NOMENCLATURE OF ORGANIC COMPOUNDS

IUPAC System [International union of pure and applied chemistry]

The most important feature of this system is that any given molecular structure has only one
IUPAC name which denotes only one molecular structure.
Salient features of IUPAC system
1. A given compound can be assigned only one name.
2. A given name can clearly direct in writing of one and only one molecular structure.
3. The system can be applied in naming complex organic compounds.
4. The system can be applied in naming multifunctional organic compounds.
5. This is simple, systematic and scientific method of nomenclature of organic compounds.
Rule for Naming
Prefix (alphabetically) root word (alk) primary suffix (ene, yne) secondary suffix (main
functional group)
So IUPAC name of any organic compounds essentially consists of two or three parts.
(i) Root word (ii) Suffix (iii) Prefix
(i) Root Words
The basic unit is a series of root words which indicate linear or continuous chains of carbon
atoms. Chains containing one to four carbon atoms are known by special root words while chains
from C5 onwards are known by Greek number roots.
Chain Length Root word Chain Length Root word
C1 Meth- C11 Undec-
C2 Eth- C12 Dodec-
C2 Prop- C13 Tridec-
C4 But- C14 Tetradec-
C5 Pent- C15 Pentadec-
C6 Hex- C16 Hexadec-
C7 Hept- C20 Eicos-
C8 Oct- C30 Triacont-
C9 Non- C40 Tetracont-
C10 Dec- C50 Pentacont-
In general, the root word for any carbon chain in alk-.

(ii) Primary Suffix

Primary suffix are added to the root words to show saturation or unsaturation in a carbon chain.

Nature of carbon chain Primary suffix Generic

name
Saturated (C – C) -ane Alkane
Unsaturated (C = C) -ene Alkene
with one double bond
Unsaturated (C  C) with one triple -yne Alkyne
bond
Unsaturated with two C = C bonds -diene Akladiene
Unsaturated with two C  C bonds -diyne Alkadiyne
 Unsaturated with three C = C -triene Alkatriene
bonds
(iii) Secondary Suffixes
Suffixes added after the primary suffix to indicate the presence of a particular functional group in the carbon chain are
known as secondary suffixes.

Functional Group Secondary suffix

Alcohol (-OH) -ol
Aldehyde (-CHO) -al
Ketone (>CO) -one-
Carboxylic acid (-COOH) -oic acid
Sulphonic (-SO3H) -sulphonic acid
Amine (-NH2) -amine
Thioalcohol (-SH) -thiol
Cyanide (-CN) -nitrile
Ester (-COOR) -oate
Amide (-CONH2) -amide
Acid halide (-COX) -oyl halide
Note:
The terminal ‘e’ of the primary suffix is removed when initial letter of secondary suffix is vowel. To illustrate the
application of above basic rule, the generic names of few classes of organic compounds are given below:

Homologous Root Primary Secondary Generic

series word suffix suffix name
Alcohols Alk -ane -ol Alkanol
(saturated)
Alcohols Alk -ene -ol Alkenol
(unsaturated)
one double bond
Alcohols Alk -yne -ol Alkynol
(Unsaturated)
one triple bond
Aldehydes Alk -ane -al Alkanal
(saturated)
Ketones Alk -ane -one Alkanone
(saturated)
Carboxylic acids Alk -ane -oic acid Alkanoic acid
(Saturated)
Acid chlorindes Alk -ane -oyl chloride Alkanoyl
(saturated) chloride
Prefix:
It should always be kept in mind that alkyl groups forming branches of the parent chain are
considered as side – chains. Atoms of groups of atoms such as fluoro (-F), chloro (-Cl), bromo
(-Br), iodo (-I), nitro (-NO2), nitroso (-NO) and alkoxy (-OR) are referred to as substituents. Roots
words are prefixed with the name of the substituent or side chain.
Arrangement of Prefixes, Root word and Suffixes

These are arranged as follows while writing the name.

