ∆E2#
E
E ⊕
Energy
Y ∆E1 H
Br⊕ R⊕ Y
F–C alkylation Para
Bromination
attack ⊕ Y ∆E
⊕ ⊕ ⊕ ⊕
NO2 RC=O +E E+H
Nitration Y
F–C acylation
H Reaction progress
E
Fig. 10: Energy profile for disubstitution of a benzene ring
5.1 Ortho - Para - Directing Groups

Except for the alkyl and phenyl substituents, all of the ortho-para directing groups are of the following general
type:
All of these ortho-para directors have at least one pair of nonbonding also known as lone pair of electrons on
the atom adjacent to the benzene ring.
This structural feature - a lone pair of electrons on the atom adjacent to the ring - determines the orientation
and influences reactivity in electrophilic substitution reactions.
O-301
⊕
NH2 NH2 NH2 NH2
H H H H
Ortho
⊕
attack E E E E
⊕
⊕
NH2 Relatively stable
NH2 NH2 NH2
contributor
Meta
attack
⊕
⊕
H H H
⊕
E E E
NH2 NH2 NH2 NH2
Para
attack ⊕
⊕
⊕
H E H E H E H E
Relatively stable
contributor
It is observed that four reasonable resonating 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 must 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.
In case of halogens inductive effect predominates over the mesomeric effect, due to which they act as ring
deactivators instead of ring activators.
5.2 Meta-Directing Groups

All meta-directing groups have either a partial positive charge or a full positive charge on the atom directly
attached to the ring. As a typical example let us consider the trifluoromethyl group.
O-302
CF3 CF3 CF3

H H H
Ortho
⊕
attack E E E
⊕
⊕
Highly unstable
contributor
CF3 CF3 CF3
CF3
Meta
⊕
attack
⊕ H H H
⊕
E E E
CF3 CF3 CF3
⊕
Para
⊕
⊕
attack
H E H E H E
Highly unstable
contributor
From above it is clear that in the resonance structures for the arenium ion arising from ortho and para attack
that one contributing structure is highly unstable relative to all the others because the positive charge is
located on the ring carbon that bears the electron-withdrawing group. No such highly unstable resonating
structure can be drawn in the arenium ion arising from meta attack. This means that the arenium ion formed
by meta attack should be the most stable of the three.
5.3 Ortho - Para Direction and Reactivity of Alkylbenzenes

Alkyl groups are ortho - para directors. One can also account for this property of alkyl groups on the basis of
their ability to release electrons - an effect that is particularly important when the alkyl group is attached
directly to a carbon that bears a positive charge.
O-303
CH3 CH3 CH3

H H H
Ortho
⊕
attack E E E
⊕
⊕
Relatively stable
contributor
CH3 CH3 CH3
CH3
Meta
⊕
attack
⊕ H H H
⊕
E E E
CH3 CH3 CH3
⊕
Para
⊕
⊕
attack
H E H E H E
Relatively stable
contributor
In ortho attack and para attack it is observed that one can write resonating structures in which the methyl
group is directly attached to a positively charged carbon of the ring. These structures are more stable relative
to any of the others because in them the stabilizing influence of the methyl group (by electron release) is the
most effective. These structures, therefore, make a large stabilizing contribution to the overall hybrid for
ortho - and para - substituted arenium ions.
5.4 Summary of Substituent Effects on Orientation and Reactivity

One can summarize the effects which the groups have on orientation and reactivity in the following way.
Classification of substituents:
Table 1:Effect of substituents on electrophilic aromatic substitution
Ortho - Para Directors Meta Directors
Strongly activating Strongly deactivating
-NH2, -NHR, -NR2 -NO2

••
-OH, −O •• − − NR +3
••
-CF3, -CCl3
Moderately activating Moderately deactivating
-NHCOCH3, -NHCOR
O-304
-OCH3, -OR -C ≡ N
Weakly activating -SO3H
-CH3, C2H5, -R -CO2H, -CO2R
C 6 H5 -CHO, -COR
Weakly deactivating
-F, -Cl, -Br, -I
5.5 Synthetic Applications

5.5.1 Nuclear Halogenation or Halogenation of the Benzene Ring
When halogenation of the alkyl or alkenyl benzenes is to be carried out in ring, a lewis acid catalyst is required
as discussed in the topic of halogenations of benzene ring. Since alkyl and alkenyl groups are ortho and para
directing, so the incoming electrophile - Cl + or Br + respectively will be oriented at either ortho or para
position.
C2H5 C2H5 C2H5
Cl2/FeCl3 +
Cl Cl
(minor) (major)
CH=CH2 CH=CH2 CH=CH2
Cl2/FeCl3 +
Br Br
(minor) (major)
For the addition of Br2 to double bond of the side chain, the reaction should be carried out in the presence of
Br2 in CCl4.
5.5.2 Halogenation of the Side Chain

It has already been observed that bromine and chlorine replace hydrogen atom on the ring of toluene when
the reaction takes place in the presence of a Lewis acid. In ring halogenation, the electrophiles are positively
charged chlorine or bromine ions or they are possibly Lewis acid complexes that have positive halogens.
These positive electrophiles attack the π electrons of the benzene ring and aromatic substitution take place.
Chlorine and bromine can also be made to replace hydrogen atoms of the methyl group of toluene or in
general the alkyl group of the side chain. Such a chemical activity is referred as side chain halogenations. Side
chain halogenation takes place when the reaction is carried out in the absence of Lewis acids and under
conditions that favour the formation of radicals. When toluene reacts with N-bromosuccinimide (NBS) in the
presence of light, the major product is benzyl bromide. N- Bromosuccinimide furnishes a low concentration
O-305
of Br2 and the reaction is analogous to that for allylic bromination. Here, it is referred as benzylic
bromination. Mechanisms of such substitutions have already been discussed in the topic "alkenes".
O O
C C
H2C light
H2C
CH3 + NBr CH2Br + NH
CCl4
H2C H2C
C C
O Benzyl bromide O
Side chain chlorination of toluene can also takes place in the gas phase at 400 - 600°C or in the presence of
UV light. When an excess of chlorine is used, multiple chlorinations of the side chain occur.
CH3 CH2Cl CHCl2 CCl3
Cl2 Cl2 Cl2

heat / light heat / light heat / light
Benzyl (Dichloromethyl)– (Trichloromethyl)–

chloride benzene benzene
These halogenations take place through the same radical mechanism as for halogenation of alkanes. The
halogens dissociate to produce halogen atoms and then the halogen atoms initiate chains by abstracting
hydrogen atoms of the methyl group.
Mechanism
Expectedly the reaction mechanism has following steps.
Chain initiation step:

Peroxides,heat
Step 1 → 2X •
X2  
or light
Chain propagation step:
Step 2 C6H5CH3 + X • → C6H5CH2 • + HX
Benzyl radical
Step 3 C6H5CH2 • + X2 → C6H5CH2X + X •
Benzyl halide
Abstraction of hydrogen from the methyl group of toluene produces a benzyl radical. The benzyl radical then
reacts with a halogen molecule to produce a benzyl halide and a halogen atom. The halogen atom then
brings about a repetition of step 2, then step 3 occurs again and so on. Benzylic halogenations are similar to
allylic halogenations in that they involve the formation of unusually stable radicals. Benzylic and allylic
radicals are more stable than tertiary radicals.
O-306
The greater stability of benzylic radicals accounts for the fact that when ethyl benzene is halogenated the
major product is the 1-halo-1-phenylethane as benzylic radical is formed faster than the 1° radical.
X
fast X2
CH2CH3 CHCH3+X
Benzylic radical 1–halo–1–phenyletane

–CH2CH3 X (more stable) (major product)
(–HX)
X2
CH2CH2 CH2CH2X+X
slow
1° radical 1–halo–1–phenyletane
(less stable) (major product)
Example 4:
(i) Give the product of the reaction of p–xylene with NBS or with 2Br2 at 125°C in presence
of light.
(ii) Why does not dibromination at the one Me occur ?
(iii) Which reacts faster, p–xylene or toluene? Explain.
Solution:
(i) CH2Br
CH2Br
α–α'–dibromo–p–xylene
(ii) Electron withdrawal by one Br makes removal of an additional H • more difficult and thus the second
substitution occurs at other Me group.
(iii) p–xylene reacts faster than toluene as the electron–releasing Me provides additional stability to the
radical.
5.5.3. Addition to the Double Bond of Alkenyl Benzenes

In the presence of peroxides, hydrogen bromide adds to the double bond of 1-phenyl propene to give
2-bromo-1-phenyl propane as the major product.
HBr
CH=CHCH3 peroxides CH2CHCH3
Br
In the absence of peroxides, HBr adds in just the opposite way.

O-307
HBr
CH=CHCH3 (no peroxides) CHCH2CH3
. Br
The addition of hydrogen bromide to 1–phenylpropene proceeds through a benzylic radical in the presence
of peroxides, and through a benzylic cation in their absence.
5.5.4 Oxidation of the Side Chain

Strong oxidizing agents oxidize toluene to benzoic acid. The oxidation can be carried out by the action of hot
alkaline potassium permanganate. This method gives benzoic acid in almost quantitative yield.
(1) KMnO ,OH–

4 → PhCO H
PhCH3      2
heat
Benzoic acid
An important characteristic of side chain oxidations is that oxidation takes place initially at the benzylic
carbon. Alkyl benzenes with alkyl groups longer than methyl are ultimately degraded to benzoic acids.
(i) KMnO ,OH– / heat

4 
PhCH2CH2CH2R      → PhCO2H
(ii) H3 O+
An alkylbenzene Benzoic acid
Side chain oxidations are similar to benzylic halogenations, because in the first step the oxidizing agent
abstracts a benzylic hydrogen. Once oxidation has started at the benzylic carbon, it continues at that site.
Ultimately, the oxidising agent oxidizes the benzylic carbon to a carboxyl group and in the process; it cleaves
off the remaining carbon atoms of the side chain. In light of the proposed mechanism, tert butyl benzene must
be resistant to such kind of oxidation activity as it does not contain a benzylic hydrogen and this has been
found to be practically true also.
Side chain oxidation is not only restricted to alkyl groups but other groups in the side chain can also be
degraded to benzoic acid. Alkenyl, alkynyl and acyl groups are oxidized by hot alkaline potassium
permanganate in the same way.
C6H5CH=CHCH3
or O
KMnO4, OH–, heat
C6H5C≡CCH3 C6H5COH
H3O+
or
O
C6H5CCH2CH3
Some more applications are discussed below.

1. The substitution reaction of aromatic rings and the reactions of the side chains of alkyl and alkenyl
benzenes, when taken together, offer us a powerful set of reactions for organic synthesis. By using these
reactions skillfully, one will be able to synthesize a large number of benzene derivatives. Part of the skill
in planning a synthesis is in deciding the order in which reactions should be carried out. For example,
let us suppose that one wishes to synthesize o-bromonitrobenzene. One can see very quickly that the
bromine has to inserted into the ring first as it is an ortho-para director.
O-308
Br Br Br
NO2
Br2 HNO3
H2SO4
+
FeBr3
NO2
The ortho and para compounds obtained as products can be separated by various methods. However,
if one had introduced the nitro group first, one would have obtained m–bromonitrobenzene as the
major product.
2. Other examples in which choosing the proper order for the reactions are important are the syntheses of
the ortho, meta and para-nitrobenzoic acids. One can synthesize the ortho and para-nitrobenzoic acids
from toluene by nitrating it, then separating the ortho and para-nitrotoluenes, and then oxidizing the
methyl groups to carboxyl groups.
CH3 CO2H
KMnO4, OH–,heat
H3O+
CH3
NO2 NO2
HNO3 p–nitrotoluene p–nitrobenzoic acid
H2SO4
CH3 CO2H
NO2 NO2
KMnO4, OH–,heat
H3O+
o–nitrotoluene o–nitrobenzoic acid
One can synthesize m-nitrobenzoic acid by reversing the order of the reactions.
CH3 CO2H CO2H
(i) KMnO4,OH–,heat HNO3

(ii) H3O+ H2SO4,heat
NO2
Benzoic acid m–nitrobenzoic acid
Suppose one needs to synthesize m-chloroethylbenzene from benzene.
Cl
CH2CH3
O-309
One must begin by chlorinating benzene and then follow with a Friedel–Crafts alkylation using CH3CH2Cl
and AlCl3, or one could begin with a Freidel Crafts alkylation followed by chlorination. However, neither
method will give the desired product. The product obtained in both the cases is a mixture of ortho and para
chloro ethyl benzene. Actually, there is a three-step method that will work if the steps are done in the right
order. First of all, one will carry out Friedel Crafts acylation using CH3COCl + AlCl3 on benzene. This is
followed by chlorination reaction with Cl2 in presence of FeCl3, in which Cl + will enter at meta position.
Finally, the product is reduced by Zn–Hg and conc. HCl (Clemmenson reduction) to give the desired
product.
COCH3 COCH3 CH2CH3
CH3COCl Cl2/ FeCl3 Zn–Hg/HCl

AlCl3
Cl Cl
Very powerful activating groups such as amino groups and hydroxyl groups cause the benzene ring to be so
reactive that undesirable reaction may take place. Some reagents used for electrophilic substitution reactions,
such as nitric acid, are also strong oxidizing agents. Both electrophiles and oxidizing agents seek electrons.
Thus, amino groups and hydroxyl groups not only activate the ring towards electrophilic substitution, they
also activate it towards oxidation. For example, nitration of aniline results in considerable destruction of the
benzene ring because it is oxidized by the nitric acid. Consequently, direct nitration of aniline is not a
satisfactory method for the preparation of o- and p-nitroaniline. Treating aniline with acetyl chloride,
CH3COCl, or acetic anhydride, (CH3CO)2O, converts aniline to acetanilide. The amino group is converted to
an acetamido group (NHCOCH3), a group that is only moderately activating and one that does not make the
ring highly susceptible to oxidation. With acetanilide, direct nitration becomes possible.
NH2 NHCOCH3 NHCOCH3 NHCOCH3
NO2
CH3COCl HNO3
+
Base H2SO4
Aniline Acetanilide
NO2
p–nitroacetanilide o–nitroacetanilide
(trace)
(1) H+,H2O
(2) OH–
NH2
O
This step removes the
CH3CO group and +CH3COH
replaces it with an –H
NO2
p–nitroaniline
O-310
Nitration of acetanilide gives p-nitroacetanilide in excellent yield with only a trace of the ortho isomer. Acidic
hydrolysis gives p-nitroaniline, also in good yield. However, if one needs ortho-nitroaniline, then the
synthesis pathway discussed right now would not be a satisfactory method as only a trace of
o-nitroacetanilide is obtained. It is because the acetamido group is purely a para director due to steric
hindrance factor. However, one can synthesize o-nitroacetanilide through the reaction sequence below,
NHCOCH3 NHCOCH3 NHCOCH3 NH2
NO2 NO2
conc. HNO3 H2O
H2SO4 H2SO4, distill,OH–
Acetanilide SO3H SO3H o–nitroaniline
Here it can be observed that how a sulfonic acid group can be used as a "blocking group". One can remove
the sulfonic acid group by desulfonation at a later stage. In this example, the reagent used for desulfonation
(dilute H2SO4) also conveniently removes the acetyl group that is employed to "protect" the benzene ring
from oxidation by nitric acid.
5.6 Ortho - Para Ratio

An aromatic substitution reaction of a benzene derivative bearing an ortho, para-directing group would give
twice as much ortho as para product if substitution were completely random, because there are two ortho
positions and only one para position available for substitution. However, this situation is rarely observed in
practice. It is often found that the para substitution product is the major one in the reaction mixture. In some
cases this result can be explained by the spatial demands of the electrophile. For example, Friedel-Crafts
acylation of toluene gives essentially all para substitution product and almost no ortho product. The
electrophile cannot react at the ortho position without developing van der Waals repulsions with the methyl
group that is already on the ring. Consequently, reaction occurs at the para position, where such repulsions
cannot occur.
Typically, para substitution predominates over ortho substitution, but not always. For example, nitration of
toluene gives twice as much o-nitrotoluene as p-nitrotoluene. This result occurs because the nitration of
toluene at either the ortho or para position is so fast that it occurs on every encounter of the reagents; that is,
the energy barrier for the reaction is insignificant. Hence, the product distribution corresponds simply to the
relative probability of the reactions. Because the ratio of ortho and para positions is 2 :1, the product
distribution is 2 :1. In fact, the ready availability of o-nitrotoluene makes it is a good starting material for
certain other ortho-substituted benzene derivatives. In summary, the reasons for the ortho, para ratio vary
from case to case, and in some cases these reasons are not well understood.
Whatever the reasons for the ortho - para ratio, if an electrophilic aromatic substitution reaction yields a
mixture of ortho and para isomers, a problem of isomer separation arises that must be solved if the reaction is
to be useful. Usually, syntheses that give mixtures of isomers are avoided because, in many cases, isomers are
difficult to separate. However, the ortho and para isomers obtained in many electrophilic aromatic
substitution reactions have sufficiently different physical properties that they are readily separated. For
example, the boiling points of o- and p-nitrotoluene, 493 K and 510 K, respectively, are sufficiently different
that these isomers can be separated by careful fractional distillation. Thus, either isomer can be obtained
relatively pure° from the nitration of toluene. The melting points of o- and p-chloronitrobenzene, 34°C and
O-311
84°C, respectively, are so different that the para isomer can be selectively crystallized. Generally,the para
isomer of an ortho, para pair typically has the higher melting point, often considerably higher. Most aromatic
substitution reactions are so simple and inexpensive to run that when the separation of isomeric products is
not difficult, these reactions are useful for organic synthesis despite the product mixtures obtained.
Example 5: Give structure of the principal organic products expected from mononitration of
(i) o-nitrotoluene (ii) m-dibromobenzene
(iii) p-nitroacetanilide (iv) m-dinitrobenzene
(v) m-cresol (vi) o-cresol
(vii) p-cresol (viii)m-nitrotoluene
(xi) p-xylene (x) terephthalic acid (p-C6H4(COOH)2)
(xi) anilinium hydrogen sulphate (C6H5NH +3 HSO4–)
Solution :
(i) CH3 (ii) Br
NO2
Br
NO2 NO2
(iii) NHCOCH3 (iv) NO2
NO2
O2N NO2
NO2
(v) OH (vi) OH
CH3
CH3
NO2 NO2
(vii) OH (viii) OH
NO2 O2N
NO2
CH3
O-312
(ix) CH3 (x) CO2H
NO2
NO2
CH3 CO2H
(xi) NH+ –
3 HSO4
NO2
6. Fused or Condensed Aromatic Hydrocarbons

Fused aromatic hydrocarbons contain more than one ring and have two carbons shared by two or more
aromatic rings. The most important members of this class are naphthalene, anthracene,phenanthrene,
durene etc. Some of these are shown below,
•
• • •
• •
• • • • • •
• • • • • • • • • • • • •
• • • • • • • • • • •
• • • • • • • • • •
• • • • • • • • • • • • •
• • • • • • •
Naphthalene Anthracene Phenanthrene

Naphthalene has two carbon atoms shared by two rings. Anthracene and phenanthrene have two pairs of
carbon atoms shared by two rings, each pair being shared by a separate pair of rings.
6.1 Naphthalene
Naphthalene is the largest constituent of coal-tar. It is obtained industrially by chilling the middle oil fraction
(bp 170-230°C), when crude naphthalene crystallizes out. It is purified by washing it successively with dilute
sulfuric acid so that the basic impurities can be removed, sodium hydroxide to remove acidic impurities, and
water. Finally the solid is sublimed or steam-distilled to yield pure naphthalene. Naphthalene as moth balls
has been used to protect woolen goods from moths for many years. Recently, p-dichlorobenzene has
replaced naphthalene in the manufacture of moth balls, as it has a less obnoxious odor. It is used for
increasing the illuminating power of coal gas. Naphthalene is used in the manufacture of phthalic anhydride,
carbaryl for insecticides, 2-naphtol for dyes and several medicinal products.
O-313
6.2 Nomenclature of Naphthalene Derivatives