Prefix (es) + Root word + Primary suffix + Secondary suffix
For Example:
4 3 2 1
H3C CH CH2COOH

Br
Prefix = Bromo (at position 3),
Root word = But,
Primary suffix = -ane
Secondary suffix = -oic acid
Hence, the name of the compound is,
3 – Bromo butanoic acid
5 4 3 2 1
H3C CH CH CHCH2OH

CH3
Prefix = Methyl (at position 4)
Root word = Pent,
Primary suffix = -ene (at position 2),
Secondary suffix = -ol
Hence, the name of the compound is,
4 – Methyl pent – 2 – en – 1 – ol
The names of simple aliphatic organic compounds containing only straight chains atoms of
various homologous series are described in table as to explain the basic rules of IUPAC system.
In case of compounds. Other than hydrocarbons, only the saturated compounds have been
considered.
NAMING OF HYDROCARBON
Compound of Hydrogen and Carbon are called hydrocarbon
Classifications
 Hydrocarbons

Open Chain hydrocarbon(Aliphatic) Closed chain (cyclic)

Saturated Unsaturated Alicyclic Aromatic

Hydrocarbon Hydrocarbon
Alkane
[C - C] Alkene Alkyne
[C = C] [C = C]

Open Chain Hydrocarbon

Alkane Alkene Alkyne

General CnH2n+2 CnH2n CnH2n-2
Formula
Value of n C–C C=C CC
n=1 CH4 (Methane) - -
n=2 C2H6 (Ethane) C2H4 (Ethene) C2H2 (Ethyne)
n =3 C3H8 (Propane) C3H6 (Propene) C3H4 (Propyne)
n=4 C4H10 (Butane) C4H8 (Butene) C4H6 (Butyne)
n=5 C5H12 (Pentane) C5H10 (Pentene) C5H8 (Pentyne)
n=6 C6H14 (Haxane) C6H12 (Hexene) C6H10 (Hexyne)
n=7 C7H16 (Heptane) C7H14 (Heptene) C7H12 (Heptyne)
n=8 C8H18 (Octane) C8H16 (Octene) C8H14 (Octyne)
n=9 C9H20 (Nonane) C9H18 (Nonene) C9H16 (Nonyne)
n = 10 C10H22 (Decane) C10H20 (Decene) C10H18 (Decyne)
Types of carbon and hydrogen atoms in alkanes
They may be classified in to four types
(i) Primary or 10 carbon: A carbon atom attached to one other carbon atom.
(ii) Secondary or 20 carbon: A carbon atom attached to two other carbon atom.
(iii) tertiary or 30 carbon: A carbon atom attached to three other carbon atoms.
(iv) Ouaternary or 40 carbon: A carbon atom attached to four other carbons atoms.
The hydrogen atom attached to 10, 20 and 30 carbon atoms are called primary (1 0), secondary (20)
and tertiary (30) hydrogen atoms.

Illustration 1. How many 10, 20, 30 and 40 carbon atoms are present in the following
hydrocarbons?
 CH3

H3C C CH2 CH CH3

CH3 CH3

Solution: 10  five, 20 one, 30  one, 40  four

10
CH3
10 30 10
H3C C 0 CH2 CH CH 3
4 20 0
10 CH3 CH3 1

Exercise 1.
How many 10, 20, 30 and 40 carbon atoms are present in the following compounds?
(CH3)3C – CH(CH3).CH(CH3)2

Alkyl group
The removal of one hydrogen atom from the molecule of an alkane gives an alkyl group.
General formula CnH2n+1 n = 1, 2, 3----------------------
Example:
CH3 Methyl
C2H5 Ethyl

C2H5CH2 Propyl (n – propyl)

C3H7
CH3 – CHCH3 20 Propyl (Isopropyl or secondary propyl)
C3H7CH2 - 10 butyl (n- butyl or primary butyl)

H 5C 2 C CH3 20 Butyl(sec. butyl)

H
C 4H 9
CH3

H 3C CH CH2 2 Methyl -1 - Propyl (Iso butyl)

H 3C C CH3 2 Methyl -2 - Propyl (ter butyl)

CH3
CH3

H3C C CH2 Neo pentyl

CH3
Nomenclature of Hydrocarbons
Alkane
The IUPAC system of alkane nomenclature is based on the simple fundamental principle of
considering all compounds to be derivatives of the longest single carbon chain present in the
compound. The chain is then numbered from one end to the other, the end chosen as number 1
is that which gives the smaller number at the first point of difference.
CH3 CH3
H3C

H3C CH3 CH3

2-methylpentane 3-methylhexane

When there are two or more identical appendages - the modifying prefixes di-, tri-, tetra-, penta-,
hexa-, and so on are used, but every appendage group still gets its own number.
CH3 CH3 CH3
H3C CH3

CH3 H3C CH3

H3C CH3
2,2-dimethylpentane 2,2,4,4-tetramethylpentane

When two or more appendage locants are employed, the longest chain is numbered from the end
which produces the lowest series of locants. When comparing one series of locants with another,
that series is lower which contains the lower number at the first point of difference.
CH3 CH3

H3C H3C CH3

H3C CH3 CH3
H3C
CH3 CH3 CH3 CH3 CH3
2,3-dimethylpentane 2,5,6-trimethyloctane 2,2,4-trimethylpentane
(not 3,4,7-trimethyloctane) (not 2,4,4-trimethjylpentane)

Several common groups have special names that must be memorized by the student.
CH3 CH3 CH3
| | |
CH3 CH– CH3CH CH2– CH3–CH2–CH–
isopropyl isobutyl sec-butyl

CH3 CH3
| |
CH3 C– CH3–C–CH2–
| |
CH3 CH3
tert-butyl neo-pentyl
or t-butyl
A more complex appendage group is named as a derivative of the longest carbon chain in the
group starting from the carbon that is attached to the principal chain. The description of the
appendage is distinguished from that of the principal chain by enclosing it in parentheses.
 CH3
|
H–C–CH3
|
H–C–CH3
|

CH3CH2CH2CH2CHCH2CH2CH2CH3

5-(1,2-dimethylpropyl)nonane

When two or more appendages of different nature are present, they are cited as prefixes in
alphabetical order. Prefixes specifying the number of identical appendages (di, tri, tetra and so
on) and hyphenated prefixes (tert-or t, sec-) are ignored in alphabetizing except when part of a
complex substituent. The prefixes cyclo-, iso-, and neo-count as a part of the group name for the
purposes of alphabetizing.
When chains of equal length compete for selection as the main chain for purposes of numbering,
that chain is selected which has the greatest number of appendage attached to it.
CH3

CH3
CH3
CH3
H3C

H3C

5-(2-ethylbutyl) – 3, 3 – dimethyl decane

When two or more appendages are in equivalent positions, the lower number is assigned to the
one that is cited first in the name (that is one that comes first in the alphabetic listing).
H3C CH3

H3C CH3 CH3

CH3
H3C H3C CH3
3-ethyl-5-methylheptane 4-ethyl-5-isopropyloctane

CH3 CH3
H3C
H3C
CH3

CH3
CH3
CH3 H3C
6-ethyl-3,3-dimethyloctane 6-ethyl-2-methyloctane
3,3,6 is lower than 3,6,6, at first point of difference 2,6 is lower than 3,7

[The complete IUPAC rules actually allow a choice regarding the order in which appendage
groups may be cited. One may cite the appendages alphabetically, as above, or in order of
increasing complexity].

Exercise 2.
Write the IUPAC name for the following
 CH3
CH3
H3C CH3

(i) H3C CH3 (ii)

H3C CH3
CH3 CH3
CH3
CH3

H3C

(iii)
CH3

CH3

Alkenes
Nomenclature and Structure:
Alkenes (olefins) contains the structural unit
C=C
and have the general formula C nH2n. These unsaturated hydrocarbons are isomeric with the
saturated cycloalkanes. The IUPAC rules for naming alkenes are similar in many respects to
those for naming alkanes.