In naming derivatives of naphthalene, the numbering system shown below is used. The numbers selected to
denote the position of a substituent on the naphthalene rings should be as small as possible.
Br CH3
8 1
7 2
6 3
H3C
5 4
Naphthalene 1–Bromonaphthalene 1,6–Dimethylnaphthalene
An alternative nomenclature system is occasionally used when there is only one substituent on the
naphthalene skeleton. This system uses the Greek letters α and β to designate the two possible orientations of
the single substituent.
NO2
α α
Br
β β
β β
α α
Naphthalene α–Nitronapthalene β–Bromonapthalene
6.3 Structure of Naphthalene

All the ten carbon atoms in naphthalene are sp2 hybridized. The sp2 hybrid orbitals overlap with each other
and with s orbitals of the eight hydrogen atoms forming C - C and C - H σ bonds (figure 11). Since the σ
bonds result from the overlap of trigonal sp2 orbitals, all carbon and hydrogen atoms in naphthalene lie in one
plane. This has been confirmed by X-ray diffraction studies.
sp2–sp2
C–C H H sp2–sp2
σ bond C–C
σ bond
C C
H
H H
C C C
H H
≡ 120°
H H
C C C H H
H
H
C C
sp2–sp2
C–C
H H
σ bond
Fig. 11: Molecular orbital diagram of naphthalene

O-314
Also each carbon atom in naphthalene possesses an unhybridized p orbital containing one electron. These p
orbitals are perpendicular to the plane containing the σ bonds. The lateral overlap of the p orbitals produces
a π molecular orbital containing ten electrons as shown in figure 12. One half of this π molecular orbitals lies
above and the other half lies below the plane of the σ bonds. Naphthalene shows aromatic properties
because the resulting π molecular orbitals satisfies the Huckel's rule and for naphthalene n = 2 in (4n + 2) π
electron rule.
π–molecular
orbital
p–orbitals
p–p
overlap
Fig. 12: π overlap in naphthalene
A common shorthand representation of naphthalene is simply two fused hexagons with a circle inside each
hexagon. The circle represent the π molecular orbital.
π–molecular orbital
According to the resonance theory, naphthalene is considered to be a hybrid of the following three forms.
8 1
7 2
6 3
5 4
(A) (B) (C)
X-Ray diffraction studies show that, unlike benzene, all carbon-carbon bonds in naphthalene are not of the
same length. In particular, the C1 − C2 bond is considerably shorter (1.36 A) than the C1 − C2 bond (1.40
A°). This difference can be understood if one examines the three resonance forms given above. It is important
to note that the C1 − C2 bond is double in two structures (A and B) and single in only one (C); whereas the
C1 − C2 bond is single in two structures (A and B) and double in only one (C). One would, therefore, expect
the C1 − C2 bond to have more double-bond character (shorter bond length), and the C2 − C3 bond to have
more single-bond character (longer bond length). The resonance energy of naphthalene is about 61
kcal/mole. This value is less twice the amount of a single benzene ring (36 kcal/mole). As a result, naphthalene
is somewhat less aromatic (more reactive) than benzene.
O-315
6.4 Synthesis of Naphthalene

Naphthalene may be obtained:
1. From petroleum: When petroleum fractions are passed over copper catalyst at 680°C, naphthalene
and methylnaphthalenes are formed. Methylnaphthalenes are separated and converted into
naphthalene by heating with hydrogen under pressure (dealkylation).
CH3
Cu
Petroleum Fractions 680°C +
Naphthalene Methylnaphthalenes
H2, ∆, pressure
(–CH4)
Prior to 1960 all naphthalene came from coal-tar, but now almost half of it is produced from petroleum
by the above method.
2. Haworth synthesis: This involves the following steps :
Step 1: Benzene and succinic anhydride are heated in the presence of aluminium chloride to form
β-benzoylpropionic acid. (Friedel-Crafts Acylation).
O O
C C
H2C AlCl3 CH2
+ O
H2C CH2
C HO–C
O O
Benzene Succinic anhydride β–Benzoylpropionic acid
Step 2: β– Benzoylpropionic acid is treated with amalgamated zinc in the presence of hydrochloric acid to
give γ–phenylbutyric acid. (Clemmensen Reduction).
O
H2
C C
CH2 Zn(Hg) CH2
HCl
CH2 CH2
HO–C HO–C
O O
β–benzoylpropionic acid γ–phenylbutyric acid
Step 3: γ-Phenylbutyric acid is heated with concentrated sulfuric acid or polyphosphoric acid form
α-tetralone. (Ring closure Reaction).
O-316
H2
C
CH2
H2SO4
+ H2O
∆
CH2
H
HO–C
O
O
γ–phenylbutyric acid Tetralone
Step 4: α-tetralone is heated with amalgamated zinc and hydrochloric acid to give tetralin. (Clemmensen
Reduction).
Zn(Hg)
HCl
O
α–tetralone Tetralin
Step 5: tetralin is heated with palladium to yield naphthalene. (Aromatization reaction).
Pd + 2H2
Tetralin Naphthalene
Substituted naphthalenes can also be obtained by using toluene, bromobenzene, or anisole instead of
benzene in Step 1.
3.From 4-phenyl-3-butenoic acid: When 4-phenyl-3-butenoic acid is heated with concentrated sulfuric
acid, 1-naphthol is produced. 1-naphthol on distillation with zinc gives naphthalene.
H
C
CH
H2SO4 Rearrangement
+ H2O
(–H2O)
CH2
H H
HO–C
O OH
O
4–Phenyl–3–butenoic acid (Unstable) 1–Naphthol
Zn
∆ + ZnO
Naphthalene
O-317
4.From 4-Phenyl-1-butene: When 4-phenyl-1-butene is passed over red hot calcium oxide, naphthalene
is produced.
H2
C
CH2 CaO + H2
∆
CH
H2C Naphthalene
4–Phenyl–1–Butene
Physical properties of naphthalene

Naphthalene is a colorless crystalline solid. It melts at 82°C and boils at 218°C. Naphthalene is insoluble in
water, but dissolves in ether, benzene, and hot ethanol due to its non polar nature. It sublimes readily when
warmed and is volatile with steam. Naphthalene has a characteristics moth ball odor. Figure show UV and 1H
NMR spectra.
0.9
0.8
5000
0.7
0.6 4000
Absorbance
0.5
3000
0.4
0.3 2000
0.2
0.1 1000
230 240 250 260 270 280 290 300 310 320 330 340 350 360 nm
Fig.13: Ultraviolet spectrum of naphthalene shows a pattern typical of an

extended conjugated system with peaks at wavelengths as lon g as 320 nm
H H
H H
Intensity
Intensity
7.9
7.9 7.87.8
ppmPPM 7.6
7.6 7.5 7.4
7.4ppm
PPM H H
H
4H 4H
H H
TMS
TMS
10 9 8 7 6 5 4 3 2 1 0 ppm
Chemical shift (δ)
Fig. 14: HNMR spectrum of naphthalene, two symmetric multiplets can
be observed at δ=7.49 and 7.86 ppm, charcteristic of aromatic hydrogens
deshielded by the ring cur rent effect of the delocalized π electrons
O-318
Chemical properties of naphthalene

Some of the important chemical reactions of naphthalene are described below :
1. Electrophilic substitution reactions: Naphthalene, like benzene, undergoes electrophilic
substitution reactions. Substitution occurs primarily at C-1 (α-position). This can be understood if we
examine the intermediate carbonium ion. Two resonance forms can be written for the intermediate
carbonium ion obtained from the attack at C-1 (without involving the other ring), whereas only one
such form is possible for substitution at C-2. E+ in the following equations represents an electrophile.
Attack at C-1
E
1 H E H E
2 +
+E+ –H+
+
Naphthalene More stable 1–Substitution
product
Attack at C-2
1 +
H E
2
+E+ E –H+
Naphthalene Less stable 2–Substitution product
Consequently the former intermediate is more stable and the product with a substituent at C–1 predominates.
Substitution at C-2 (β-position) occurs only when the reactions are carried at higher temperatures or when
bulkier solvents are used.
(i) Sulfonation: Naphthalene undergoes sulfonation with concentrated sulfuric acid. If the reaction is
carried at 165°C, 2-naphthalenesulfonic acid is obtained.
SO3H
SO3H
H2SO4 H2SO4
60°C 60°C
1–naphthalene– 2–naphthalene–
Naphthalene
sulfonic acid sulfonic acid
(ii) Nitration: Naphthalene undergoes nitration with concentrated nitric acid in the presence of sulfuric acid
at 60°C to produce 1-nitronaphthalene.
O-319
• •
NO2 • • •
• •
H2SO4
• • • •
+HNO3
60°C • • • •
•
1–nitronaphthalene • •
Naphthalene • •
Mechanism
The mechanism of this reaction involves the following three steps:
Step 1: The electrophile NO 2+ is generated.
2H2SO 4 + HONO 2 → NO 2+ + 2HSO 4− + H3O +
Step 2: The electrophile attacks naphthalene at C-1 to form the resonance-stabilized carbonium
ion.Here,only those resonance forms are shown below which do not involve the other ring.
H NO2 H NO2
1
2 + +
+ NO2
Step 3: A hydrogen ion is eliminated to yield 1-nitronaphthalene.

– –
HSO4 HSO4
NO2
H NO2 H NO2
+
H2SO4
+
+
1–nitronapthalene
Similar steps may be written for other electrophilic substitution reactions of naphthalene.
(iii) Halogenation: Naphthalene undergoes chlorination or bormination in boiling carbon tetrachloride to

give 1-chloronaphthalene. Unlike benzene, no Lewis acid catalyst is required.
Cl
CCl4
+ Cl2 + HCl
∆
1–chloronaphthalene
Naphthalene
When this reaction is carried at room temperature, naphthalene dichloride (1,4-addition product) is
obtained. On heating, naphthalene dichloride loses HCl to yield 1-chloronaphthalene.
O-320
Cl
H Cl
CCl4
+ Cl2
Room –HCl
temperature
H Cl
Naphthalene Naphthalene dichloride 1–chloronaphthalene
(iv) Friedel-Crafts acylation: Naphthalene undergoes acylation with acetyl chloride and AlCl3 in carbon
disulfide to give 1-acetylnaphthalene. When nitrobenzene is used as a solvent, 2-acetylnaphthalene is
obtained.
O CH3
C O
O O
C–CH3
CH3–C–Cl, AlCl3 CH3–C–Cl, AlCl3
in CS2 in C6H5NO2
1–acetylnaphthalene naphthalene 2–acetylnaphthalene
(v) Friedel-Crafts alkylation: Naphtahelene undergoes alkylation with alkyl halides in the presence of
AlCl3 to give 2-alkylnaphthalene.
CH2CH3
AlCl3
+ CH3CH2Cl + HCl
Naphthalene 2–ethylnaphthalene
(vi) Chloromethylation: Naphthalene reacts with formaldehyde and HCl in the presence of zinc chloride
to form 1-chloromethylnaphthalene.
CH2Cl
O
ZnCl2
+ H—C—H + HCl
Naphthalene Formaldehyde 1–chloromethylnaphthalene
6.5 Other Reactions

1.Oxidation: Naphthalene is much more easily oxidized than benzene. With chromium trioxide in acetic
acid at room temperature, it gives 1,4-naphthaquinone.
O-321
CrO3
CH3COOH
O
Naphthalene 1,4–naphthaquinone
Oxidation of naphthalene with oxygen and vanadium pentoxide at 475°C yields phthalic anhydride. This
method is used industrially.
O
C COOH
Air, V2O5 H2O/H+
O
475°C
C COOH
O
Naphthalene Phthalic anhydride Phthalic acid
Phthalic acid is an important industrial material. It is used in the manufacture of resins paints, dyes and plastics.
2.Reduction: Naphthalene undergoes reduction more readily than benzene. With sodium and ethyl
alcohol (bp 78°C) it gives 1,4-dialin or 1,4-dihydronaphthalene. With sodium and isopentanol (bp 130°C) it
gives tetralin or 1,2,3,4-tetrahydronaphthalene.
Na/C5H11OH Na/C2H5OH
Boil Boil
Tetralin Naphthalene 1,4–dialin
Catalytic reduction completely hydrogenates both rings and produces decalin or decahydronaphthalene.
8 1
9
7 2
+ 5H2 Ni or Pt
∆, Pressure
6 3
10
5 4
Naphthalene Decalin
Decalin consists of two cyclohexane molecules (in chair forms) used together along a common side. It exists
in cis and trans isomeric forms which differ in the space relationship of hydrogen atoms at C-9 and C-10
positions. When nickel is used as a catalyst, the main product is trans-decalin. When platinum is used as a
catalyst, the main product is cis-decalin. Decalin sold commercially is the mixture of both these forms, and is
used as a solvent in the varnish and lacquer trade.
O-322
H H
H
trans–decalin cis–decalin
(bp 185°C) (bp 195°C)
7. Anthracene
Anthracene occurs in coal-tar and is obtained from the green oil fraction (boiling point 270-360°C). On
cooling this fraction crude anthracene crystallizes out. Crude anthracene contains phenanthrene and
carbazole as impurities. It is purified by washing it successively with solvent naphtha in order to remove
phenanthrene and pyridine to remove phenanthrene and pyridine to remove carbazole. Finally the solid is
sublimed to give pure anthracene. In naming derivatives of anthracene, the numbering system shown below
is used. The numbers selected to denote the position of a substitutent on the anthracene rings should be as
small as possible. Anthracene is used in the manufacture of anthraquinone.
Br SO3H
8 9 1
7 2
6 3
5 10 4
Anthracene 9–bromoanthracene 1–anthracenesulfonic acid
7.1 Structure of Anthracene

All 14 carbon atoms in anthracene are sp2 hybridized, so it is a
H H H
planar molecule. The sp2 hybrid orbitals overlap with each
other and with s orbitals of the ten hydrogen atoms forming C - H H
C and C - H σ bonds. Since the bonds result from the overlap of
trigonal sp2 orbitals, all carbon and hydrogen atoms in H
H
anthracene lie in the same plane (figure 13). This has been
H H H
confirmed by X-ray diffraction studies.
σ bonding framework in anthracene
Also each carbon atom in anthracene possesses an
unhybridized p orbitals containing one electron. These p orbitals are perpendicular to the plane of the σ
bonds. The lateral overlap of these p orbitals produces a π molecular orbital containing fourteen electrons
(figure 15). One half of this π molecular orbital lies above and the other half lies below the plane of the σ
bonds. Anthracene shows aromatic properties because the resulting molecular orbital satisfies the Huckel's
rule as n = 3 in (4n + 2) π electron.
O-323
π molecular
or
bital
Fig. 15: π molecular orbital diagram of anthracene
A common shorthand representation of anthracene is simply three linearly fused hexagons with a circle inside
each hexagon. The circles represent the molecular orbital.
π molecular orbital
According to the resonance theory, anthracene is considered to be a hybrid of the following canonical forms,
X-ray diffraction studies show that, like naphthalene, all carbon-carbon bonds in anthracene are not of the
same length. In particular, the C1 − C2 bond is considerably shorter (1.37 A°) than the C2 − C3 bond. (1.42
A°). This difference in bond lengths can be understood if we examine the four resonance forms given above.
Notice that the C1 − C2 bond is double in three structures (A, B and C) and single in only one (D); whereas
the C2 − C3 bond is single in three structures (A, B and C), and double in only one (D). We would, therefore,
expect the C1 − C2 bond to have more double-bond character (shorter bond length), and the C2 − C3 bond
to have more single-bond character characterized by longer bond length.The resonance energy of
anthracene is 84 kcal/mole. This averages to 28 kcal/mole per ring, which is substantially lower than that of
benzene (36 kcal/mole). As a result, anthracene is much less aromatic than benzene and behaves more like
an unsaturated aliphatic hydrocarbon.
7.2 Synthesis of Anthracene

Anthracene is obtained with the help of a number of reaction. Some of these reactions are discussed below,
1. By Haworth synthesis: This involves the treatment of benzene with phthalic anhydride in the
presence of aluminium chloride to form o-benzoylbenzoic acid. This is then heated with concentrated
sulfuric acid to give 9, 10-anthraquinone. Distillation of the anthraquinone with zinc dust yields
anthracene.
O-324
O O
C C
AlCl3 H2SO4
O+ (–H2O)
H
C C
OH
O O
Phthalic anhydride Benzene o–benzoylpropionic acid
Zn
Distil
O
9,10–anthraquinone Anthracene
2. By Friedel-Crafts reaction: Benzyl chloride reacts with itself to form 9,10-dihydroantheracene,

which readily loses two hydrogen atoms to yield anthracene.
H H
CH2–Cl H
AlCl3 –2H
+ (–2HCl)
H Cl–CH2
H H
Benzeyl chloride (2 molecules) 9,10–dihydroanthracene Anthracene
Anthracene may also be prepared by the Friedel-Crafts reaction between benzene and
1,1,2,2-tetrabromoethane (acetylene tetrabromide), or between benzene and dibromomethane.
H
Br–C–Br AlCl3
+ + (–4HBr)
Br–C–Br
H
Benzene Acetylene Benzene Anthracene
tetrabromide
H H
H H
C
Br Br AlCl3 –2H
+
BrBr (–4HBr)
C
H H H H
Dibromomethane
9,10–dihydroanthracene Anthracene
O-325
3. By Elbs reaction: The conversion of a diaryl ketone containing a methyl or methylene group ortho to
the carbonyl function is known as the Elbs Reaction. For example, when o-methylbenzophenone is
heated at 450°C, anthracene is formed.
O
C
450°C
+ H2O
CH3
o–methylbenzophenone Anthracene
4. By Diels-Alder reaction: This involves the reaction of 1,4-naphthaquinone with 1,3-butadiene. The
product of this reaction is oxidized with chromium trioxide in glacial acetic acied to form
9,10-anthraquinone. Distillation of anthraquinone with zinc dust yields anthracene.
O H2 O H
C
CH CrO3
+ CH3COOH
CH
O C O H
H2
1,4–naphthaquinone 1,3–butadiene Diels–Alder adduct
Zn
Distil
O
9,10–Anthraquinone Anthracene
Physical properties of anthracene

Anthracene is a colorless solid. It melts at 218°C and boils at 340°C. Anthracene is insoluble in water, but
dissolves in benzene. It shows a strong blue fluorsence when exposed to ultraviolet light. The fluorescent
property of anthracene on clothing, skin, money, etc., is not detected under ordinary light but easily noticed
when exposed to ultraviolet light.
Chemical properties of anthracene

Anthracene undergoes addition and electrophilic substitution reactions. These reactions preferentially occur
at the C-9 and C-10 positions. This can be understood if one examines the intermediate carbonium ions
obtained from attack at C-1, C-2 and C-9 (all other positions at equivalent to either 1 or 2 or 9 by symmetry).
E+ in the following equations represent an electrophile.
O-326
Attact at C-1
8 9 1 H E H E
7 2 +
+ E+
6 3
5 10 4 +
Anthracene
Attact at C-2
+
H
+ E+ E
Anthracene
Attact at C-9
H E
+ E+
+
Anthracene
Attack at C-9 yields a carbonium ion intermediate in which two benzene rings are retained; whereas attack at
C-1 or C-2 yields an intermediate in which a naphthalene system is retained. The former intermediate is more
stable and its formation favored because the resonance energy of two benzene rings (2 × 36 = 72 kcal)
exceeds that of naphthalene (61 kcal). This carbonium ion intermediate can lose a proton to give the
corresponding substitution product, or it can react with a nucleophile to form the 9,10-addition product. Nu :
in the following equations represents a nucleophile.
E
H E
+
–H
H + Substitution product
H E H E
+ Nu:–
+
H H Nu
Addition product
Substitution at C-1 or C-2 occurs only when the reaction is reversible as in the case of sulfonation. The main
chemical reactions of anthracene are described below:
1. Diels-Alder reaction: Anthracene undergoes a Diels-Alder reaction with maleic anhydride to yield
the corresponding adduct.
O-327
C
HC
+ O
HC
C O
O C
Anthracene Maleic anhydride HC
O
HC
C
O
Diels–Alder adduct
2. Reaction with halogens: Anthracene reacts with chlorine in carbon tetrachloride at room
temperature to give 9,10-dichloro-9,10-dihydroanthracene (an addition product). On heating, this
addition product loses a molecule of hydrogen chloride by 1,4-elimiantion to form 9-chloroanthracene
(a substitution product).
H Cl Cl
In CCl4 ∆
+ Cl2
(–HCl)
H Cl
Anthracene 9, 10–chloro–9,10– 9–chloroanthracene
dihydroanthracene
9-Chloroanthracene may also be obtained by chlorinating anthracene at 100°C, or by treating

anthracene with cupric chloride in CCl4. Bromine reacts similarly.
3. Friedel-Crafts acylation: Anthracene undergoes acylation with acetyl chloride and aluminium
chloride to form 9-acetylanthracene.
H3C O
C
O
AlCl3
+ CH3–C–Cl
Anthracene 9–acetylanthracene
4. Nitration: Anthracene undergoes nitration with concentrated nitric acid in acetic anhydride at room
temperature to yield a mixture of 9-nitroanthracene and 9,10-dinitroanthracene. The usual nitrating
mixture (HNO3 + H2SO4) is not used because it leads to the formation of 9,10-anthraquinone by
oxidation.
O-328
NO2 NO2
(CH3CO)2O
+ HNO3 +
∆
NO2
Anthracene 9–nitroanthracene 9,10–dinitroanthracene
5. Sulfonation: Anthracene undergoes sulfonation with concentrated sulfuric acid to yield a mixture of
1-anthracenesulfonic acid and 2-anthracenesulfonic acid. At lower temperatures 1-anthracenesulfonic
acid is the major product; whereas at higher tempertures 2-anthracenesulfonic acid is the major
product.
SO3H
SO3H
H2SO4
+
Anthracene 1–anthracenesulfonic acid 2–anthracenesulforic acid
6. Oxidation: Anthracene undergoes oxidation with sodium dichromate and sulfuric acid to form
9,10-anthraquinone. Other oxidizing agents like nitric acid and air in the presence of V2O5 also lead to
the formation of 9,10-anthraquinone.
O • • •
• • • • •
Na2Cr2O7 • • • •
H2SO4 • • • •
• • • • •
Anthracene O • • •
Anthraquinone
(9, 10–anthraquinone)
7. Reduction: Anthracene undergoes reduction with sodium and ethyl alcohol to form
9,10-dihydroanthracene.
H H
Na/C2H5OH
∆
H H
Anthracene 9,10–dihydroanthracene
Catalytic reduction using nickel at 225°C first gives 9,10-hydroanthracene, and on continued hydrogenation
this is converted into 1,2,3,4-tetrahydroanthracene and 1,2,3,4,5,6,7,8-octahydroanthracene. Notice that the
9,10-hydrogen atoms migrate to the neighboring ring.
9,10–dihydroanthracene 1,2,3,4–tetrahydroanthracene 1,2,3,4,5,6,7,8–Octa–

hydroanthracene
O-329
8. Reaction with Sodium: Anthracene reacts with metallic sodium in liquid ammonia to form a deep
blue 9,10-disodioanthracene.
H –
••
Liq. NH3 +
+ 2Na 2Na
••
–
H
Anthracene 9,10–dihydroanthracene
(Deep blue)
When the disodio-derivative is heated with an alkyl halide, it gives the corresponding
9,10-dialkylanthracene.
CH2CH3
H –
••
+ ∆
2Na + CH3CH2Cl
••
–
H
CH2CH3
9,10–disodioanthracene 9,10–diethylanthracene
8. Biphenyls
Biphenyl or phenylbenzene or 1,1'-biphenyl is an organic compound that forms colorless crystals. It has
a distinctively pleasant smell. Biphenyl is an aromatic hydrocarbon with a molecular formula (C6H5)2. It is
notable as a starting material for the production of polychlorinated biphenyls (PCBs), which were once
widely used as dielectric fluids and heat transfer agents.
Biphenyl is also an intermediate for the production of a host of other organic compounds such as emulsifiers,
optical brighteners and plastics. Biphenyl is insoluble in water, but soluble in typical organic solvents. The
biphenyl molecule consists of two connected phenyl rings. Biphenyl occurs naturally in coal tar, crude oil,
and natural gas and can be isolated from these sources via distillation.
8.1 Methods of Preparation of Biphenyl

Some important methods of preparation of biphenyls are discussed below,
1. Biphenyl is produced industrially as a byproduct of the dealkylation of toluene to produce benzene:
C6H5CH3 + C6H6 → C6H5-C6H5 + CH4
2. The other principal route is by the oxidative dehydrogenation of benzene:
2 C6H6 + 1/2 O2 → C6H5-C6H5 + H2O
3. Fittig reaction: It is an extension of Wurtz reaction and consists of heating an ethereal solution of
bromobenzene with metallic sodium.
O-330
–Br+2Na+Br– +2NaBr
4. Ulmann biaryl synthesis: Iodobenzene on heating with copper in a sealed tube forms biphenyl.
–I+2Cu+I– +2Cul
Chloro–or bromobenzene fails to undergo this coupling reaction unless some strong electron
withdrawing group (e.g. NO2) is present in the ortho or para position. In the laboratory, biphenyl can
also be synthesized by the treatment of PhMgBr with copper salts.
Chemical properties
Lacking functional groups, biphenyl is fairly non-reactive, which is the basis of its main application. Biphenyl
is mainly used as a heat transfer agent and as a eutectic mixture with
diphenylether. This mixture is stable to 400 °C. Biphenyl does H3C
undergo sulfonation followed by base hydrolysis produces CH3
p-hydroxybiphenyl and p,p'-dihydroxybiphenyl, which are useful
fungicides. In another substitution reactions, it undergoes
halogenation. As a general rule of thumb, chiral molecules must have
at least one chiral center-that is, a carbon that has four unique
substituents coming off of it. However, like most rules of thumb, there
are exceptions, and there are indeed examples of chiral molecules that OH
have no chiral centers, biphenyl's belong to that category. As discussed HO
earlier, biphenyls or in general bi-aryls are the compounds that have Fig. 16: A biphenyl that can be
separated into enantiomers
two aromatic rings joined by a single bond, can be chiral if they have
bulky groups in their ortho positions that provide a barrier to the single
bond free rotation.
These compounds are chiral because the steric bulk of the groups in the ortho positions provide a large
energy barrier to the free rotation around the carbon-carbon single bond, and the conformations are not
easily interconverted. Such stereoisomers that can be interconverted through a single bond rotation are
called atropisomers. Butane, for example, has conformations that are atropisomers; however, unlike the
biaryls, the barrier to rotation is so small that they are interconverted rapidly at room temperature, and they
are, for practical purposes, achiral.
H3C HO
CH3 CH3
OH OH
HO H3C
Fig. 17: Interconversion between the enantiomers of this biphenyl is extremely
slow at room temperature because of the high barrier to rotation.
O-331
Exercise
(iii) SbCl5
Long Answer Type Questions Cl ?
1. Write structures of the products A, B, C, D and E in
the following scheme.
O (iv)
N2O5
?
CH2CH2CH3 Cl2/FeCl3
(v) CH3
Cl
Na–Hg/HCl HNO3/H2SO4 +CH3-CH–CH2–Cl
(A) (B)
2. Given structures and names of the principal organic Anhydrous AlCl3

products expected from mononitration of ?
4. Give the major product obtained from the reaction
(i) m–dinitrobenzene
of each of the following compound with conc.
(ii) CH3
HNO3/conc. H2SO4
(i) NO2
OH ?
(iii) m–dibromobenzene COOH
(iv) NHCOCH3 CH3
(ii)
NO2 NO2
3. Complete the following sequence of reactions with
appropriate structures. (iii) Cl
(i) O
CH2–CH2–C–Cl ?
AlCl3
? Cl
(iv) OCH3
(ii) Ph H
?
C=C + Br2(Fe) ?
H CH3
Cl
O-332
(v) Cl 8. The ionization potential of cyclopropene is 9.95 volt

while that of cyclopentadiene is 9.27 V. Explain
9. Fill in the blanks with appropriate structures of
? reaction products in the following transformation.
2→ SOCl
O– HOOC – C6H4 – CH2 – C6H5  
anhydrous Zn − Hg
NO2 (G)  
→ (H)  
→ (I)
AlCl3 HCl
5. Give the structures of the principal products
10. Toluene reacts with bromine in the presence of light
expected from the ring monobromination of each of
to give benzyl bromide while in the presence of
the following compounds. In each case tell whether FeBr3 it gives p–bromotoluene. Give explanation
bromination will occur slower or faster than with for the above observations.
benzene itself.
11. What do you understand by aromaticity? State and
(i) Acetanilide (ii) Iodobenzene explain Huckel's rule.
or
(iii) Sec-butylbenzene (iv) N-methylaniline
(v) Ethylbenzoate (vi) acetophenone Explain the following mechanism of benzene :
(vii) Phenetole (C6H5-O-CH2CH3) (i) Sulphonation (ii) Nitration

[Bund. 2009; Agra 2009]
(viii) Diphenylmethane (C6H5CH2C6H5)
12. Explain the mechanism of Friedel Crafts alkylation
(ix) Benzonitrile (C6H5CN) and acylation both in benzene ring.
(x) Benzotrifluoride (C6H5CF3) [Bund. 2010; Agra 2008; Kanpur 2008,09,11]
(xi) Biphenyl (C6H5-C6H5) 13. Discuss the mechanism of chlorination in benzene.

Explain why chlorination takes place at ortho and
6. Propose the probable mechanism of following
para-positions in toluene and not at meta-position.
reactions. [Meerut 2008]
(i) O
•• O 14. What is meant by term orientation ? Discuss the di
••
NO2 and tri-substitution products of benzene.
N2O5
[Meerut 2008, 09, 11]
CH3CN
15. What do you understand by electrophilic
substiution reactions ? Discuss the mechanism of
NH2 NH2 nitration, sulphonation and Fredal-Crafts alkylation
(ii)
of benzene. [Meerut 2009,11,12]
16. Discuss the methods of preparation, properties and
Cons. HNO3
uses of benzene. [Meerut 2011]
+H2SO4
NO2 17. Describe the preparation and properties of
naphthalene. [Meerut 2011]
7. Identify the products in given reaction sequence: 18. Give preparation, properties and uses of toluene.
O [Meerut 2012]
19. Explain why nitration of phenol occurs at o- and
anhydrous
+ O p-posit ions whereas nitrobenzene gives
AlCl3
m-distributed product only. [Agra 2008]
O 20. How will you convert benzene into naphthalene ?
SOCl2 AlCl3/CS2 Explain its structure in detail explaining that in
Zn–Hg/HCl
(A) (B) (C) (D) naphthalene two benzene rings are fused at ortho
position. [Kanpur 2008]
O-333
21. Explain the following 26. (i) Write four methods for the prepartation
(i) Phenol is brominated easily than benzene. of chlorobenzene.
(ii) Nitration of toluene is easier than benzene. (ii) How will you prepare the following from
chlorobenzene?
(iii) Ortho and para products are formed in
substitution reaction of chlorine (a) Phenol
(iv) Formic acid is stronger than acetic acid. (b) Aniline
(v) Mehtylamine is stronger base than ammonia (c) Phenyl cyanide

(d) D.D.T [Kashi 2008]
(vi) Chlorine of methyl chloride is more reactive than
chlorine of chlorobenezne. [Kanpur 2008] 27. (i) Discuss molecular orbital structure of
22. How can ethyl benzene and styrene be benzene.
distinguished ? Give the products on the expected (ii) Give the mechanism of Friedel-Crafts
reaction of each of the following reagents with ethyl reaction.
benzene. Give equation : (iii) Write short notes on Brich reduction.
(i) Hot KMnO4 (aq) [Kashi 2010]
(ii) Bromine / Iron 28. (i) What is Huckel rule of aromaticity?

(iii) Br2 (hv) (ii) Write mechanism of the following
(iv) Conc. H NO3/H2SO4 [Kanpur 2009] (a) Friedel–Crafts reaction,
23. What is Haworth synthesis? How will you prepare (b) Birch reduction. [Kashi 2011]
the following from naphthalene? 29. How will you convert the following :
(i) Teralin (i) Benzene to biphenyl,
(ii) 1,4 Naphtha-quinone (ii) Phenylacetyene to acetophenone
(iii) α–naphthol (ii) Nitrobenzene to chlorobezene [Lko. 2008]
(vi) β −naphthol [Kanpur 2010]
30. (i) Why nitrobenzene is used as solvent
24. How will you obtain naphthalene from 4-phenyl instead of benzene for Friedel - Crafts
butylenes? Obtain the following compounds from alkylation of bromobenzene ? Explain.
the naphthalene : (ii) How will you synthesise the following from
(i) β −naphthol benzene or toluene ?
(ii) 1,4-napthaquinone (a) p – Br. C6H4 – CH2 – CI
(iii) β −naphthylamine (b) p – Br. C6H4 CH = CH2

(c) CH3
(iv) Benzene
(v) Phthalic acid [Kanpur 2011] C6H5 C OH
25. (i) Discuss the mechanism of halogenation CH3

[Lko. 2009]
and sulphonation of benzene.
31. (i) Discuss the mechanism of halogenation
(ii) Classify the following groups as activating or and sulphonation of benzene.
deactivating when attached to benzene.
(ii) Classify the following groups as activating or
[Kashi 2008]
deactivating when attached to benzene.
–NO2, –NH2, –Cl, –CH3,–COCH3
[Hazaribagh 2008]
O-334
32. (i) What are aromatic compounds? Discuss the 6. What is aromaticity? Explain with examples.
mechanism of the following reactions : [Agra 2008]
(a) Friedel Crafts reaction
7. How will you prepare the following compounds
(b) Nitration
from benzene ?
(ii) How is toluene prepared? Describe its (i) Benzaldehyde
important reactions. [Hazaribagh 2008] (ii) Acetophenone [Kanpur 2008]
33. (i) What is deactivating groups? Explain the
8. How can you explain that –NO2 group is meta
deactivating effect of NO2 group when it is
directing while –NH2 group is ortho and para
present in benzene ring.
directing? [Kanpur 2008]
(ii) What are the different isomers represented by
the molecular formula C7H7Cl? Write them. 9. How can you prepare the following from toluene
[Hazaribagh 2008] (i) T.N.T (ii) Xylene
34. (i) Explain orbital structure of benzene (iii) C6H5COOH [Kanpur 2008]
molecule.
(ii) Discuss Huckel's rule. 10. How you will get the following from napthalene
(iii) Starting from benzene how will you prepare : (i) Tetralin (ii) β–Napthol
[Kanpur 2009]
(a) Phenol
(b) Benzoic acid? [Hazaribagh 2010] 11. What happens when :
35. Write short notes on the following : (i) Naphthalene is heated with conc.H2SO4.
(i) Relative methods of orientation. (ii) Naphthalene is heated with O2 in the
(ii) Action of chlorine in toluene under different presence of V2O5. [Kanpur 2011]
conditions.
12. Explain the structure of benzene on the basis of
(iii) σ and π complexes.
molecular orbital theory and resonance theory.
(iv) –OH group in phenol is o- and p-directing. [Kanpur 2011]
[Hazaribagh 2011]
13. On the basis of σ − complex stability , explain why
Short Answer type Questions −NH3 ⊕ group is meta – directing group whereas -
1. Explain in detail why cyclopentadienyl anion is OCH3 group is ortho and para – directing group.
[Avadh 2008]
aromatic while cyclo octatetraene is not aromatic.
[Bund. 2008,09] 14. Discuss the mechanism of Friedel – Crafts reaction.
2. Discuss the mechanism of nitration of benzene. [Avadh 2008,09]
[Bund. 2008; Agra 2009] 15. Why phenol is more reactive than nitrobenzene for
3. What happens when toluene reacts with chlorine : electrophilic aromatic substitution reactions?
(Give reactions only) [Avadh 2009]
(i) At low temperature, in absence of light and 16. Give the mechanism of nitration of benzene.
in presence of Lewis acid. [Avadh 2010]
(ii) At high temperature, in presence of light and
absence of catalyst. [Bund. 2009] 17. Explain why -OH group is ortho, para director and
activator whereas -NO2 group is meta director and
4. Discuss the difference in reaction of benzyl chloride
deactivator for aromatic electrophilic substitution
and chlorobenzene. [Bund. 2009]
reaction. [Avadh 2010]
5. Give the preparation and uses of B.H.C. B.H.C is
obtained by heating benzene with chlorine in 18. Chlorine is ortho/para directing but still deactivating
presence of sunlight. Write the reaction. in nature. Why? [Lko. 2011]
[Meerut 2009; Agra 2009]
O-335
19. Identify the product A, B and C and name the type

, ,
of reaction involved in each step :
CH3COCl ⊕
(i)
AlCl3 [Bund. 2010]
Zn/Hg NBS 4. What happens when benzene is oxidized in
A B C
HCl presence of V2O5 ? [Meerut 2012]
CH3Cl
(ii) 5. Complete the following reaction :
AlCl3
3→ AlCl
C6H + CH3Cl   [Kanpur 2009]
Cl2/hν NH2SO4/HNO3
A B C
Alcl3 Alcl3 6. Write note on electrophilic reagent. [Kanpur 2009]
[Lko. 2011]
7. How can you convert toluene into benzoic acid?
20. (a) State Huckel rule of aromaticity and [Kanpur 2009]
explain it with two examples.
8. Convert: Benzene → Acetophenone.
(b) Why do o- and p- directing groups usually [Kanpur 2009]
activate the ring? [Rohd. 2011] 9. Which of the following groups activate or deactivate
21. Explain the directive influence of –NH2 and –NO2 benzene ring ? Explain.
groups on the basis of electron displacement. –NO2 ,−C2H5 ,−SO3H [Kanpur 2009]
[Rohd. 2011]
10. Convert
22. Prove that two benzene rings are fused in a
(i) Ethyl bromide into diethyl ether
naphthalene molecule in ortho positions.
[Rohd. 2012] (ii) Bromobenzene into benzoic acid
23. Describe mechanism of sulphonation of benzene. (iii) Benzene into Benzyl chloride
[Rohd. 2012]
(iv) Chlorobenzene into D.D.T [Kanpur 2009]
24. Explain ortho/para ratio. [Rohd. 2012]
11. Convert:Benzene into T.N.T. [Kanpur 2010]
25. Explain giving reason why NO2 and group is
12. Which group of the following two activates and
meta-directing and NH2 group is ortho and
deactivates the benzene ring?
para-directing. [Hazaribagh 2010]
-NO2 and -CH3. [Kanpur 2010]
26. Give the mechanism of electrophilic substitution in
benzene. [Hazaribagh 2010] 13. Explain why phenol is more easily brominated than
benzene. [Kanpur 2010]
27. Give the mechanism of sulphonation of benzene. In
what respect does it differ from nitration? 14. Explain that in naphtahlene two benzene rings are
[Hazaribagh 2011] fused at ortho positions. [Kanpur 2010]
15. How can you get the following?