 Determine the root word by selecting the longest chain that contains the double bond and
change the ending of the name of the alkane of identical length from ane to ene.
 Number the chain so to include both carbon atoms of the double bond, and begin
numbering at the end of the chain nearer the double bond. Designate the location of the
double bond
 by using the number of the first atom of the double bond as prefix :
CH3 CH3
H C H 3C
2
but-1-ene hex-2-ene

 Indicate the locations of this substituent groups by the numbers of the carbon atoms to
which they are attached.
CH3
CH3
CH3
H3C H3C H2C Cl
CH3
CH3 H3C 4-chlorobut-1-ene

2,5-dimethylhex-2-ene (2E)-5,5-dimethylhex-2-ene

 Two frequently encountered alkenyl groups are the vinyl group and the allyl group.
CH2 = CH — CH2 = CH CH2 —
The vinyl group The allyl group (are not included in IUPAC system)
The following examples illustrate how these names are employed
CH2 = CH — Br CH2 = CH — CH2 Cl
vinyl bromide allyl chloride (are not IUPAC name)
 The geometry of the double bond of a disubstituted alkene is designated with the
prefixes, cis and trans. If two identical group are on the same side of the double bond, it
is cis, if they are on opposite sides; it is trans.
Cl Cl Cl H
C=C C=C
H H H Cl
cis - 1,2 - Dichloroethene trans - 1,2 - Dichloroethene

Illustration 2. The IUPAC name for

CH2 H3C CH3
H3C

H3C
CH3
CH2
CH3 H3C CH3 Cyclopropyl ethene
4-(1-methylbutyl)hexa-1,4-diene 7-ethyl-4,8-dimethyldec-4-ene

H H H3C H

H3C

CH3 H

H H H2C
(2Z,4Z)-hexa-2,4-diene (3E)-penta-1,3-diene

Exercise 3.
Give the IUPAC name of the following
CH3 (ii H3C CH2
(i) (iii
H2C CH3
CH ) )
3
H3C CH3
H3C CH3

Alkyne

Nomenclature of Alkynes:
Alkynes contains the structural unit
C C
and have the general formula CnH2n-2.
The simple alkynes are readily named in the common system as derivatives of acetylene itself.
CH3C  CH CH3—CC—CH2—CH3 F3CCCH
methylacetylene ethylmethylacetylene trifluoromethylacetylene
In the IUPAC system the compounds are named as alkynes in which the final – ane of the parent
alkane is replaced by the suffix – yne. The position of the triple bond is indicated by a number
when necessary.
CH3C  CH (CH3)2CHCCH CH3CH2CH2CHC  CCH3
Propyne 3-methyl –1-butyne
CH2CH2CH3
4-propyl-2-heptyne
When both a double and triple bond are present, the hydrocarbon is named an alkenyne with
numbers as low as possible given to the multiple bonds. In case of a choice, the double bond
gets the lower number.
In complex structures the alkynyl group is used as a modifying prefix.
C CH

Cyclopentyl ethyne

Aromatic Hydrocarbons
These compounds consists of at least one benzene ring, i.e., a six – membered carbocylic ring
having alternate single and double bonds.
CH CH CH
CH HC HC C CH

HC CH HC C CH
CH CH CH
Benzene (Monocyclic)
Napthalene (Bicyclic)

CH CH CH
HC C C CH

HC C C CH
CH CH CH
Anthracine (Tricyclic)

�
R -H �� -H
��R - G� ( G is functional group, R is Alkyl group)
FUNCTIONAL GROUP � +G CnH2n+1 �
�
CnH2n+1 �

1. Alkyl Halide
The alkyl halides have the general formula C nH2n+1X or RX, where X denotes fluorine, chlorine
bromine or iodine.
CH3