(i) Benzoic acid from benzene.
1. Define and explain Huckel's rule.
[Bund. 2008; Meerut 2012; Kanpur 2011] (ii) Saccharine from toluene. [Kanpur 2011]
2. Benzene has three double bonds but it does not 16. Convert: Chlorobenzene into picric acid.
decolourise bromine water. Why? [Kanpur 2011]
[Bund. 2010]
3. Which among the followings are aromatic and why? 17. Give one example of Friedel - Crafts reaction.
Explain it. [Kashi 2008; Hazaribagh 2008,11]
O-336
18. What is Huckel' s rule of aromaticity ? [Kashi 2008] 2. The major product obtained when Br2/Fe is treated
with
19. Define aromaticity and state Huckel's rule.
[Kashi 2010] O
HN
20. Benzene is planar molecule and burns with a sooty
H3C CH3
flame. Why? [Lko. 2009]
21. Alkoxy group in benzene is ring activating though

oxygen is more electronegative. Why? [Lko. 2009]
22. Choose the correct answer then justify: The is

compound which will give only meta derivative on (a) O
HN
nitration
H3C CH3
(i) Anisole
(ii) Chlorobenzene
(iii) Nitrobenzene [Lko. 2009]
23. Explain acetylation of benzene in presence of Lewis

Br
acid. [Lko. 2010]
(b) O
24. Why nitrobenzene gives m-dinitro benzene on HN
nitration? [Lko. 2010] H3C CH3
25. Explain, why aniline does no undergo Friedel-
craft's reaction. [Lko. 2011]
26. Write a note on activating nature of NH2 group and

Br
deactivating nature of COOH group.
[Lko. 2011] (c) O
HN
27. State Huckel's rule of aromticity and explain it with
H3C CH3
two examples.
[Rohd. 2009; Hazaribagh 2008]
28. Why –NO2 group is meta directing group? Br

[Rohd. 2009]
(d) O
29. Benzene does not give deal Alder reaction. Explain. HN
[Rohd. 2013]
H3C CH3

Br
3. The compound that is most reactive towards
1. Among the following, the compound that can be electrophilic nitration is
most readily sulphonated is (a) Toluene (b) Benzene
(a) Benzene (c) Benzoic acid (d) Nitrobenzene
(b) Nitrobenzene 4. The reaction of toluene with chlorine in presence of
(c) Toluene ferric chloride gives predominantly
(d) Chlorobenzene (a) Benzoyl chloride
(b) M–chlorotoluene
O-337
(c) Benzyl chloride 8. Which of the following carbocations is expected to

(d) O– and p–chlorotoluene be most stable?
5. The correct product of mono nitration of (a) CH3
CH2–COO
+
NO2
is H Y
(a) (b) CH3

CH2–COO
+
(b)
CH2–COO
H Y
NO2 CH3
(c)
(c) +
NO2 CH2–COO
H
Y
(d) (d) CH3
CH2–COO NO2
H
6. When nitrobenzene is treated with Br2 in presence Y
of FeBr3, the major product formed is +
m–bromonitrobenzene. Statements which are
related to obtain the m–isomer are 9. A deactivating group
(a) The electron density on meta carbon is more (a) Deactivates only ortho and para positions
than that on ortho and para positions.
(b) Deactivates meta position
(b) The intermediate carbonium ion formed
(c) Deactivates ortho and para more than meta
after initial attack of Br+ at the meta position
is least destabilized (d) Deactivates meta more than o– & p–
(c) Loss of aromaticity when Br+
attacks at the 10. In aniline, the –NH2 group
ortho and para positions and not at meta (a) Activates the benzene ring via both inductive
position and resonance effects
(d) Easier loss of H + to regain aromaticity from
(b) Deactivates the benzene ring via both
the meta position than from ortho and para
inductive and resonance effects
positions
(c) Activates the benzene ring via resonance
7. An activating group
effect and deactivates it via inductive effect
(a) Activates only ortho and para positions
(d) Activates the benzene ring via inductive effect
(b) Deactivates meta position
and deactivates it via resonance effect
(c) Activates ortho and para more than meta
(d) Deactivates meta more than o– & p–
O-338
11. In the Friedel –Crafts acylation, the electrophile is (d) NO2

(a) C6H5+ (b) AlCl3−
(c) CH3CO+ (d) C6H5CH2+

H
12. The main reaction product when toluene is treated
+
with concentrated HNO3 in the presence of Y
concentrated H2SO4 is
15. Which of the following species is expected to have
(a) 2,4,6 –trinitrotoluene
maximum enthalpy in an electrophilic aromatic
(b) 2,4 –dinitrotoluene
substitution reaction?
(c) p–nitrotoluene
+
(d) m–nitrotoluene H Eδ H
13. In chlorobenzene, the –Cl group δ+
(a) Activates the benzene ring more via +E+ +
resonance effect than deactivating it via
inductive effect (I) (II) (III)
(b) Deactivates the benzene ring more via E
inductive effect than activating it via δ+H
resonance effect
δ+
(c) Activates the benzene ring via resonance
effect and deactivates it via inductive effect.
Both these effects are evenly matched.
(IV) (V)
(d) Is a net deactivating group with meta director
characteristics.
14. Which of the following carbocations is expected to (a) Species (II) (b) Species (III)
be most stable? (c) Species (IV) (d) Species (V)
(a) NO2
16. Which of the following sequence regarding the rate
+ of halogenation is correct ?
(a) Fluorination > chlorination > bromination
(b) Fluorination < chlorination < bromination
(c) Fluorination < chlorination > bromination
H Y (d) Fluorination > chlorination < bromination
(b) NO2
17. For the electrophilic substitution reaction involving
nitration, which of the following sequence regarding
the rate of reaction is true?
+
(a) KC H > KC D > KC T
6 6 6 6 6 6
(b) KC H < KC D < KC T
6 6 6 6 6 6
H Y (c) KC H = KC D = KC T
6 6 6 6 6 6
(d)K C H > K C D < K C T
(c) NO2 6 6 6 6 6 6
18. Which of the following statements made on
+ H nitration is/are false?
(a) Nitration of benzene is faster than
Y
ethylbenzene
(b) Nitration of benzene is slower than
C6H5NHCOCH3
O-339
(c) Nitration of benzene is faster than

22. What is the bond length between C-C in benzene
chlorobenzene.
(a) 1.54 A° (b) 1.34 A°
(d) Nitration of chlorobenzene gives
m–chloronitrobenzene (c) 1.39 A° (d) 1.21 A°
[Bund. 2009]
(e) Nitration of benzene is faster than
hexadeuterobenzene 23. Nitration of Benzene is
19. Which of the following statements made on
(a) Nucleophilic substitution
Friedel-Crafts reaction is/are false?
(b) Electrophilic substitution
(a) Friedel Crafts alkylation and acylation leads
to new carbon-carbon bond formation. (c) Nucleophilic addition
(b) Arylhalide/anhydrous AlCl3 combination can (d) Free radical substitution [Rohd. 2009,10]
be used as reagent for Friedel-Crafts alkylation.
24. The –COOH group in benzoic acid is
(c) When benzene and nitrobenzene, both liquids,
(a) Ortho directing
are mixed and treated with CH3COCl/AlCl3
(b) Meta directing
under proper reaction conditions the products
obtained after acidification are meta acetyl (c) Para directing
nitrobezene and acetophenone. (d) Ortho and Para directing [Rohd. 2009,10]
(d) n-propylbenzene can be made in good yield
25. The –CHO group in benzaldehyde is :
from benzene using n-propyl chloride and
anhydrous AlCl3 combination as reagent. (a) Ortho directing
20. (b) Meta directing
To transform into (c) Para directing

(d) Ortho and para directing [Rohd. 2010]
26. When chlorobenzene reacts with methyl chloride

, two initial steps could be and sodium metal in ethereal solution, gives
toluene. The reaction is called as :
O2N
(a) Wurtz reaction
(b) Friedel Craft reaction
(a) Nitration followed by Friedel - Crafts
(c) Wurtz-Fitting reaction
alkylation.
(d) Perkin's reaction [Rohd. 2011]
(b) Friedel - Crafts alkylation followed by
nitration. 28. The electrophile in aromatic nitration is
(c) Nitration followed by Friedel - Crafts (a) Nitronium ion
acylation.
(b) Nitrite ion
(d) Friedel - Crafts acylation followed by
(c) Nitrinium ion
Clemmensen's reduction followed by
nitration (d) Nitrate ion [Rohd. 2012]
21. -NH2 group is 29. In Friedel-Craft acylation the electrophile is

(a) o-directing (b) p-directing (a) CH3CO + (b) C6H5+
(c) o and p-directing (d)m-directing
(c) AlCl3 (d) CH3+
[Bund. 2008]
[Rohd. 2013]
O-340
Fill in the Blank True /False

1. If a ring is planar then it will be aromatic.
1. Benzene is ……… due to 6 π electrons.
2. Aromatic hydrocarbons are immiscible in water.
2. Benzene normally does not participate in ………... .
3. Mixture of concentrated nitric acid and
3. The effective electrophile in sulphonation of concentrated hydrochloric acid is termed as
benzene is ………. . nitrating mixture.
4. Acoording to Huckel's rule, for a ring to be aromatic
4. Cyclobutadiene is ………. .
it should have (4n+2) π electrons.
5. Cyclooctatetraene is ………. . 5. In halogenation of benzene using Cl2 along with

anhydrous AlCl3 as a catalyst, Cl2 is electrophile.
6. In the Friedel–Crafts acylation, the electrophile is
6. Reaction of benzene with 1- chloropropane in the
………. .
presence of anhyd. AlCl3 give n-propyl benzene.
7. Out of aniline and toluene, ……… is more reactive
7. In Friedal craft reactions, anhyd. AlCl3 is used as a
towards Friedel–Craft reaction.
catalyst.
8. Friedel–Crafts acylation consumes……… amount of 8. At high temperature, benzene on reaction with
Lewis acid catalyst than Friedel Crafts alkylation. hydrogen with nickel as catalyst undergo addition
reaction to give cyclohexane.
9. Out of p–xylene and toluene, p-xylene is ……… 9. Activating groups direct the upcoming electrophile
reactive towards nitronium ion. to meta position in benzene ring during
electrophillic substitution.
10. Out of naphthalene and anthracene ……… does
10. Benzene is the only aromatic ring in organic
not participate in Diels Alder reaction.
chemistry.
O-341
Answers
1. (c) 2. (a) 3. (a) 4. (d) 5. (d)
6. (a), (d) 7. (c) 8. (b) 9. (c) 10. (c)
11. (c) 12. (c) 13. (b) 14. (d) 15. (a)
16. (a) 17. (c) 18. (a),(d),(e) 19. (b,c,d) 20. (d)
21. (c) 22. (c) 23. (b) 24. (b) 25. (b)
26. (c) 27. (a) 28. (a) 29. (a)
Fill in the Blank

1. aromatic 2. electrophilic 3. SO3
4. antoaromatic 5. non aromatic 6. CH3CO +
7. toluene 8. more 9. more
10. naphthalene
True/False
1. False 2. True 3. False
4. True 5. False 6. False
10. False
Hints and Solutions

1.
O-342
Na Hg and HCl reduces the \/ C = O to \/ CH2 .

2. (i) NO2 (ii) OH (iii) Br (iv) NHCOCH3
NO2
NO2 NO2 CH3 Br
NO2 NO2 NO2
3. (i) (ii) CH=CH–CH3
Br
(iii) (iv) NO2 (v) H3C CH3
C
+ SbSl6–
CH3
4. (i) NO2 (ii) CH2
NO2
O2N COOH
NO2
(iii) Cl (iv) OCH3 (v) Cl
NO2 NO2
Cl
NO2 Cl NO2
5. (i) NHCOCH3 (ii) I
, faster , slower
Br Br
O-343
(iii) CH3 (iv) NH–Me

CH2CH3
CH
, faster
, faster
Br
Br
(v) O O–C2H5 (vi) O CH3

C C
, slower , slower
Br Br
(vii) OC2H5 (viii) CH2–C6H5
, faster , faster
Br Br
(ix) CN (x) CF3
, slower , slower
Br Br
(xi)
Br, faster
6. (i) CH2 CH3 CH2 CH3

CH2 O CH2 ⊕O
••
NO2–ONO2 NO2
–NO3– H
CH2 CH3 CH2 CH3

CH2 O CH2 O
••
NO2 ⊕ NO2
–H+ H
O-344
(ii) ⊕ ⊕
NH2 NH3 NH3 NH2
H+ NO+
2 OH –
NO2 NO2 NO2

7. (A): O O (B): CH2CH2CH2COOH
C–CH2–CH2–C–OH
(C): O (D):
CH2CH2CH2–C–Cl
8. Cyclopropene on ionization forms cyclopropene anion, which is an antiaromatic

compound. While ionization of cyclopentadiene leads to the formation of an aromatic species
cyclopentadiene anion, . So it is formed more easily.
It is why the energy required for the ionization i.e., ionization potential of cyclopropene is higher than
that of cyclopentadiene.
9. O O
C C
Cl
(G)= (H)=
CH2 CH2
CH2
(I)=
CH2
10. Side chain bromination is favoured under photochemical irradiation and involves a free radical
mechanism. In the presence of FeBr3, electrophilic substitution in the benzene ring occurs.
❍❍❍
UnitO-345
-IV
C HAPTER 7
Alkyl and Aryl Halide
1. Introduction
Organic halogen compounds are a large class of natural and synthetic chemicals that contain one or more
halogens (fluorine, chlorine, bromine, or iodine) combined with carbon and other elements. The simplest
organochlorine compound is chloromethane, also called methyl chloride (CH3Cl). Other simple
organohalogens include bromomethane (CH3Br), chloroform (CHCl3), and carbon tetrachloride (CCl 4 ).
There is an interesting aspect-if the halogen atom is directly attached to aliphatic hydrocarbon, the resultant
compound is alkyl halide. Similarly, if the halogen atom is directly attached to aromatic hydrocarbon, the
resultant compound is termed as aryl halide.
2. Alkyl Halides
Alkyl halides are the derivatives of alkanes which can be obtained by replacing one hydrogen atom by
halogen atom. The general formula of monohalogen derivative of alkanes is CnH2n+1X, here X is any halogen
atom. The monohalogen derivatives of alkanes are commonly called as alkyl halides.
2.1 Nomenclature and Classification of Alkyl Halides

Common names of alkyl halides are derived from the name of parent hydrocarbon.
CH3Br Br
CH3CH2Br
(methyl bromide) (ethyl bromide)
(n–propyl bromide)
Br Br
Br
(isopropyl bromide) (n–butyl bromide) (sec–butyl bromide)

O-346
Br Br
Br
(isobutyl bromide) (tert–butyl bromide) (n–pentyl bromide)
Br
Br
Br
(isopentyl bromide) (tert–pentyl bromide) (neopentyl bromide)
2.2 Classification
Alkyl halides are formally derived from alkanes by exchanging hydrogen for halogen atoms like fluorine,
chlorine, bromine, and iodine. Depending on the degree of substitution at the carbon atom carrying the
halogen, alkyl halides are classified into primary, secondary and tertiary alkyl halides.
R
R–CH2–X R–CH–R R–C–R
X X
Primary alkyl halide Secondary alkyl halide Tertiary alkyl halide
Fig. 1: Primary, secondary and tertiary alkyl halides
Vinyl halides are often classified as the fourth type of alkyl halides.
2.3 IUPAC Nomenclature

In the generally accepted nomenclature of alkyl halides, the name of the alkyl residue is followed by the
name of the halide, for example methyl iodide and ethyl chloride. However, the IUPAC nomenclature
considers an alkyl halide a substituted alkane, halogens are treated the same way as alkyl groups. An
example is shown here in which the IUPAC name is written in brackets in the illustration below.
CH3–Cl CH3–CH2–F
Methyl chloride Othyl fluorido
(chloromethane) (fluoro ethane) CH3
CH3–CH–CH3 CH3–CH2–CH–CH3 H3C–C–CH3
I Br Br
isopropyl iodide sec–butyl bromide tert–butyl bromide
(2–iodopropane) (2–bromobutane) (2–bromo–2–methylpropane)
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The name of the halogen is followed by the name of the alkane, for example, iodomethane and
chloromethane. If an alkyl halide contains more than one halogen, the halogen names are noted in
alphabetical order, such as 1-chloro-2-iodobutane. Some more names are,
CH3 CH3
Cl—CH2—C—CH3 C—I
H
H
1–chloro–2–methylpropane (1–odoethyl) cyclooctane
In the nomenclature of unsaturated alkyl halides, unsaturated bonds have a higher priority than halogen
substituents. This requires special attention when numbering the carbon chain.
CH3
H3C—C=CH—CH2—CH2—Cl
5–chloro–2–methylpent–2–ene
Some commonly used chlorinated organic solvents, such as carbon tetrachloride (tetrachloromethane),
chloroform (trichloromethane) and methylene chloride (dichloromethane), are known more by their trivial
name than by their IUPAC name. Hydrocarbons in which all hydrogens are replaced by halogens are
commonly named as perhaloalkanes or perhaloalkenes e.g., perfluoroethylene or 1,1,2,2 -tetrafluoroethene.
2.4 Isomerism in Haloalkanes

Isomerism in haloalkanes is primarily of two types one is chain isomerism and another is position isomerism.
In addition to these two types, haloalkanes always show optical isomerism when properly substituted.
1. Chain isomerism: Haloalkanes containing four or more carbon atoms exhibit chain isomerism in
which the isomers differ in the chain of carbon atoms. For example, C4H9Br has three chain isomers,
such as:
CH3
CH3 CH3–C–Br
CH3CH2CH2CHBr CH3–CH–CH2Br CH3
1–bromobutane 1–bromo–2–methylpropane 2–bromo–2–methylpropane
2. Position isomerism: Haloalkanes with three or more carbon atoms exhibit position isomerism in
which the isomers differ in the position of halogen atom. For example, C3H7I has two position isomers:
CH3CHCH3
CH3CH2CH2I
I
1–iodopropane 2–iodopropane
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Solved Examples
Example1: How many structural isomers are possible when C5H12 is subjected to
monobromination?
Solution: 8.
2.5 Methods of Preparation of Alkyl Halides

There are a number of methods available for the preparation of alkyl halides. This is an important category of
organic compounds and these can be prepared from alkanes, alkenes, alkynes, alcohols, aldehydes, ketones,
carboxylic acids etc. Some of the prominent methods are discussed below,
1. From alcohols: A variety of reagents can be applied to synthesize alkyl halides from alcohols. These
are discussed below,
(i) By using hydrogen halide

HX
R — OH  → RX + H2O
It must be noted that the HX used should be dry, which is produced, in situ, as follows
heat
2NaCl + H2SO4  → 2HCl↑ + Na2SO4
heat
2NaBr + H2SO4  → 2HBr↑ + Na2SO4
heat
6NaI + 2H3PO4  → 6HI↑ + 2Na3PO4
It may be noted that H3PO4 instead of H2SO4 is used to prepare HI. This is because HI is a reducing agent and
H2SO4 is an oxidising agent. The above substitution reactions proceed via SN1 and SN2 mechanism. Both the
above mechanisms are operative during reaction having competition among them.
Mechanism
H+ ⊕ –H O +X–
R–OH R–O–H S 21 R R–X+(Some rearranged product if possible)
N
H
X– SN2
R–X+H2O
Details about SN1 and SN2 will be discussed later in this capter
(ii) By using phosphorous halides: Both phosphorus pentahalides and trihalides when allowed to react
with alcohol yield alkyl halide as shown below,
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ROH + PCl5 → RCl + POCl3 + HCl
3ROH + PCl3 → 3RCl + H3PO3
3ROH + PBr3 → 3RBr + H3PO3
3ROH + PI3 → 3R–I + H3PO3
Phosphorous halides are prepared by treating red phosphorous and halogen. The merit of using
phosphorous halides is that free carbocation is not generated and so rearrangement does not take place.
(iii) By using SOCl2 (thionyl chloride)