CH3 H3C

H3C H3C

Br Br Cl
bromoethane 2-bromopropane 1-chloro-2-methylpropane
H3C
CH3
CH3 Br Br
H3C
H3C
CH3
Cl Br H3C CH3
2-chloro-2-methylpropane 1-bromo-2,2-dimethylpropane 2,4-dibromopentane
Br
H2C
H2C
Cl
Br H2C CH3
3-bromoprop-1-ene 6-bromohepta-1,5-dien-3-yne chloroethene
H
Br

Br

Br Cl
1,2-dibromoethane bromocyclohexane Phenyl chloro methane
2. Alcohols
General formula [CnH2n+1.OH], IUPAC name is alkanol.
For the simpler alcohols the common names, are most often used. These consist simply of the
name of the alkyl group followed by the word alcohol. For example:
OH
CH3
H3C
OH OH
H3C CH3 H3C
propan-1-ol propan-2-ol 2-methylpropan-1-ol

CH3 b
CH3
H3C a
OH
OH CH3 O 2N OH
2-methylbutan-2-ol (3-nitrophenyl)methanol 1-phenylethanol

We should notice that similar names do not always mean the same classification; for example,
isopropyl alcohol is a secondary alcohol, whereas isobutyl alcohol is a primary alcohol.
Finally, there is the most versatile system, the IUPAC. The rules are:
1. Select as the parent structure the longest continuous carbon chain that contains the
-OH group; then consider the compound to have been derived from this structure
by replacement of hydrogen by various groups. The parent structure is known
as ethanol, propanol, butanol, etc., depending upon the number of carbon
atoms; each name is derived by replacing the terminal -e of the corresponding alkane name
by -ol.
2. Indicate by a number the position of the -OH group in the parent chain, generally using the
lowest possible number for this purpose.
3. Indicate by numbers the positions of other groups attached to the parent chain.
H3C OH

H3C OH CH3 OH
ethanol 2-methylbutan-1-ol 2-phenylethanol
OH
H3C
CH3 CH3 OH
H3C
H3C OH CH2
OH CH3 Cl H3C
2-methylbutan-2-ol 3-methylbutan-2-ol 2-chloroethanol but-3-en-2-ol

Alcohols containing two hydroxyl groups are called glycols. They have both common names
and IUPAC names.
CH3
OH
H3C
CH3
H3C
H
OH
HO OH
HO OH H
3,4,5-trimethylcyclopentane-1,2-diol
Ethane-1, 2 - diol Propane-1, 2 - diol
Note:
2 or 3 OH group can not present on same carbon atom, decomposes to give
aldehyde/ketone or carboxylic acid respectively.

OH
-H2O
R C OH R C O

H H
Aldehyde
OH O
-H2O
R C OH R C O

R R
Ketone
OH OH
-H2O
R C OH R C O

OH Carboxylic acid

3. Ether (R  O  R]
Ethers are compounds in which two C atoms are connected to a single O atom. In IUPAC
nomenclature, name one of the alkyl group plus the O atom (RO) as an alkoxy and comes
as a prefix to the parent hydrocarbon. (Oxygen is to be counted with least number of carbon
atom)
IUPAC name of ether is alkoxy alkane

CH3OCH(CH3)2 2 – Methoxy propane (isopropyl methlyl ether)

OCH3

1 – isopropoxy – 2 – methaoxy – cyclohexane

OCH(CH3)2

H3C O
CH3 Methoxy ethane

4. Aldehydes
IUPAC names the longest continuos chain including the C of – CH = O and replaces – e of the
alkane name by the suffix – al i.e. alkanal. The C of CHO is number 1. For compounds with two –
CHO groups, the suffix – dial is added to the alkane name. When other functional groups have
naming priority, – CHO is called formyl.
Common names replace the suffix –ic (–oic or – oxylic) and the word acid of the corresponding
carboxylic acids by – aldehyde. Locations of substituents on chains are designated by Greek
letters e.g.
e d g b a
 C C C C C C = O
|
H
The terminal C of a long chain is designated w (omega)
The IUPAC names of aldehydes follow the usual pattern. The longest chain containing the –CHO
group is considered the parent structure and named by replacing –e of the corresponding alkane
by –al. The position of the substituent is indicated by a number, the carbonyl carbon always being
considered C-1. Here, as with the carbonyl acids, the C-2 of the IUPAC name corresponds to
alpha of the common name.
H
H H H