Pyridine
R — OH + SOCl2  
→ R– Cl + SO2↑ + HCl↑
The reaction follows SN2 pathway. The usefulness of this method is that there is no side product which has to
be separated. It makes this reaction of converting an alcohol into alkyl halide as one of the better synthetic
pathways. The side products are gaseous SO2 which escape from the reaction mixture and HCl which forms a
salt with the base (pyridine) named pyridinium chloride (C 5H5N +Cl − ). In the absence of pyridine reaction
follows SN1 mechanism in which configuration of the alcohol is retained.
X
2. By direct halogenation of hydrocarbons: R—H  
2 → R—X + HX Reactivity of above reaction
hv
with respect to type of hydrogen to be replaced follows the order,
Tertiary hydrogen > Secondary hydrogen > Primary hydrogen
As far as the reactivity of halogen is concerned, F 2 is most reactive while I 2 is least reactive. In fact
reaction with I 2 is reversible and is carried out in the presence of some oxidising agents like HIO 3 ,
HNO 3 etc. to oxidise HI.HI is being scavenged by oxidising agents like HIO 3 , HNO 3 thereby inhibiting
the reversibility of the reaction and making it useful. Mechanisms of these reactions has been discussed
in the topic "alkanes".
3. By halide exchange: Alkyl iodides can be prepared from alkyl chlorides and alkyl bromides by
nucleophilic substitution. This can be achieved by treating them with NaI, using acetone as a solvent. It
is known as Finkelstein Reaction. Feasibility of this reaction is due to the solubility of NaI in acetone
and more nucleophilic character of I − ion. It follows SN2 mechanism.
NaI
R — Cl  → R — I + NaCl
Acetone
R − Br  → R − I + NaBr
NaI
Acetone
4. By addition of HX to alkenes: Generally alkyl halides like alkyl chlorides, bromides and iodides can
be prepared by treating an alkene with corresponding hydrogen halides (HCl, HBr and HI). The
addition of these compounds to alkene takes place according to Markovnikov's addition rule as
discussed earlier in the topic "alkenes". The reaction proceeds by electrophilic addition of H + to give
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more stable carbocation followed by attack of X − . Anti–Markovnikov addition of HBr can be achieved
if reaction is carried out in presence of peroxide like H2O 2 or benzoyl peroxide. This reaction
proceeds by the attack of bromine free radicals ( • Br). These mechanisms are schematically shown
below,
HX X−
CH 3 — CH = CH2  → CH 3 — CH — CH 3  → CH3 − C H − CH3
⊕ |
X
HBr HBr
CH 3 — CH = CH 2  → CH 3 — CH — CH 2 — Br  → CH 3 — CH 2 — CH 2 Br + Br•
Peroxide •
5. From silver salts of carboxylic acid: Even carboxylic acids can be directly converted to alkyl
halides by an appropriate choice of reagents as shown. Although the the reaction is limited to chlorine
and bromine only.
CCl
4 → RX + AgX + CO
RCOOAg + X 2  
 2
(X 2 = Cl 2 or Br 2 )
This reaction is popularly known as Hunsdieker reaction.
Mechanism
The mechanism is uncertain but probably in the first step acyl hypohalite is formed which subsequently
decomposes into free radicals.
RCOO 2 Ag + X2 → RCOOX + AgX
RCOOX → RCOO• + X•

RCOO• → R• + CO 2
R• + X 2 → RX + X•
R• + RCOOX → RX + RCOO• etc.
In Hunsdieker reaction, Br 2 in CCl4 gives better yield than Cl 2 in CCl4. The yield and ease of formation of R
— X is
1°RX > 2°RX > 3°RX
If I 2 is used in Hunsdieker reaction in CCl4, then an ester is formed. This is known as Birnbaum—Simonini
reaction.
O
||
2RCOOAg + I2 → R − C − Or + 2AgI + CO 2
6. Preparation of allylic or benzylic halides

(i) Direct halogenation of any aromatic hydrocarbon preferably gives benzylic halide. This is
because benzyl radical is resonance stabilized.
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CH2–CH3 X–CH–CH3
X2
hν
(ii) If an alkene is treated with halogen at high temperature or in presence of radiations or any
reagent which is able to provide halogen radicals in low concentrations, then allyl halides are
formed.
X•
CH3 — CH = CH2  
→ X — CH2 — CH = CH2
high temperature
CH3 — CH = CH2 + Cl2  → C H2 − CH = CH2
400 to 500 ° C |
Cl
NBS
CH3 — CH = CH2  → CH2 — CH = CH2
|
Br
SOCl
2 → CH − CH = CH
CH3 — CH = CH2   2 2
|
Cl
7. Preparation of polyhalides
(i) Addition of halogen to alkenes produces vicinal dihalides.
2 2 2 (X = Cl or Br )
CH2 = CH2 + X2   → CH2 − CH2
| |
Cl Cl
(ii) Addition of halogen (Cl2 or Br2) to alkynes produces tetra halo derivatives.
X X
| |
X2 X2
HC ≡ CH  
→ C H = C H  
→ H − C − C − H
| | | |
X X X X
Mechanism of addition of halogen to alkenes has been discussed in the topic "alkenes".
8. Preparation of vinyl halides

HCl
CH ≡ CH  → CH2 = CH
CuCl2 |
Cl
The above reaction proceeds via electrophilic addition. The mechanism of the reaction is discussed
below.
Mechanism
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2.6 Properties of the Alkyl Halides

The properties of alkyl halides can be of two types - one is physical properties like boiling point, density, water
solubilty etc. The second type is definitely the chemical reactivities shown by these compounds. These are
discussed below one by one.
Physical properties of the alkyl halides

1. Boiling point: Due to the presence of slight polarity in alkyl–halides as carbon halogen bond is polar
due to difference in electronegativities of the two atoms as well as greater molecular weights, alkyl
halides have considerably higher boiling points than alkanes containing same number of carbon
atoms. Branching leads to decrease in surface area due to which Van der Waals force decreases. So
boiling point of isomeric alkyl halides decreases with branching. For similar alkyl halides with different
halogen atoms, boiling point increases with molecular mass. Consequently, alkyl iodides have
maximum boiling point whereas alkyl fluorides have minimum boiling point. Boiling points of alkyl
fluorides are lower than those of hydrocarbons of comparable molecular weight. The difference is due
to the small size of fluorine, the tightness with which its electrons are held, and their particularly low
polarizability, so, 2-methylpropane has a bp =–1° whereas the bp of 2-fluoropropane is –11°C.
2. Water solubility: Alkyl halides are negligibly less soluble in water because of their inability to form
hydrogen bonds. However alkyl fluoride are comparatively more soluble in water. Their solubility
further decreases with increase in the size of alkyl group. They are soluble in typical organic solvents.
3. Density: The density of alkyl halides is more than that of alkane and decreases from alkyl iodides to
alkyl fluorides. Alkyl iodides and alkyl bromides are denser than water whereas monochloro alkanes
and monofluoroalkanes are lighter than water. More the number of halogen atoms more will be the
density if carbon skeleton remains same.
4. Dipole moment: Dipole moment of RX depends on:
(i) The sizes of the partial charges,
(ii) The distance between them, and
(iii) The polarizability of the unshared electrons on halogen.
As such, dipole moments of all the haloalkanes are comparable.
Example 2: Write a short note on the dipole moment of haloalkanes.
Solution :
l Electronegativities of the halides:
F > Cl > Br > I
l Bond lengths increase as the size of the halogen increases: H µ
+
C—F < C—Cl < C—Br < C—I C X
l Bond dipoles: H δ + δ–
C—Cl > C—F > C—Br > C—I H
1.56D 1.51D 1.48D 1.29D

l Molecular dipoles depend on the geometry of the molecule.
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Chemical properties of the alkyl halides

Carbon halogen bond in alkyl halide is polar owing to partial positive charge on carbon and partial negative
charge on halogen. Due to the positive charge on carbon, any nucleophile can attack the molecule and if it is
a stronger nucleophile than halide, it can substitute halide. So, nucleophilic substitution reactions are the
most common reactions of alkyl halides. Some of the prominent chemical reactivity of alkyl halide is
discussed below,
1. Preparation of Organometallic compounds
Alkyl halide on treatment with Mg metal in presence of dry ether yields Grignard reagent. Using the
same pathway these alkyl halides can be converted to alkyl lithium as shown below,
Mg
R — X  → RMgX
ether
(Grignard reagent)
Li
R — X 
→ R — Li + LiX
ether
(Organo lithium compound)
Mechanism
R — X + Li → [R — X] − + Li+
[R — X] − → R• + X−
R • + Li → R – Li
The extra electron in free radical anion occupies an antibonding molecular orbital. It must be noted that the
reactivity of alkyl halides to form organometallic compounds increases from alkyl fluorides to alkyl iodides.
Infact alkyl fluorides do not respond to the reaction and alkyl chloride and aryl halides give considerable yield
only if THF (Tetrahydrofuran) is used as a solvent. Further, more the stability of free radical, more will be
reactivity of alkyl halide to form organometallic compound. Alkyl organometallic compounds is a good
sources of carbanions (as carbon is more electronegative than the metals) and are very useful in organic
synthesis.
2. Reduction of alkyl halides
Reduction
R — X  → R — H
The reagents used for reduction of alkyl halide to alkane are Zn and CH3COOH, Zn and HCl, Zn and
NaOH, Zn — Cu couple and alcohol, aluminium amalgam and alcohol etc.
3. Wurtz reaction
ether
→ R — R
2R — X + Na  
Details about this reaction had already been discussed during preparation of alkanes.
4. Dehydrohalogenation of alkyl halides
alcoholic KOH
R — X  
→ Alkene
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alcoholic KOH
CH3 − CH − CH2 − CH3      → CH3 − CH = CH − CH3 + CH2 = CH − CH2CH3
|
X (major) (minor)
Details of this reaction had been discussed during preparation of "alkenes". A very important reaction
of alkyl halides i.e., Aliphatic nucleophilic substitution is dealt as a separately heading.
Example 3 : 36.4 g of 1,1,2,2– tetrachloropropane was heated with Zn dust and the product
was bubbled through ammonical AgNO 3 . What is the weight of the precipitate obtained? Give
equations for the reactions involved.
Solution :
Zn dust Ag O +
2
CHCl2 — CCl2CH3   → CH ≡ C — CH3    → AgC − ≡ CCH3
∆ Ammonical
AgNO3
∵ 182 g compound gives 147 g precipitate
147 × 36.4
∴ 36.4 g compound gives = 29.4 g
182
3. Aliphatic Nucleophilic Substitution

In nucleophilic substitutions, the attacking reagent which is a nucleophile brings an electron pair to the
substrate, which uses this pair to form a new bond and the leaving group comes away with an electron pair.
When nucleophile is a solvent, the reaction is called solvolysis.
R — X + Y → R — Y + X
Y is a nucleophile which may be neutral or negatively charged while RX may be neutral or positively charged.
R — I + HO − → R – OH + I −
+
R — I + NMe3 → R — N Me3 + I−
+
R — N Me3 + OH − → R — OH + NMe3
+ +
R — N Me3 + H2S → R — SH2 +NMe3
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aq. NaOH or KOH

R–OH+NaX or KX
or moist Ag2O
R'O–Na+
R–O–R'+NaX
KSH or NaSH
R–SH+Kx or NaX
R'S–Na+ R–S–R'+NaX
NH3
R–X RNH2+HX
R'NH2
R–NHR'+HX
R'2NH
R–NR'2+HX
AgCN/KCN
R–C≡N+R–N C+X–
–
C≡C—R'
R–C≡C–R'
I–,acetone
R–I+X–
NO2–
R–O–N=O+R–NO2+X–
–
CH (CO2Et)2
R–CH(CO2Et)2
Before going on for discussion of the mechanism of nucleophilic substitution reactions in alkyl halides, one
must have an idea about the few basic terms. These are mentioned below.
Basicity and nucleophilicity

Basicity is the tendency of a base of abstract H + and nucleophilicity is its tendency to attack as a nucleophile
on carbon. All the bases are nucleophiles and all the nucleophiles are bases.
3.1 S N 1Reaction
S N 1 stands for substitution nucleophilic unimolecular. The ideal version of S N 1 consists of two steps. The first
step is the slow ionization of the substrate and is rate determining step. The second step is the rapid reaction
between the carbocation and nucleophile. As the rate determining step involves only one molecule (it is alkyl
halide), so it becomes an unimolecular process.
RDS
R — X  → R + + X − Step 1 (slow)
+ −
R + Y → R — Y Step 2 (fast)
Moreover, the order of reaction is also equal to 1. So, the rate expression of the reaction is,
Rate = k1[RX];
k1 is rate constant of first order reaction.
The ionization is always assisted by solvent, since the energy of activation required for breaking of the bond is
largely recovered from solvation of ions produced. For example, ionization of t–BuCl in gas phase requires
about 150 kcal/mol but in water it requires only 20 kcal/mol. So, a polar solvent facilitates S N 1 reaction.
Moreover, in pure S N 1 reactions, solvent molecules assist the departure of leaving group from the front side.
As the reaction involves formation of carbocation, it is expected that only those alkyl halide par take in S N 1
mechanism which can yield a stable carbocation. The carbocation generated by first step has an sp2
hybridized carbon i.e. the structure is trigonal planar. Thus nucleophile will attack the carbocation from the
front side as well as from the rear side with equal ease, leading to the formation of two isomers, if the chiral
carbon is present in the substrate.
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3.2 Stereochemical Aspects of S N 1Mechanism

Let us understand the mechanistic details of S N 1 reaction in the following manner keeping the spatial
arrangement of groups in mind,
R'
C
–
R' R' OH R OH
front side R"
slow attack
C r.d.s. C+
–Br–
–
R Br OH R'
R R" front side
R"
attack
C
HO R
R"
Fig. 3: Stereochemical view of S N1 mechanism
A planar carbocation is formed during the slow rate determining step of the reaction, thus it may be expected
−
that the nucleophilic attack by OH (or solvent H2O) would occur from either side of the carbocation leading
to the formation of 50/50 mixture of substituted products having same and opposite configuration as that of
starting material. It means that the reaction is accompanied by racemisation leading to an optically inactive
(±) product.
However, in practice, the complete racemisation is never observed. It is always accompanied by some degree
of inversion. The relative proportion of the two depend on (a) the stability of carbocation (b) the ability of
solvent as nucleophile (c) the ionizing ability of the solvent and (d) the bulkiness of the groups on the
substrate. Till the formation of free carbocation, the nucleophile attacks from the rear side of the compound
leading to inverted product while once the carbocation is formed the probability of attack from both sides are
equally feasible. As a result, overall inverted product exceeds the retained product. So, it is a case of
racemisation with inversion of configuration. The energy profile of the reaction can be shown as,
⊕
δ δ
(CH3)3C---Cl
⊕
δ δ
(CH3)3C---OH
E2a
Potential energy
E1a (CH ) C
3 3
(CH3)3CCl
(CH3)3COH
Progress of the reaction
Fig. 4: Energy profile of SN1 reaction

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3.3 S N 2 Reaction Mechanism

S N 2 stands for substitution nucleophilic bimolecular. In this mechanism, there is a backside attack of the
nucleophile. The nucleophile approaches the substrate from a position 180° away from the leaving group.
The reaction is a one–step process with no intermediate. As both the molecules (alkyl halide as well as
nucleophile participates in the step) the molecularity of the reaction becomes two. Moreover, the order of
reaction is also equal to 2 as suggested by its rate law expression,
Rate =k2[RX][:Nu—]
k2 is rate constant of first order reaction.
In the mechanism below, the C — Y bond is formed as C — X bond is broken,
δ– δ–
Y– +C – X RDS [Y C X]# Y – C + X–
Transition state
Fig 5: SN2 mechanism
The energy necessary to break the C — X bond is supplied by the simultaneous formation of C — Y bond.
The position of atoms at the top of the curve of activation energy can be represented as transition state (TS).
The group X must leave as Y comes in, because at no time the carbon atom can have more than 8 electrons in
its outermost shell. In the transition state, the carbon is sp 2 hybridized. One lobe of unhybridised p orbital is
available for overlapping with an orbital of the incoming Nu − while the other lobe overlaps with an orbital of
the leaving group X − . These overlaps account for the partial bonds (shown by dotted lines) drawn in figure 5.
The reaction is initiated by Nu − beginning to overlap with the small lobe (tail) of the sp 3 hybrid orbital
bonding with X. In order to provide more bonding volume to give a stronger bond, the tail becomes the larger
lobe (head) and the head becomes the tail, inverting the configuration of carbon. The configuration of the
original compound is the opposite to that of the compound obtained. As Nu − starts to bond to carbon, it loses
some of its full charge and in the transition state has a δ − charge, as does X as it begins to leave as an anion.
The corresponding energy profile is shown below,
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In S N 2 mechanism, the front side attack has never been observed. In a hypothetical front side attack, both the
nucleophile and nucleofuge or leaving group would have to overlap with the same lobe of p–orbital whereas
the back side attack involves the maximum amount of overlap throughout the course of reaction. During the
transition state, the three non–reacting groups and the central carbon atom are approximately coplanar.
#
R R R
δ– δ–
–
Nu: C X Nu C Nu C + :X
H H
H D
D sp3 hybridized D
sp3 hybridized
sp3 hybridized
with p orbital R Configuration
S Configuration Transition State (Nu and X of same priority)
Fig. 7: Lobal arrangement of carbon in S N2 mechanism
In the above representation it is clear that the carbon atom is linked to five groups so it is highly overcrowded.
Due to high overcrowding it is easier to understand that bigger the groups attached to carbon, more unstable
will be the transition state. Hence steric factors will have important role in S N 2 substitution. Due to this reason
the reactivity towards S N 2 is as follows.
R H H H
R–C–X < R–C–X <R–C–X < R–C–X
R R H H
3.4 Stereochemistry of SN2 Reaction

S N 2 reaction is necessarily accompanied with inversion of configuration. Some of the examples are shown
below,
One more example is,
CH2CH3 CH2CH3
H3C CH3 –
C Cl HS C + Cl
HS
–
H H
Chiral center Chiral center
1 2
O-359
This behavior is also labeled as Walden inversion. It can be diagrammatically expressed as below. In the
presence of high speed wind an umbrella generally acquires an inverted configuration as below. It is
comparable to the inversion of configuration observed in case of organic molecules.
Fig. 8: A large invested umbrella due to high speed wind
S N 2 reactions are stereospecific because stereoisomeric reactants give stereochemically different

products. They are also stereoselective because they form exclusively or predominantly only one of a
possible pair of enantiomers or one of the possible diastereoisomers.
Example 4 : Which of the reactions (i) and (ii) would give a better yield of the desired ether
product?
(i) H3C X H3C
CH – O– +CH2CH3 CH – O – CH2CH3
1°
H3C H3C
(ii) H3C O– H3C

CH – X + CH 2CH3 CH – O – CH2CH3
2°
H3C H3C
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Solution : Both the reactions (i) and (ii) gives the same ether by S N 2 mode of substitution. In S N 2 reaction,
nucleophile can attack less hindered alkyl halide more effectively. Now, reaction (i) involves the attack on a
primary alkyl halide while reaction (ii) involves more hindered secondary alkyl halide. Hence, reaction (i)
would give a better yield while reaction (ii) is also accompanied by elimination.
Table 1: Comparative details of SN1 and SN2 reactions
SN 1 SN 2
(a) Number of steps 2 steps 1 step
slow + − − −
(i) R : L  → R + : L R : L + : Nu → R : Nu +: L
fast or
(ii) R + + : NuH  → R:Nu
−
+H+ R : L + : NuH → R : N + uH + : L
Here, L stands for leaving
group-halide ion(X–).
(b) Reaction rate & order Rate = k1[RL]; first order Rate =k2[RL][:Nu ]; second order
(c) Molecularity Unimolecular Bimolecular
+ +
(d) TS of slow step δ+ +
HNu: ……. C δ …….. δ L ……. Nu ….. C …. :L δ (with : Nu– )
HNu: δ+ +
HNu…….C…….:L δ (with
:HNu)
(e)Stereochemistry Inversion and retention Inversion
(Racemisation + inversion)
+
(f) Reacting nucleophile Nucleophilic solvent; stable R may Added nucleophile
react with added nucleophile
(g) Structure of R 3° > 2° > 1° > Me Me > 1° > 2° > 3°

(h) Nature of Leaving Weakest base is best leaving group, Weakest base is best leaving group,
group i.e.. i.e., I − > Br − > Cl − > F −
I − > Br − > Cl − > F −
(i) Solvent effect Rate α H–bonding ability and Depends on charge type.Polar
dielectric constant aprotic solvents leaves "freest" most
reactive Nu.
+
(j) Determining factor Stability of R Steric hindrance
(k) Rearrangement Observed Not observed, except for allylic
(l) Catalysis Lewis and Bronsted acids: No specific catalyst

Ag , AlCl3 and strong HA
+
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The energy profile of the two reactions can be compared as below,
First step in the RDS for [S N1]
[SN2]
[SN1]
⊕
Free energy
C L
⊕
C=L
+ –
– C–Nu + L
Nu
Progress of the reaction
Fig. 9: Comparision of energy profiles of SN1 and SN2 reactions
Example 5: C2H5O–
CH3
SN2
CH3 – C – CH2Br
C2H5OH
CH3
SN1
Identify the products of both reactions.
Solution : In SN2 reaction, the rate determining step involves the simultaneous bond making and bond
breaking through a transition state. Hence there is no scope of rearrangment and the product in neopentyl
ethyl ether.
SN1 reaction involves the formation carbonium ion in the rate determining step. It can undergo
rearrangement for better stability as follows.
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Hence, the rearranged product will be obtained.Since the carbonium ion is sterically hindered, elimination
will occur at a faster rate than the nucleophile attack by C2H5OH. So the alkene will be the major product.
Example 6: When CH3 — CH = CH — CH2Cl reacts with alcoholic KCN, a mixture of isomeric
products is obtained. Explain.
Solution : It can undergo both SN1 and SN2 reaction. By SN2 reaction only one product is formed. But by
SN1 reaction, intermediate is carbonium ion, which may lead to rearrangment for better stability.
CH3
CH
CH
SN2 δ–
CH3–CH=CH–CH2Cl+CN– Cl C δ–CN
slow
H H
slow SN1
Transition state
fast
⊕
CH3–CH=CH–CH2 CH3–CH–CH=CH2 CH3–CH=CH–CH2CN
⊕
(A)
CN– CN– 2°Carbonium ion
(more stable)
CH3–CH=CH–CH2CN CH3–CH–CH=CH2
(A) (minor) (B) (major)
Cn
Thus we get two isomeric products using SN1 reaction.
3.5 Ambident Nucleophiles

Some nucleophiles have lone pair of electrons on more than one atom and can attack through more than one
site. Such nucleophiles are called ambident nucleophiles. In such cases different products due to attack by
different sites are possible. Attack by a specific site can be promoted under special conditions. Two well
known examples are discussed in detail.
Case 1:Attack by CN − nucleophile (: − C ≡ N :)
CN −
R — X  → R – CN + R – NC + X −
Nitriles Isonitriles
In CN − , carbon atom, which is negatively charged, will be a soft base as compared to nitrogen which is a hard
base. So if the reaction proceeds via SN1 mechanism, it produces a free carbocation which is a hard acid. It is
very natural that attack takes place exclusively through nitrogen, the hard base. But if the reaction proceeds
via SN2 mechanism which yields small positively charged carbon which is a soft acid then attack takes place
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through carbon atom which is the soft base. So if one wishes to increase the relative yield of nitriles, use of
NaCN or KCN etc in a less polar solvent is prescribed because these conditions facilitates SN2 substitution.
Similarly if one wishes to increase the yield of isonitrile, use of AgCN is prescribed. Ag+ has very high affinity
+
for X − so it favours the formation of R and the reaction proceeds via SN1 mechanism. This will result in
attack by hard base giving R – NC. Further if one compares primary, secondary and tertiary alkyl halides,
formation of R – NC should be favoured due to more favourable SN1 substitution in tertiary alkyl halide.
Case 2: Attack by NO 2− nucleophile ( − O– N = O)
NO−
2 → R – O – N = O +
R – X  R – NO2 + X −
Alkane nitrite Nitro alkane
In NO 2− , oxygen atom, which is negatively charged, will be a hard base as compared to nitrogen. So if the
reaction proceeds via SN1 mechanism, then attack through oxygen atom (hard base) will take place yielding
alkane nitrite. But if the reaction takes place via SN2 mechanism then attack takes place through nitrogen (soft
base) to yield nitro alkane.
If we want to increase the yield of nitro alkane the reaction should proceed via SN2 mechanism. i.e. we can
use NaNO2, KNO2 etc. Moreover the yield will be best if we use primary alkyl halide and less polar solvent.
Formation of nitrite will dominate if we use tertiary alkyl halide, more polar solvent and AgNO2 because Ag+
has strong affinity for X − and can form a carbocation to force the reaction to proceed via SN1 mechanism.
Primary alkyl halide with AgNO2 chiefly gives nitroalkane but if secondary and tertiary alkyl halides are used
then AgNO2 will yield nitrite as the major product.
Table 2: Comparative details of E2 and SN2 reactions
Factor Favors E2 Favour SN2
(1)Alkyl group 3° > 2° > 1° 1° > 2° > 3°
(2)Leaving group I − > Br − > Cl − > F − I − > Br − > Cl − > F −
(3)Reagent Strong, bulky Bronsted base Strong nucleophile

(4)Solvent Favored Slightly favored
(i) Low polarity Disfavored Disfavored
(ii) Protic Polar Strongly favored Favored
(iii) Aprotic polar
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Table 3: Comparative details of E2 and SN1 reactions
Factor Favors E2 Favors SN1
(1) R group 3° > 2° > 1° 3° > 2° > 1°

(2) X I − > Br − > Cl − > F − I − > Br − > Cl − > F −
(3)Base Strong and High Very weak and low

(i) Strength and
(ii) Concentration
Example 7: Give the major product (with proper explanation) when following halogen
compounds are treated with sodium ethoxide?
(i) CH3–CH–CHCH3 (ii) (iii) CH2Br

Br CH3 CH3 CH3
Cl
Solution : (i)
Since sodium ethoxide is a strong base, it has a tendency to abstract proton to give alkene rather than a
nucleophilic attack.
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(ii) H
CH3 slow CH3
⊕
Cl
2° carbonium ion (A)
+
–H
H
1, 2 hydride shift
CH3
⊕
CH3
⊕
3° carbonium ion (A)
CH3 C2H5O–
OC2H5
CH3
⊕ (minor)
(major)
(iii) CH2Br
⊕
CH2 1,2 methyl shift CH2CH3
slow
⊕
CH3 CH3
H H
1° carbonium ion 3° carbonium ion (more stable)
∼ ring expansion –H+

⊕
⊕ CH2CH3
CH3 (minor)
–H+
CH3
Example 8: (i) Give the product from the reaction of Mg/Et2O with (a) BrCH2CH2Br,
(b) BrCH2CH2CH2Br and (c) BrCH2CH2CH2CH2Br.
(ii) Discuss the difference in behavior of (b) and (c) in part (i).
(iii) Give the product of the reaction of CBr4 + MeLi + cyclohexene.
Solution : (i) (a) H2C = CH2 (elimination of vic X's), (b) cyclopropane, (c) BrMg(CH2)4MgBr
(ii) (a) Unlike compound (b), compound (c) does not react intramolecularly because a 4
–membered ring does not form as readily as does a 3–membered ring.
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(iii) halogen metal

CBr4 + MeLi     → [Br3CLi] + MeBr,
exchange
Br3CLi → Br2C: + LiBr

Dibromocarbene
The carbene then adds to the alkene in the typical fashion giving
Br
Br
7, 7–dibromo [4.1.0]–bicycloheptane
Example 9 : Give the organic products of the following reactions

•O•
(i) • •
–
• •
• •
n–PrBr+••N–O ••
i–PrBr+[••SC ≡ N••–] (isocyanate)

• •
• •
(ii)
• ••
(iii) EtBr+[••SSO3]2–(thiosulfate)
•
(iv) ClCH2CH2CH2I + CN − (One mole each) →
(v) − H+
H2NCH2CH2CH2CH2Br   →
∆
Solution : The nucleophiles in (i), (ii) and (iii) are ambident since they each have more than one reactive
site. In each case, the more nucleophilic atom reacts even though the other atom may bear a more negative
charge.
−
(i) n–PrNO2 (ii) i–PrSCN (iii) [EtSSO3] (with its cation it is called a Bunte salt).
(iv) ClCH2CH2CH2CN. I − is a better leaving group than Cl − .
(v) When the nucleophilic and leaving groups are part of the same molecule, an
intramolecular displacement occurs if a three, a five– or a six–membered ring can
N form.
H
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4. Polyhalogen Compounds
Polyhalogenated compounds are organic compounds with multiple substitutions of halogens - F, Cl. Br and I.
They are of particular interest and importance because halogens are highly reactive and comprise a superset
of which has many toxic and carcinogenic industrial chemicals as members. They are generally non-miscible
in organic solvents or water, but miscible in some hydrocarbons from which they often derive. PHCs are
highly useful in a vast array of manufactured products, from wood treatments, to cookware coatings, to
non-stick, waterproof, and fire-resistant coatings, cosmetics, medicine, electronic fluids, food containers and
wrappings, in everything from furniture and furnishings. Two representative examples are chloroform and
carbon tetra chloride discussed below one by one.
4.1 Chloroform
Chloroform is an organic compound with formula CHCl 3 . It is one of the four chloromethanes yielded post
chlorination of methane. The colorless, sweet-smelling, dense liquid is a trihalomethane, and is considered
hazardous. Now a days, its use for refrigerants is being phased out. Chloroform volatilizes readily from soil
and surface water and undergoes degradation in air to produce phosgene, dichloromethane, CO, carbon
dioxide, and hydrogen chloride. In chloroform carbon atom is sp3 hybridised and the tetrahedral structure of
the compound is shown below,
H
C
Cl Cl
Cl
In industry, chloroform is produced by heating a mixture of chlorine and either chloromethane or methane.
At 400-500°C, a free radical halogenation occurs, converting these precursors to progressively more
chlorinated compounds:
CH4 + Cl2 → CH3Cl + HCl
CH3Cl + Cl2 → CH2Cl2 + HCl
CH2Cl2 + Cl2 → CHCl3 + HCl
Chloroform undergoes further chlorination to yield CCl4 as shown below,
CHCl3 + Cl2 → CCl4 + HCl
Uses
1. The major use of chloroform today is in the production of the chlorodifluoromethane, a major
precursor to tetrafluoroethylene:
CHCl3 + 2 HF → CHClF2 + 2 HCl

The reaction is conducted in the presence of a catalytic amount of antimony pentafluoride.
Chlorodifluoromethane is then converted into tetrafluoroethylene, the main precursor to teflon.
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2. Chloroform is also used as a solvent for fats, oils, rubber, alkaloids, waxes, gutta-percha, and resins, as
a cleansing agent, grain fumigant, in fire extinguishers, and in the rubber industry. CDCl 3 is a common
solvent used in NMR spectroscopy.
3. As a reagent, chloroform serves as a source of the dichlorocarbene CCl 2 group. It reacts with aqueous
sodium hydroxide usually in the presence of a phase transfer catalyst to produce dichlorocarbene,
CCl 2 ,a potent electrophile. This reagent affects ortho-formylation of activated aromatic rings such as
phenols, producing aryl aldehydes in a reaction known as the Reimer-Tiemann reaction. Alternatively
the carbene can be trapped by an alkene to form a cyclopropane derivative. In the Kharasch addition
chloroform forms the CHCl2 free radical in addition to alkenes.
4. Chloroform was once a widely used anesthetic. however, it was quickly abandoned in favor of ether
upon discovery of its toxicity, especially its tendency to cause fatal cardiac arrhythmia analogous to
what is now termed "sudden sniffer's death".
4.2 Haloform Test

Haloform reaction is a characteristic test reaction shown by all methyl ketones. The schematic diagram of the
reaction is shown here,
O
+ 3I2 + 4NaOH
R CH3
O
+ 3NaI + 3H2O + CHI3 (s)
R O– Na+
Among aldehydes ethanol is a rare aldehyde to respond to haloform reaction. CH3COR are readily oxidsed
by NaOX (NaOH + X2) to haloform, CHX3, and RCO2Na. Even alcohols having CH3CH(OH)- functionality
respond positively to haloform test. For example,
C2H5–C–CH3+3NaOI C2H5CO2– Na+ + CHI3+2OH–

Iodoform yellow;
O mp. 119°
KOCl H2SO4
(CH3)2C=CH–C–CH3 60°C (CH3)2C=CHCO2K (CH3)2C=CHCO2H
+ 3–Methyl–2–butenoic acid
O CHCl3
Example 10 : Which of the following compounds does not give haloform test?
(i) CH3CH2COCH3 (ii) CH3OH
(iii) CH3CHO (iv) PhCOCH3
Solution : CH3OH will not respond to haloform test as it is devoid of CH3CO– or CH3CH(OH)– structural
unit.
∴ (ii)
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Mechanis
As stated earlier, methyl ketones are characterized through the haloform test. The mechanism of haloform
test is shown below,
O O
–
+ OH + H2O
Ph CH2 Ph CH2
–
H Br Br
O O
+ H2O + Br
Ph CHBr – Ph CHBr
– OH
H
Br Br
O O
–
Br + – + H2O
Ph CBr2 OH Ph CBr2
–
H
Br Br
•• O
CBr3
••
O
+ Br –
••
•• –
Ph OH OH Ph CBr3
••
O O
–
+ CBr3 – + H CBr3
Ph O H Ph O
4.3 Carbon Tetrachloride

Carbon tetrachloride, also known by many other names like tetrachloromethane (IUPAC name), is the
inorganic compound with the chemical formula CCl 4 . It was formerly widely used in fire extinguishers, as a
precursor to refrigerants, and as a cleaning agent. It is a colourless liquid with a "sweet" smell that can be
detected at low levels.
Method of Preparation
1. Carbon tetrachloride was originally synthesized by the French chemist Henri Victor Regnault in 1839
by the reaction of chloroform with chlorine, but now it is mainly produced from methane:
CH4 + 4 Cl2 → CCl4 + 4 HCl
2. The production often utilizes by-products of other chlorination reactions, such as from the syntheses of
dichloromethane and chloroform. Higher chlorocarbons are also subjected to "chlorinolysis:"
C2Cl6 + Cl2 → 2 CCl4
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3. Prior to the 1950s, carbon tetrachloride was manufactured by the chlorination of carbon disulfide at
105 to 130 °C:
CS2 + 3Cl2 → CCl4 + S2Cl2
The production of carbon tetrachloride has steeply declined since the 1980s due to environmental
concerns.
Structure
In the carbon tetrachloride molecule, four chlorine atoms are positioned symmetrically as corners in a
tetrahedral configuration joined to a central carbon atom by single covalent bonds.
Cl
C
Cl
Cl
Cl
Due to this symmetrical geometry, CCl4 is non-polar. Methane gas has the same structure, making carbon
tetrachloride a halomethane.
Uses
1. As a solvent, it is well suited to dissolving other non-polar compounds, fats, and oils. It can also dissolve
iodine. It is somewhat volatile, giving off vapors with a smell characteristic of other chlorinated
solvents.
2. Historically, carbon tetrachloride was used as a pesticide to kill insects in stored grain, but in 1970 it
was banned in consumer products in different countries.
3. Carbon tetrachloride has practically no flammability at lower temperatures. Under high temperatures
in air, it forms poisonous phosgene.
4. As it has no C-H bonds, carbon tetrachloride does not easily undergo free-radical reactions. Hence, it is
a useful solvent for halogenations either by the elemental halogen or by a halogenation reagent such as
N-bromosuccinimide (these conditions are known as Wohl-Ziegler bromination).
5. It is sometimes useful as a solvent for infrared spectroscopy, because there are no significant absorption
bands > 1600 cm–1.
6. As carbon tetrachloride does not have any hydrogen atoms, it was historically used in proton NMR
spectroscopy. However, carbon tetrachloride is toxic, and its dissolving power is low. Its use has been
largely superseded by deuterated solvents.
5. Aryl Halides
Aryl halides are compounds containing halogen attached directly to an aromatic ring. The general formula of
aryl halides is ArX, where Ar is phenyl, substituted phenyl or any aryl groups. Some of the frequently
observed aryl halides are shown below,
Cl I Br
NO2
Chlorobenzene Iodobenzene m–bromonitrobenzene
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Cl CO2H
Br
NO2
p–chloronitrobenzene o–bromobenzoic acid
Example11: Draw the structures of bromobenzene, fluorobenzene and 2,4-dichloromethyl

benzene.
Solution: Br F CH3
Cl
Cl
Bromobenzene Fluorobenzene 2,4–dichloromethylbenzene
(2,4–dichlorotoluene)
An aryl halide is not just any halogen compound containing an aromatic ring. For example, benzyl chloride is
not an aryl halide, because halogen is not directly attached to the aromatic ring. Its structure and properties
resemble substituted alkyl halide. The aryl halides differ a lot from alkyl halides in their preparation and
properties. Aryl halides are comparatively unreactive towards the nucleophilic substitution reactions, which
are characteristics of the alkyl halides. However, the presence of electron withdrawing groups on the aromatic
ring greatly increases the reactivity of aryl halides towards nucleophilic substitution reaction. However, in the
absence of such groups, reaction can still be brought about by very strongly basic reagents or under drastic
conditions. Nucleophilic aromatic substitution follow two very distinct mechanistic pathways.
1. The bimolecular displacement mechanism–involving the carbanion as intermediate and applicable to
activated aryl halides due to the presence of electron withdrawing groups like nitro group.
2. The elimination addition mechanism–involving the bizarre reaction intermediate called benzyne and
applicable to unactivated (due to the absence of any electron withdrawing group) and deactivated aryl
halides(due to the presence of electron donating group).
Example12: Why a vinyl halide show an interesting parallelism to aryl halides?
Solution: Vinyl halides are the compounds in which halogen is attached directly to a doubly bonded carbon
as shown here,
| |
− C = C− X
A vinyl halide is equally unreactive towards nucleophilic substitution reactions as an aryl halide, for basically
the same reason. Moreover, this low reactivity is caused partly by the partial double bond character of the
carbon-halogen bond. The partial double bond character is attributed to resonance as shown below,
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5.1 Structure and Reactivity of Aryl and Vinyl Halides

The low reactivity of aryl and vinyl halides towards nucleophilic substitution reaction has been attributed to
two different factors,
1. Delocalization of electrons by resonance and
2. Differences in σ bond energies due to difference in hybridization of carbon.
Cl Cl +Cl +Cl +Cl
H H
H
(I) (II) (III) (IV) (V)
Chlorobenzene is considered to be hybrid of not only the two Kekule structures I and II, but also structures, III,
IV, and V, in which chlorine is joined to carbon by a double bond. In structures III, IV, and V chlorine bears a
positive charge and the ortho and para positions bear a negative charge.
In a similar way, vinyl chloride is considered to be a hybrid of structure VI and structure VII (in which chlorine
is joined to carbon by a double bond). In (VII), chlorine bears a positive charge and C-2 bears a negative
charge. Other aryl and vinyl halides have structures exactly analogous to these.
Contribution from III, IV and V, and from VII stabilizes the chlorobenzene and vinyl chloride molecules, and
gives a double bond character to the carbon–chlorine bond. Carbon and chlorine (and halogen, in general)
are thus held together by something more than a single pair of electrons, and the carbon chlorine bond is
stronger than if it were a pure single bond. It becomes difficult to break a double bond and eventually results
into low reactivity. So, it can be said that the low reactivity of these halides towards nucleophilic substitution is
due to resonance stabilization of the halides.
In alkyl halides, the carbon holding halogen atom is sp3 hybridized whereas in aryl and vinyl halides, carbon
is sp2 hybridized. It results into the shorter and stronger carbon–halogen bond. Thus the C-X bond becomes
more stable towards nucleophilic substitution which reinforces the low reactivity of aryl and vinyl halides.
Chlorobenzene and bromobenzene have dipole moments of only 1.7 D, and vinyl chlorides and vinyl
bromides have dipole moments of only 1.4 D. This is consistant with the resonance picture of these
molecules. In the structures that contain double bonded halogen (III, IV, V and VII) there is a positive charge
on halogen and a negative charge on carbon, to the extent that these structures contribute to the hybrids, they
tend to oppose the usual displacement of electrons towards halogen. Although there is still a net displacement
of electrons towards halogen in aryl halides and in vinyl halides but it is less than other organic alkyl halides.
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5.2 Preparation of Aryl Halides