H O H3C O H3C O H3C O

formaldehyde acetaldehyde propionaldehyde butyraldehyde
H H
O 2N CHO H3C
O O
benzaldehyde 4-nitrobenzaldehyde 4-methylbenzaldehyde
H

O
H
OH O
salicylaldehyde phenylacetaldehyde
CH3 CH3

O O O
H3C H3C H3C

H CH3 H H
2-methylpentanal 3-methylpentanal 4-methylpentanal

5. Ketones
Common names use the names of R or Ar as separate words, along with the word ketone. The
IUPAC system replaces the –e of the name of the longest chain by the suffix –one. In molecules
with functional groups such as – COOH, that have a higher naming priority, the carbonyl group is
indicated by the prefix keto or oxo. Thus, CH3COCH2CH2COOH is 4-ketopentanoic acid.

The simplest aliphatic ketone has the common name acetone. For most other aliphatic ketones
we name the two groups that are attached to carbonyl carbon and follow these names by the
word ketone. A ketone in which the carbonyl group is attached to a benzene ring is named as
phenone, all illustrated below. The positions of various groups are indicated by numbers.
O O
CH3
H3C

H3C CH3 H3C CH3

O
acetone butan-2-one pentan-2-one
CH3

CH3
H3C CH3 H3C
CH3
O O O
pentan-3-one 3-methylbutan-2-one 1-phenylacetone

CH3
CH3

O O O
1-phenylethanone 1-phenylbutan-1-one benzophenone

6. Carboxylic acid
(i) Common or Trivial names:
The names of lower members are derived from the Latin or Greek word that indicate the source of the particular
acid.
Common or trivial
Formula Source
names
HCOOH Red ant (Latin ant – formica) Formic acid
Vinegral (Latin vinegar
CH3 – COOH Acetic acid
acetum)
Proton-pion
CH3 – CH2 – COOH (Greek = Proton = first, pion = Propionic acid
fat)
(ii) Derived System:
Monocarboxylc acid may be named as alkyl derivative of acetic acid.
CH3
H3C H3C
COOH COOH
Methyl acetic acid Dimethyl acetic acid

(iii) IUPAC System:

Acids are named as alkanoic acids. The name is derived by replacing ‘e’ of the corresponding
alkane by oic acid.
HCOOH Methanoic acid
CH3COOH Ethanoic acid
CH3CH2COOH Propanoic acid
In case of substituted acids, the longest chain including carboxyl group is selected and numbering is done from the
carbon of carboxylic group.
CH3
Example
:
H3C COOH

CH3
3,4-dimethylpentanoic acid

Illustration 3. Give the IUPAC name of the following compounds

O OH

CH3 CH2 CH CH COOH

(b
(a) )
H O
O
H2C COOH
COOH
(d C(OH) - COOH
(c) )
H2C COOH
OHC

Solution: (a) Pent-2-enoic acid

(b) 2-formyl ethanoic acid
(c) 4- formyl -2- oxocylo hexananoic acid
 (d) 3-hydroxy propane-1, 2, 3-tricarboxylic acid

Exercise 4.
Write IUPAC name of the following:
(i) X (ii)

(iii)
H3C COOH
(iv OH
)
CHO

H3C
H3C Cl
OH

7. Derivative of Carboxylic acid

O O
--OH
R C O H R C Z
Z
Alkanoic acid Acid derative

Z = derivative of carboxylic acid

Acyl Group
(i) Naming Acyl Groups- Acid halide and Anhydrides
The group obtained from a carboxylic acid by the removal of the hydroxyl portion is known as
an acyl group. The name of an acyl group is created by changing the - ic acid at the end of
the name of the carboxylic acid to –yl, examples:
O O
|| ||
H –C – O – H H –C –
Formic acid Formyl group

O O
|| ||
 C – OH C–

Benzoic acid Benzoyl group

(a) Acid Halide

IUPAC name of acid halide is alkanoyl halide.

where X may be Cl, Br, I

Acid chlorides are named systematically as acyl chlorides.

(b) Acid anhydride
An acid anhydride is named by substituting anhydride for acid in the name of the
acid from which it is derived.

IUPAC name of acid anhydride is alkanoic anhydride.

O O

R C O C R
Example:
O O

H3C C O C C3 H7

Butanoic, ethanoic anhydride

(ii) Naming Salts and Esters

General formula of ester RCOOR
O

R C O R'

IUPAC name: Alkyl alkanoate

Example:
CH3COOC2H5 (Ethyl ethanoate)

The name of the cation (in the case of a salt) or the name of the organic group attached to the
oxygen of the carboxyl group (in the case of an ester) precedes the name of the acid.

(iii) Name of Amides and Imides

The names of amides are formed by replacing –oic acid (or –ic acid for common names) by
amide or –carboxylic acid by carboxamide.
IUPAC name of acid amide is alkanamide
O

R C NH2
Example:

If the nitrogen atom of the amide has any alkyl groups as substitutents, the name of the
amide is prefixed by the capital letter N; to indicate substitution on nitrogen, followed by the
name(s) of alkyl group(s).

If the substituent on the nitrogen atom of an amide is a phenyl group, the ending for the name
of the carboxylic acid is changed to anilide

Exercise 5.
Write IUPAC name of the following
(i) CH2(OH), CH(CH3)COCl
(ii) CH3COOCOC6H5
(iii) CH3CHOHCHClCHOCH3CONH2
(iv) CH3CHCH3CHOHCH2COCl

Some dicarboxylic acids form cyclic amides in which two acyl groups are bonded to the
nitrogen atom. The suffix imide is given to such compounds.
O O

NH NH

O O
Succinimide Phthalimide

8. Amine
Nomenclature of amines

Nomenclature of amines is quite simple. Aliphatic amines are named by naming the alkyl
group (or) groups attached to nitrogen , and following that by the word amine.
More complicated amines are often named as prefixing amino - (or-N-methylamino -, N-N,
diethyl amino -, etc) to the name of the parent chain.

Aromatic amines - those in which nitrogen is attached to an aromatic ring - are generally
named as derivatives of the simplest aromatic amine, aniline.
Br
CH3
NH2 N
C2H5

Br Br
(N-ethyl-N-methyl aniline)
(2,4,6-Tribromo aniline)

Salts of amines are generally named by replacing - amine by - ammonium (or - aniline by -
anilinium), and adding the name of the anion.
NH3Cl–

(CH3)3NHNO3–
(Trimethylammonium nitrate) (Anilinium chloride)

9. Nitro Alkane

General formual CnH2n+1.NO2

CH2 CH2

R N or R N

O O
Nitro alkane
Example:
NO 2
NO2

H3C CH CH3 H3C CH3

2-nitro propane

H3C CH3

2 nitro 3, 3 dimethyl pentane

NO 2
Alkyl nitrites
Common name is alkyl nitrite there is no IUPAC name of nitrite.
R–O–N=O Alkyl nitrite
CH3CH2 – O NO Ethyl nitrite
10. Alkyl Cyande
R–CN Alkane nitrile
Example:
CH3 – C  N Ethane nitrile
H3C

CN
2 methyl propane nitrile
H3C
Alkyl iso cyanide RNC
R N C
Alkyl iso nitrile or alkyl iso cyanide.
There is no specific IUPAC name for alkyl iso cyanide or isonitrile.
CH3NC Ethyl isonitrile
When a compound contains more than one functional group, the numbering and the suffix in the
name of multifunctional compound are determined by nomenclature priority.
Preference Order