1. From diazonium salts: Benzene diazonium salt is an important compound in the synthesis of
various aryl halides. Depending upon the nature of reagent selected various products can be obtained
as shown below,
BF4– ,∆
C6H5F
CuCl,∆
HNO C6H5Cl
redn. HONO
C6H6 H SO3 C6H5NO2 Sn/HCl C6H5NH2 0°C C6H5N2+
2 4 CuBr,∆
C6H5Br
I–,∆
C6H5I
2. By Halogenation of arenes or substituted arenes: Benzene can be directly halogenated by the

application of dihalogen in the presence of a Lewis acid catalyst as shown here,
Lawis acid
ArH + X2  → ArX + HX
Here X2 = Cl2 or Br2 , Lewis acid = FeCl3, AlCl3, Tl (OAc)3 etc.
For example,
NO2 NO2
Cl2.FeCl3
Cl
m–chloronitrobenzene
NHCOCH3 NHCOCH3
Br2
Br
Acetanilide p–bromo acetanilide
(Major product)
Chemical properties of the aryl halides

1. Low reactivity of aryl and vinyl halides towards SN reaction: An alkyl halide is conveniently
detected by the precipitation of insoluble silver halides when it is warmed with alcoholic AgNO3. The
reaction occurs instantaneously with tertiary alkyl or benzyl bromides, and within five minutes or so
with primary and secondary bromides. But bromobenzene or vinyl bromide does not react at all with
alcoholic AgNO3. So, these can be heated with alcoholic AgNO3 for days without the slightest trace of
AgBr being detected.
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Ag+
–
X OH
– No reaction under
OR
Aryl halide NH3 normal conditions.
or
CN–
–
–
– C=C – X
ArH,
Vinyl halide
AlCl3
The typical reaction of alkyl halides, is nucleophilic substitution as discussed earlier in the chapter,
R – X +:Z − → R – Z + :X −
Here, Z = OH − , OR − , NH3, CN − , NH2− , ROH, H2O etc.
On the other side, aryl halides undergo nucleophilic substitution only with extreme difficulty. Except for
certain industrial processes where very severe conditions are applied, one does not ordinarily prepare
phenols (ArOH), ethers (ArOR), amines (ArNH2), on nitriles (ArCN) by nucleophilic attack on aryl halides.
Moreover, the aryl halides cannot be used in the Friedel-Crafts reaction for arylation.
However, aryl halides undergo nucleophilic substitution readily if the aromatic ring is activated by the
placement of strongly electron withdrawing groups like –NO 2 , –CF 3 at ortho or para position to the halogen
atom. Even unactivated aryl halides can undergo nucleophilic substitution reaction if a strong base is applied
at high temperature. In such cases, the reaction proceeds via the intermediate benzyne. For example, Dow's
process used for the manufacture of phenol involves benzyne intermediate.
2. Electrophilic aromatic substitution: Aryl halides can always undergo the typical electrophilic
aromatic substitution reactions like nitration, sulphonation, halogenation, Friedel–Craft reactions etc.
The unusual feature is that the halogen atom which is attached directly to the benzene ring is
deactivating the benzene ring towards an incipient electrophile, yet ortho and para-directing towards
disubstitution.
5.3 Formation of Grignard Reagent

Aryl halides on treatment with magnesium metal in dry ether yields a Grignard reagent. The reaction scheme
is shown below,
dry ether
ArBr + Mg  
→ ArMgBr
tetrahydrofuran
ArCl + Mg  → ArMgCl
1. Electrophilic aromatic substitution: Although halogen is a deactivating group but still it directs
the incoming electrophile to ortho and para position as discussed earlier.
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For example,
Cl Cl Cl
NO2
H2SO4
+ HNO3 +
NO2
Cl Cl Cl
CH3
CH3Cl
+
AlCl3
CH3
Cl Cl Cl
Br
Br2/Fe
+
Br
2. Nucleophilic aromatic substitution: The nucleophilic aromatic substitution can be done in two
possible ways,
(i) Bimolecular addition elimination mechanism
(iii) Benzyne or elimination -addition mechanism
These two are discussed below one by one.
(i) Bimolecular SNAr or Addition-Elimination mechanism
ArX + Z − → ArZ + X −
For facile reaction, aryl group must contain strongly

Cl OC2H5
electron withdrawing groups at ortho and/or para
position to the halogen atom. The reaction involves the NO2 NO2
C2H5OH
formation of intermediate as carbanion. More 300°C, 10 atm
importantly, the presence of electron withdrawing group
stabilizes the carbanion and facilitates the reaction.
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Cl OC2H5
NO2 NO2
C2H5OH
150°C, 5 atm
NO2 NO2
Cl OEt
O2N NO2 O2N NO2
C2H5OH
75°C, 2 atm
NO2 NO2
Reaction proceeds by carbanion intermediate. The rate of the reaction increases with the increase in number
of electron withdrawing groups, since the carbanion formed would be stabilized more. The mechanism of the
reaction is of addition–elimination type.
Step: 1
X
X Nu X Nu X Nu O
NO2 NO2 NO2 N
•• •• O
Nu–
slow (RDS)
••
X Nu O
N
O
Step: 2
Nu
X Nu
NO2 NO2
•• X–
fast
It can be seen that the presence of –NO2 group at ortho or para position would facilitate to disperse the
negative charge of the carbanion, thus stabilizing it more and making the reaction to occur fast.
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Example 13: Identify (A), (B), (C), (D) (E) and (F) in the following series of reactions.
Br2 aq. KOH Na

hν
(A) (B) (C)
alc. KOH
+(C)
(D) NBS (E) (F)
Solution:
Br OH ONa
Br2 aq.KOH Na
hν
(A) (B) (C)
alc.KOH
NBS
Br
ONa Br
(D) (E)
Williamson
+ O
synthesis
(C) (E) (F)
Example 14: 1–Fluoro–2,4–dinitrobenzene is highly reactive toward nucleophilic substitution

through an SNAr mechanism. What product would be formed when 1– fluoro–2,4–dinitrobenzene
reacts with each of the following reagents?
(i) CH3CH2ONa (ii) NH3
(iii) C6H5NH2 (iv) CH3CH2SNa
Solution:
(i) F OCH2CH3
NO2 NO2
+ CH3CH2ONa
NO2 NO2
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(ii)
(iii)
Since lone pair on N–atom of aniline will not be available for nucleophilic attack as it is in resonance with
benzene ring.
(iv) F
NO2
+ C6H5NH2SNa no reaction
NO2
Due to large size of S–atom, the overall nucleophile becomes a bulky one and attack of it on the given
substrate gives a sterically hindered species which is not stable at all. Hence, the substitution will not occur.
(ii) Benzyne or elimination: addition mechanism: Ring not activated toward nucleophilic substitution
reaction participates through benzyne mechanism. The reaction scheme is shown below,
strong base
ArX + :Z −  → ArZ + :X −
Some of the examples are shown below,

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Unactivated aryl halide means either no electron withdrawing substitutent is present or it is present at meta
position. On the other hand, deactivated aryl halides mean the presence of electron releasing groups at any
position. Rate determining step of the reaction is the formation of benzyne intermediate.
Mechanism
Br NH2 NH2
– •NH –
NH2 • 2 NH3
–Br–,–NH3 fast –NH2– ,fast
slow step ••
H
Benzyne
Some of the examples are,

(a)
(b)
14 14
Chlorobenzene with chlorine bonded to C gives almost 50% aniline having NH2 bonded to C and 50%
aniline with NH2 bonded to normal 12 C atom.
O-380
(c) CH3 CH3 CH3
Cl NH2
NH2– NH2– NH3
–Cl,–NH3
(d) OCH3 OCH3 OCH3
NH2– NH2– NH3

–Cl,–NH3
Cl NH2
(e) CH3 CH3 CH3
NH2– NH2– NH3

–Cl,–NH3
Cl NH2
(f)
(g) CH3 CH3 CH3
NH2– NH2– NH3

–Cl,–NH3
NH2
Cl
Example15: When 2–bromo–1,3–dimethylbenzene is treated with sodium amide in liquid

ammonia, no substitution takes place. Explain this fact as an evidence of elimination-addition
reaction.
Solution : Br
H3C CH3
NaNH2
no reaction
liq. NH3
2–bromo–1,3–dimethyl benzene
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In deactivated/unactivated halobenzene, substitution takes place by elimination–addition mechanism, i.e.

benzyne mechanism. But for this, an α −H atom is required which is not present in the given compound.
Hence, it will not react with NaNH2 to give any substituted product.
Example 16: Explain the success of the following reaction where hydride is the leaving group in
nucleophilic aromatic substitution (SNAr).
Solution:
In the case SNAr occurs with hydride (H − ) substitution. This is not a normal process. The reaction occurs by
following mechanism.
Step–I
NO2 NO2
OH– –
+H
NO2 NO2
H OH
Step–II
H − + Fe3+ + H3O+ →Fe2+ + H2 + H2O

Oxidizing agent
Thus the oxidizing agent ferricyanide makes the H − transfer feasible by oxidizing it to H2 gas in presence of
acid. This is an unusual nuclephilic substitution reaction.
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3. Fittig reaction: It is an extension of Wurtz reaction and consists of heating an ethereal solution of
bromobenzene with metallic sodium.
4. Ulmann biaryl synthesis: Iodobenzene on heating with copper in a sealed tube forms biphenyl.
I+2Cu+I +2CuI
Chloro–or bromobenzene fails to undergo this coupling reaction unless some strong electron withdrawing
group (e.g. NO2) is present in the ortho or para position.
6. Synthesis and Uses of DDT

DDT is acronym for dichloro diphenyl trichloroethane and its IUPAC name is 2, 2-bis (p-Chlorophenyl)
-1,1,1-trichloroethane. D.D.T. is almost insoluble in water but it is moderately soluble in polar solvents. The
structural formula of the compound is,
Cl
Cl Cl
Cl Cl
One important synthetic pathway is being outlined below,
O-383
Uses of D.D.T:
D.D.T. is a powerful insecticide. It is widely used as an insecticide for killing mosquitoes and other insects.
Hazards of D.D.T:
D.D.T. is not biodegradable. Its residues accumulate in environment and its long term effects could be highly
dangerous. It has been proved to be toxic to living beings. Therefore, its use has been abandoned in many
western countries. However, inspite of its dangerous side effects, D.D.T. is still being widely used in India due
to non-availability of other cheaper insecticides.
Example 17: Full name of DDT is

(i) 1, 1, 1-trichloro-2, 2-bis(p-chlorophenyl) ethane
(ii) 1, 1-dichloro-2, 2-diphenyl trimethylethane
(iii) 1, 1-dichloro-2, 2-diphenyl trichloroethane
(iv) None of these.
Solution: (iii)
7. Synthesis and Uses of BHC

Benzene hexachloride was first prepared in 1825; the insecticidal properties were identified in 1944. Benzene
hexachloride (BHC) is any of several stereoisomers of 1,2,3,4,5,6-hexachlorocyclohexane. The structural
formula of the compound is,
Cl
Cl Cl
Cl Cl
Cl
The Y-isomer is about 1,000 times more toxic than any of the other diastereomers formed in the reaction.
The structural differences between these individuals are in the orientations of the chlorine atoms with respect
to the ring of carbon atoms. The chemical addition of chlorine to benzene produces a mixture of several
stereoisomers of 1,2,3,4,5,6-hexachlorocyclohexane. The Y-isomer, which makes up 20-25 percent of this
mixture, is more soluble than the other isomers in certain solvents and can be separated from them. More
volatile than D.D.T., BHC has a faster but less protracted action upon insects.
Hazards of BHC
Lindane has been shown to accumulate in the food chain. This occurs because animals, including humans,
eat foods grown in lindane-contaminated soils, and fishes and other marine life are exposed to
lindane-contaminated waters. In fishes and mammals, exposure to high levels of lindane may cause acute
poisoning, which is evidenced by nervous system dysfunction. Chronic exposure may adversely affect liver
O-384
function in humans. Use of lindane as an insecticide has been banned in many countries. Topical use in
lotions to combat lice is permitted.
Example 18: The halide which undergoes nucleophilic substitution most readily is
(i) p – H3C C6H4Cl (ii) o – MeOC6H4Cl
(iii) p – ClC6H4Cl (iv) C6H4CH(Cl)CH3
Solution : Alkyl halides undergoes nucleophilic substitution faster than aryl halides.
∴ (iv)
Example 19: In order to obtain (CH3)3CCl(g), which reactants are most suitable?
(i) (CH3)3CBr + HCl (ii) (CH3)2C = CH2 + Cl2
(iii) (CH3)2C = CH2 + HCl (iv) (CH3)2CO + CH3OH
Solution : Alkenes in presence of an acid generates a carbocation which will be attacked by nucleophile Cl −
to give the required product.
H+ Cl − Cl −
(CH3)2C = CH2  → (CH3)2C ⊕ – CH3  → (CH3)3C – Cl
∴ (iii)
Example 20: Formation of CH3CH = CHCH2Br on treatment of 1–butene with N–Bromo

succinimide is an example of
(i) Hoffmann rearrangement (ii) 1,3–shift
(iii) Allylic rearrangement (iv) α −chlorination
Solution : NBS is a reagent used selectively to carryout allylic bromination.

• •
NBS
CH3 – CH2 – CH = CH2  → CH3CH –CH=CH2 ↔CH3CH=CH–C H2
Such substitutions are referred as allylic rearrangements.
∴ (iii)
Example 21: In the reaction of p–chlorotoluene with KNH2 in liq. NH3, the major product is
(i) o – toluidine (ii) m – toluidine

(iii) p – toluidine (iv) p – chloroaniline
O-385
Solution :
Cl
NH2 NH2
–
KNH2 NH2 +NH3
–NH3, –Cl
CH3 CH3 CH3 CH3

m–toluidine
The position of -NH2 group is controlled by +I effect of -CH3 group.
∴ (ii)
Example 22 : Following halide(s) does not give precipitate with alcoholic silver nitrate
(i) Ethyl iodide (ii) Tert butyl chloride
(iii) Vinyl chloride (iv) n–propyl bromide
Solution : Precipitation of silver halide could take place if halogen is expelled from the halide readily, which
will be feasible only when there is a single bond between R and X. In vinyl chlorides, there are double bond
characteristics between C — Cl bond due to resonance, which makes it difficult to be expelled, thus
precipitation does not occur with it.
∴ (iii)
Example 23 : A carbon compound (A) forms (B) with sodium metal and again (A) forms (C) with
PCl5 but (B) and (C) form diethylether. Therefore (A), (B) and (C) are
(i) C2H5OH, C2H5ONa, C2H5Cl (ii) C2H5Cl, C2H5ONa, C2H5OH
(iii) C2H5OH, C2H6, C2H5Cl (iv) C2H5OH, C2H5Cl, C2H5ONa
Solution : The compound reacting with sodium would be an alcohol (A) which gives alkoxide (B) with it.
Alcohol reacting with PCl5 gives an alkyl halide (C). (B) and (C) reacts by nucleophilie substitution to give
diethyl ether. Since diethylether is a symmetrical ether, so both the alkyl parts of (B) and (C) should be ethyl.
∴ (i)
O-386
Example 24: Which chloroderivative of benzene among the following would undergo hydrolysis
most readily with aq.NaOH to furnish the corresponding hydroxy derivative?
(i) NO2 (ii)
O2N Cl
O2N Cl
NO2
(iii) (iv) C6H5Cl

Me2N Cl
Solution : The nucleophilic substitution in aryl halides is assisted by the presence of electron withdrawing
groups at ortho para–positions. More is the number of electron withdrawing groups, more easier would be
the hydrolysis.
∴ (i)
Nu
|
Example 25 : CH 3 − C H − CH 2 − X gives the CH 3 − C − CH 3 on treatment with a
| |
CH 3 CH 3
nucleophile. In which condition, the yield of product will be maximum
(i) H 2O as a solvent, X = Cl (ii) CHCl 3 as a solvent, X = Br
(iii) H 2O as a solvent, X = I (iv) CHCl 3 as a solvent, X = Cl
Nu
|
Nu −
Solution : CH3 − CH − CH2 − X  → CH3 − C − CH3 + X −
| |
CH3 CH3
As it is evident that reaction involves rearrangement, this means that reaction proceeds via carbocation
formation. The carbocation formation is possible by the ionization of given alkyl halide. The ionization is
assisted by a higher polar solvent like H2O and a weaker base as the leaving group like I − .
∴ (iii)
Example 26: A hydrocarbon (A) having molecular weight 70 gives a single monochloride but
three dichlorides on chlorination in the presence of ultra violet light. The hydrocarbon (A) is
(i) 2–pentene (ii) cyclopentane
(iii) 2–methyl–2–butene (iv) methylcyclobutane
Solution: Since the hydrocarbon (A) gives only a single monochloride, it implies that all the C—H bonds
must be of the same type. So the given hydrocarbon should be cyclopentane.
∴ (ii)
O-387
Example 27: In the following groups,
(I) –OAc (II) –OMe
(III) –OSO2Me (IV) –OSO2CF3
the order of leaving group ability is
(i) (I) > (II) > (III) > (IV) (ii) (IV) > (III) > (I) > (II)
(iii) (III) > (II) > (I) > (IV) (iv) (II) > (III) > (IV) > (I)
Solution: The anions of strong acids, i.e. weak conjugate base always act as good leaving groups
particularly in polar solvent.
Since the decreasing order of acidic strength is following.
F3CSO3H > CH3SO3H > CH3COOH > CH3OH
The order of leaving group ability is
F3CSO −3 > CH3SO −3 > CH3COO − >H3CO −
∴ (ii)
Example 28: Identify (Z) in the following reaction series,

NaOH(aq.)
2 3 2Al O
2 Cl / H O
CH3.CH2CH2Br  → (X)   → (Y)   → (Z)
heat
(i) Mixture of CH 3 − C H − C H 2 and CH 3 − C H − C H 2

| | | |
Cl Cl OH Cl
(ii) CH 3 − C H − C H 2
| |
OH Cl
(iii) CH 3 − CH − C H 2
| |
Cl OH
(iv) CH 3 − C H − C H 2
| |
Cl Cl
aque . NaOH 2 3 Al O
Solution: CH3CH2CH2Br  → CH3CH2CH2OH   → CH3CH = CH2
∆
(X) (Y)
Cl / H O
2 2
  → CH3 − CH − CH2
| |
OH Cl
∴ (ii)
O-388
Example 29: For the reaction,

CH3CH=CHCH3
NaNH2
CH3CH CH2CH3
(X) CH2=CHCH2CH3
(i) CH3 – CH = CH – CH3 predominates.
(ii) CH2 = CH – CH2 – CH3 predominates.
(iii) Both are formed in equal amounts.
(iv) The product ratio is dependent on the halogen (X).
Solution: When alkyl halide undergoes elimination reaction in presence of base, more substituted alkene
(Saytzeff's product) will be the major product.
But either in presence of bulky base or the poor leaving group may give rise to the less substituted alkene
(Hoffmann's product) as the major product.
Since base is a non–bulky strong one, the ratio of product is determined by the halogen atom.
∴ (ii)
Example 30: 1–phenylethyl chloride undergoes alkaline hydrolysis to give 1–phenylethanol with
(i) Complete inversion of configuration (ii) Racemization plus some inversion
(iii) Retention of configuration (iv) Complete racemization
Solution:
So there is racemization plus some inversion.
∴ (ii)
Example 31: Me Me Me Me
–
OH OH–
HO H H Cl H HO + HO H
(II) (I)
Et Et Et Et
Steps (I) and (II) are

(i) both SN1 (ii) both SN2
(iii) (I): SN1, (II): SN2 (iv) (I): SN2, (II): SN1
Solution: By (I) there is a product with no change in configuration while by (II) there is inversion hence (I) is
SN1 and (II) is SN2.
∴ (iii)
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Example 32: Br CH3 OH–

(A). The product (A) is
H H SN2
(i) HO CH3 (ii) H CH3

H H HO H
(iii) both (iv) none
Solution: Inversion takes place by SN2 reaction.
∴ (ii)
Example 33: (I) CH3CH2CH2CH2Cl (II) CH3CH2–CH(Cl)–CH3 (III) (CH3)3C – Cl
Increasing tendency for SN1 and SN2 reaction is
(A) SN1: (I) < (III) < (II) (B) SN2: (II) < (III) < (I)
(i) (A) and (B) both are correct (ii) Only (A)
(iii) Only (B) (iv) Both (A) and (B) are incorrect
Solution: For SN1, order of reactivity is 1° < 2° < 3°
For SN2, order of reactivity is 1° > 2° > 3°
∴ (ii)
Example 34: SN2 reaction at an asymmetric carbon of a compound always gives
(i) An enantiomer of the substrate. (ii) A product with opposite optical rotation.
(iii) A mixture of diastereomers. (iv) A single stereoisomer.
Solution: SN2 reaction proceeds with inversion of configuration. Since the attacking nucleophile is not same
as that of leaving group, the product cannot be enatiomer of the substrate so the product will not necessarily
have opposite optical rotation. Moreover only one product is obtained, so we cannot obtain diastereomers.
∴ (iv)
Example 35: The hydrolysis of 2– bromo 3– methylbutane yields
(i) 3–methyl –2– butanol (ii) 2– methyl –2– butanol
(iii) 3– methylbutanol (iv) 1– methylbutanol
Solution: The intermediate is a 2° carbocation which rearranges to a more stable 3° carbocation by the shift
of hydride.
O-390
CH3 CH3 CH3
⊕
1,2hydride
CH3–CH–CH–CH3 CH3–CH–CH–CH3 CH3CH2–C–CH3
shift
⊕
Br
H2O
CH3
CH3CH2–C–CH3
OH
2–methyl–2–butanol
∴ (ii)
NEt 2
|
OH −
Example 36: CH 3 − CH − CH 2  
→ ?
|
Cl
The product of the above reaction is
(i) CH3 CHCH2NEt2 (ii) CH3 CHCH2 OH

| |
OH NEt2
(iii) CH3CHCHNEt2 (iv) CH3 CHCH2 – N– OH

| |
OH Et
Cl
Solution: Et Et
NEt2
N
⊕
–Cl– OH–
CH3–CH–CH2 CH3–CH–CH2 CH3CH–CH2NET2
Cl OH
This is an example of neighbouring group participation.

∴ (i)
2 5 C H OK/C H OH
2 5 → ?
Example 37: CH3CH2CH(F)CH3  
The product of the above reaction is
(i) CH3CH2CH = CH2 (ii) CH3CH = CHCH3
(iii) CH3CH2CH(OEt)CH3 (iv) None of the above
Solution: Since F − is a poor leaving group, attack of base (C2H5O − ) will form less substituted alkene.
∴ (i)
O-391
(a) Benzyl chloride

(b) p- methoxy - benzyl chloride
1. How does S N 1 reaction differ from S N 2 and
(c) p - nitro benzyl chloride. [Lko. 2009]
discuss S N 1 mechanism.
[Bund. 2009; Hazaribagh 2009] 7. Explain with examples S N 1 and S N 2 reactions.
[Lko. 2010]
2. Explain the mechanism of S N 2 and S N 1 reaction
and also discuss the stereochemistry of these 8. (i) Write four methods for the
reactions. [Bund. 2010; Meerut 2009, 12] preparation of Chlorobenzene.
3. Describe the action of chlorine on toluene under (ii) How will you prepare the following from
difference experimental conditions. Name different chlorobenzene?
products formed and short also how they behave (a) Phenol
towards (i) Caustic soda and (ii) Oxidising agents?
(b) Aniline
[Kanpur 2011]
4. (i) Differentiate between S N 1 and S N 2 (c) Phenyl cyanide

reaction. (d) D.D.T. [Hazaribagh 2008]
(ii) Starting with cholorbenzene, how will you
obtained the following : Short Answer Type Questions
1. (i) Explain why chloroform is stored in
(a) Aniline (ii) Phenol
dark coloured air tight bottle.
(b) D.D.T. (iv) Benzene (ii) Bleaching powder reacts with acetone.
[Kashi 2010, 11] [Bund. 2009]
5. Write short note on the following : 2. Write chemical reactions only
(i) S N 1 reaction, (i) Oxidation of chloroform in presence of air

and sun light.
(ii) Chlorination of toluene in presence of
(ii) Reimer-Tiemann reaction.
sunlight
3. Write a short note on BHC. [Bund. 2010]
(iii) BHC [Lko. 2008]
4. Discuss the preparation and properties of D.D.T.
6. (i) Which one of the following is an [Meerut 2012; Agra 2008]
example of S N 2 reaction? Give the
5. Why benzyl chloride undergoes nucleophilic
product and outline the mechanism of
displacement easily like allyl chloride? [Agra 2008]
reaction :
6. How will you convert the following ?
(a) H3C - CH = CH - CI + NaNH2 →?
(i) C6H5CH2Cl into C6H5CH2OC2H5
(b) (CH3)3 C - Br + C2H5 OH → ?
(ii) C6H5Br into C6H5CH3 [Kanpur 2010]
(c) CH3. CH2 - CH2 - Br + LiAiH4 → ?
(ii) Arrange the following compound in order of 7. Write short notes on the following :
decreasing reactivity towards S N 1 reaction (i) Westron (CHCl2 - CHCl2)
and justify:
(ii) Freon (CCl2F2) [Kanpur 2011]
O-392
8. Discuss the mechanism of S N 2 reaction. 3. Give method of preparation and uses of the
[Avadh. 2008] following
9. What is Haloform reaction? [Avadh. 2009] (i) Chloretone (ii) D.D.T [Kanpur 2009]
4. Write note on iodoform reaction. [Kanpur 2009]

10. Give the mechanism of S N 1 reaction of alkyl
halides. [Avadh. 2010] 5. How can you convert the following C2H5Cl into
T.E.L? [Kanpur 2010]
11. How will you synthesize chlorobenzene,
6. How will you distinguish between benzyl chloride
bromobenzene, iodobenzene and fluorobenzene
and p-chlorotoulene ? [Kanpur 2010]
from benzene diazonium salt?
7. Give method of preparation and uses of the
12. Explain haloform reaction and its mechanism following :
[Rohd. 2010]
(i) D.D.T. (ii) Westron [Kanpur 2010]
13. Describe mechanism of S N 2 giving energy profile
8. Chlorine of methyl chloride is more reactive than
diagram. [Rohd. 2012] chlorine of chlorobenzene. Why? [Kanpur 2010]
14. Write a note on Walden inversion. [Rohd. 2012] 9. Convert: Ethyl alcohol into chloroform.
[Kanpur 2011]
15. Write short notes on the synthesis of DDT and BHC.
[Rohd. 2013] 10. Why vinyl choride is inert towards nucleophilic
substitution reaction? [Kashi 2011]
16. Cl atom of ethyl chloride is more reactive than Cl
11. Write two methods of the preparation of
atom of vinyl chloride. Explain why? [D.D.U. 2008]
chlorobenzene. [Kashi 2011]
17. Discuss the mechanism of S N 2 reaction by taking
12. Allyl chloride hydrolyses more rapidly than tertiary
the example of hydrolysis of ethyl bromide by butyl halide. Why? [Lko. 2009]
aq.NaOH. [D.D.U. 2008]
13. Allyl halides are more reactive than alkyl halides
18. Discuss the mechanism of hydrolysis of towards nucleophilic substitution reaction. Why?
1-bromomethane with aq. NaOH. [Lko. 2011]
[D.D.U. 2010]
14. Write a note on the synthesis and used of DDT and
19. Define haloform reaction. [Hazaribagh 2009,11]
Lindane. [Lko. 2011]
20. Define Ulmann reaction. [Hazaribagh 2009] 15. CH3Br and (CH3)3CBr hydrolyze involving different
mechanisms. What are these mechanisms? Explain.
21. Discuss the factors which affect S N 1 and S N 2
[Lko. 2011]
reactions. [Hazaribagh 2011]
16. Explain S N 2 nucelophilic substitution reaction in
alkyl halide. [Hazaribagh 2010]
17. Explain why chlorine of vinyl chloride in inert.
1. Explain that chlorine of vinyl chloride is inert. [Hazaribagh 2010]
[Meerut 2011]
18. Why are S N 1 and E1 competing reactions?
2. Give the IUPAC name of following compounds : [Hazaribagh 2011]
BrCH 2 − CH 2 − CH 2 − CHO and 19. Distinguish between the transition state and an
CH 3 CH − CH 2 − CH 2 − Br [Kanpur 2009] intermediate. [Hazaribagh 2011]
|
Cl 20. Classify haloalkanes.
O-393
7. If 1,3–dibromopropane reacts with zinc, the product is

Objective Type Questions (a) Propene (b) Propane
(c) Cyclopropane (d) Hexane
Multiple Choice Type Questions
8. Which of the following is an organometallic
1. Which compound has the lowest boiling point
compound?
(a) n-pentyl chloride
(a) Lithium methoxide
(b) n-butyl chloride
(b) Lithium acetate
(c) sec-butyl chloride
(c) Lithium dimethylamide
(d) t-butyl chloride
(d) Methyl lithium
2. CH2 = CH – CH2Cl + OH − → (A). The compound
9. (CH3)3CMgCl on reaction with D2O produces
(A) in the reaction is
(a) (CH3)3CD (b) (CH3)3COD
(a) Ethyl chloride
(c) (CD3)3CD (d) (CD3)3COD
(b) Ethyl alcohol
10. The exchange reaction given below
(c) Ethylene and methyl alcohol
(d) Allyl alcohol Cl – CH2 – CH = CH2  Nal
→I – CH2 – CH = CH2
Acetone
3. Ethylidene chloride on treatment with aqueous
+ NaCl↓ is known as
KOH gives
(a) Wurtz reaction
(a) acetaldehyde (b) ethylene glycol
(b) Fittig reaction
(c) formaldehyde (d) none of them
(c) Feinklestein reaction
4. Which compound reacts fastest by S N 1 mechanism?
(d) Koble's reaction
(a) (CH3)2CHI (b) CH3CH2I
(c) (CH3)3CI (d) CH3CH2CH2I 11. CH2
5. RCl + NaOH (aq) → ROH + NaCl

The rate law for this reaction is given by Rate = k' HBr
(A)
ROOR
[RCI]
The rate of the reaction will be
Theproduct (A) is
(a) doubled on doubling the concentration of
(a) CH2Br
sodium hydroxide
(b) halved on reducing the concentration of alkyl
halide to one-half
(c) increased on increasing the temperature of the
reaction
(b) CH3
(d) unaffected by increasing the temperature of the
Br
reaction
6. In the reaction, Acetylene + HBr (excess) → ?

The product is
(a) Vinyl bromide (c) Both are correct
(b) Ethyl bromide (d) None is correct
(c) Ethylene bromide 12. What is the end product of the following sequence
(d) Ethylidene bromide of reaction?
O-394
OH (a) CH3CH2Cl (b) CH=CH–Cl

H2SO4 2NBS
(A) Product (c) C6H5–Cl (d) HC≡ C–Cl [Agra 2008]
∆
(a) BrCH2CH = CHCH2Br 18. Formation of PVC takes place from which
compound?
(b) CH3CH =CH – CHBr2
(a) Ethyl chloride
(c) CH3 – C(Br) = C(Br) –CH3
(b) Methyl chloride
(d) None of the above
(c) Vinyl chloride
13. When 3– ethyl –2– pentene reacts with HBr in the
presence of peroxide, the major product is (d) Propyl chloride [Agra 2008]
Br H 19. What is full name of DDT

(a)
(a) Diphenyl diethyl trichloroethane
CH3–CH–C–CH2CH3
(b) Dichloro diphenyl trichloroethane
C2H5
(c) Diamine dichloro trichlorobenzene
(b) Br (d) None of these [Agra 2008]
CH3CH2–C–CH2CH3 Fill in the Blank

C2H5 1. S N 2 reaction at an asymmetric carbon of a
(c) Both of these compound always gives its ………. .
(d) None of these 2. Vinyl chloride is ……… reactive than ethyl chloride
towards nucleophilic substitution reaction.
14. When 3– ethyl –2– pentene reacts with Br2/H2O, the
major product is 3. Benzyne is ……… in nature.
C2H5 4. S N 1 reaction is accompanied with ………. .
(a)
5. Butane on dichlorination yields………… structural
CH3–CH–C–CH2CH3 isomers.
Br OH 6. Pentane on monobromination yields ……… chiral

carbon centres.
(b) C2H5
7. Out of –OAc and –OMe, ……… is a better leaving
CH3–CH–C–CH2CH3 group.
8. Chlorine is a/an ……… director to nitroniumion.
OH Br
(c) Both of these 9. Bromobenzene is ……… reactive than allyl
bromide towards nucleophilic substitution reaction.
(d) None of these
10. In the reaction of p–chlorotoluene with KNH2 in liq.
15. Which is inert towards nucleophilic substitution NH3, the major product is ………. .
reaction?
(a) CH2 = CHCl (b) CH2 = CH – CH2Cl
(c) C6H5CH2Cl (d) C6H5CH2CH2Cl
16. To prevent oxidation of chloroform one of the
following is added :
(a) CH3Cl (c) CH2Cl2
(b) C2H5OH (d) CH3COCH3 [Bund. 2008]
17. Which will be more reactive towards nucleophilic
substitution?
O-395
True/False 6. Due to the polar nature of haloalkanes, they are

1. Order of reactivity of alkyl halides for S N 1 highly soluble in water.
mechanism is 1° >2° > 3°. 7. In S N 1 mechanism, rate of reaction depend upon
2. Allylic and benzylic halides are more reactive the concentration of nucleophile.
towards nucleophillic substitution. 8. According to Saytzeff rule, " In dehydrohalogena–
3. Preperation of alkyl chloride in the presence of tion reactions, the preferred product is that alkene
SOCl2 from alchohol is preferred. which has gretaer number of alkyl groups attched to
the doubly bonded carbon atoms."
4. Reaction of Br2 /CCl4 with alkene is one of the
method to test unsaturation in the compound. 9. Aqueous and alchoholic KOH both are used to
convert alkyl halides to alchohols.
5. For the same alkyl group, boiling points of alkyl
halide increases in the order RF > RCl > R Br > RI. 10. Aryl halides are less reactive towards nucleophillic
substitution reactions.

1. (d) 2. (d) 3. (a) 4. (c) 5. (b)
6. (d) 7. (c) 8. (d) 9. (a) 10. (c)
11. (a) 12. (a) 13. (a) 14. (a) 15. (a)
16. (c) 17. (a) 18. (c) 19. (b)
Fill in the Blank

1. enantiomer 2. Less 3. aromatic
4. racemisation with inversion 5. 9 6. 3
7. –Oac 8. O/P 9. less
10. m–Toluidine
True/False
1. False 2. True 3. True 4. True 5. False
6. False 7. False 8. True 9. False 10. True

O-396
Hints and Solutions

6. (i) C H O − Na +
C6 H 5 CH 2 − Cl  2 5  → C6 H 5 CH 2 − O − C2 H 5
(ii) Na 1
C6 H 5 Br + CH 3 Br C6 H 5 CH 3
dry ether
11. Cl
CuCl
Br
+ CuBr
N2
KI I
HBF

6. AgNO3 yields white curdy ppt with
CH2–Cl
I
9. CH 3 − CH 2 − OH 2+ CHI 3 + HCOONa
NaO4
20. H R R
R–C–X R–C–X R–C–X
H H R
1° 2° 3°

6. (d) It is an electrophilic addition reaction involving 2 moles of HBR.
15. (a) Vinyl halides are reluctant to participate in S N reaction.
mmm

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Krishna's

As per U.P. Unified Syllabus (w.e.f. 2011-12)

Ex. Scientist (Nuclear)

R.P. Singh Babita Agrawal

Ashish Dwivedi Prashant Singh

KRISHNA Prakashan Media (P) Ltd.

The book is written with the following special features:

3. In each Chapter, Solved Examples are given based on different Topics.

July 2015 –Authors

Chapter 2 Mechanism of Organic Reactions O–63-102

Chapter 3 Alkanes & Cycloalkanes O–103-134

Chapter 7 Alkyl and Aryl Halide O–345-396

Chapter 6 : Arenes and Aromaticity

2. Localised and Delocalized Chemical Bonding

2.2 Covalent Bond

2.3 Types of Covalent Bonds Sigma (σ) and Pi (π) Bonds

1s arbital of 1s arbital of s–s overlap

Fig. 1: Overlap of s orbital

1-s orbital 2pz orbital s–p overlap

2pz orbital p–p overlap

Fig. 3: Overlap of p–p orbital

Fig. 4: Formation of O2 molecule

N–atom N–atom N2 molecule

Fig. 5: Formation of nitrogen

2.4 Multiple Bonding

2.5 Co–ordinate Bond

3. Characteristics of Covalent Bond

3.1 Bond Length

153.5 pm 133.9 pm 120.3 pm

C2H6 C2H4 C2H2

Tabel 1: Bond lengths in organic compounds

C—H Length (pm) C—C Length(pm) Multiple–bonds Length (pm)

sp3—H 110 sp3—sp3 154 Benzene 140

sp2—H 109 sp3—sp2 150 Alkene 133.9

sp—H 108 sp2—sp2 147 Allene 120.3

3.2 Bond Angle

Example1: Predict all bond angles in the following molecules.

(i) CH3Cl (ii) CH3CN (iii) CH3COOH

Solution: (i) The Lewis structure of methyl chloride is:

(ii) The Lewis structure of acetonitrile, CH3CN is:

(ii) The Lewis structure of acetic acid is:

3.3 Bond Energy

Table 2: Average bond energies (kj/mol)

Single Bonds Multiple Bonds

H—H 432 N—H 391 I–I 149 C=C 614

H—F 565 N—N 160 I–Cl 208 C≡C 839

H—Cl 427 N—F 272 I–Br 175 O=O 495

H—Br 363 N—Cl 200 S–H 347 C = O* 745

H—I 295 N—Br 243 S–F 327 C≡O 1072

C—H 413 N—O 201 S–Cl 253 N=O 607

C—C 347 O—H 467 S–Br 218 N=N 418

C—N 305 O—O 146 S–S 266 N≡N 941

C—O 358 O—F 190 Si–Si 340 C≡N 891

C—F 485 O—Cl 203 Si–H 393 C≡N 615

C—Cl 339 O—I 234

C—Br 276 F—F 154 Si–C 360

C—I 240 F—Cl 253 Si–O 452

C—S 259 F—Br 237

Some of the characteristics of bond energy values are:

Is the reaction written above exothermic or endothermic? Explain.

3.4 The Shape of Molecules

4. Delocalized Chemical Bonding and Resonance

4.1 Resonance Energy Concept along with Development

(Krishna's Text Book) Alok Bariyar, R.P Singh, Babita Agrawal, Babita Agrawal, Prashant Singh - Organic Chemistry-I-Krishna Prakashan Media (2015)

(Krishna's Text Book) Alok Bariyar, R.P Singh, Babita Agrawal, Babita Agrawal, Prashant Singh - Organic Chemistry-I-Krishna Prakashan Media (2015)