Class Formula Suffix Prefix

(if present as (if present as
a functional a substituent)
group)
Carboxylic acid O oic acid Carboxy
C OH
Acid ahydrides O O oic anhydride
C O C
Eaters O Alkyl alkanoate Alkoxycarbonyl
C O
Acyl halides O oyl halide Haloalkanoyl
C X
Amides O -amide Carbamoyl
C NH2
Nitriles CN Nitrile Cyano
Aldehydes O al Formyl
C H
Ketones O one Oxo
C
Alcohols OH ol Hydroxy
Amines H/R Amine Amino
N
H/R
Ethers O Alkoxy alkane oxy
Alkenes ene Alkenyl

Alkynes CC -yne Alkynyl

Halides X  Halo
 Nitro NO2  Nitro
Alkanes ane Alkyl
C C

Benzene Benzene Phenyl

BENZENE COMPOUND
For naming aromatic compounds, no special rules are required, but are named substituted
benzene.
The benzene ring is considered to be a parent and alkyl groups, halogens and the nitro group are named as prefix to
benzene.
CH3 Br NO2

Methyl benzene Bromobenzene

Nitrobenzene

Br Cl

Br O 2N NH2

2 – chloro – 4 – nitro aniline

Br
1, 3, 5 – tribromobenzene
OH

O2N COOH

2 – hydroxyl – 4 – nitro – benzoic acid

When a benzene ring is attached to an alkane chain with a functional group or to an aklane chain of two or more carbon
atoms, then benzene is considered as a substituent (phenyl) instead of a parent.
CH2CH2OH
OH

HC CH2CH2Br
2- phenyl ethanol 2- bromo - 1 - phenyl propanol

When more than one group is present on benzene ring then following prefix are giving to certain
organic compound.
G
2 & 6 = Ortho or ‘o’
1
3 & 5 = Meta or ‘m’
6 2
4 = Para or ‘p’
With respect to G.
5 3
4
 CH3 CH3 CH3
CH3

CH3
O - Xylene m - Xylene CH3
p - Xylene

The following names are given to certain aromatic hydrocarbon residues formed by the loss of one or more hydrogen
atoms from the parent hydrocarbon.
CH3

C2H5--- C6H4
(Phenyl) CH3C6H4---
(O-Phenylene)
(O-Tolyl)

CH2 CH C

C6C5CH2---
C6C5CH- C6C5C
(Benzyl or Phenyl
methyl))
(Benzal or Benzylidene) (Bezo or Benzylidene)

ALICYCLIC (CYCLIC COMPOUNDS)

IUPAC name-cycloalkane (saturated), cyclo alkene, cyclo alkyne (unsaturated)……………….
Examples:
CH2

or (cyclo pentene)
(cyclo propane)
H 2C CH 2

(cyclo butyne)

Note:
Naming of cyclic compounds containing functional group – same as open chain
compound.

Exercise 6.
Write the IUPAC name of compounds
OH H3C CH CH2COOH
(i) (ii
)

BOND CLEAVAGE
Organic reactions take place through the formation of reactive intermediates. These
intermediates are formed due to cleavage of covalent bonds. These intermediates can be
�
(i) free radicals like CH3
�
(ii) carbocation like CH3
 
(iii) carbanion like CH3

Homolytic (symmetrical) cleavage

In which the two electrons shared in a  bond become unpaired as the bond is broken.
Light/Heat
CH3 CH3 CH3 CH3

Light/Heat
CH3 NH2 CH3 NH2
The species formed are called free radicals
(i) They are electrically neutral.
(ii) They are extremely reactive.
Their stability is in the order of
R
R

R C > CH > RCH2 > CH3

R
R

30 20 10

Benzylic and allylic free radicals are resonance stabilized hence are more stable than alkyl free
radicals.


 H2C H2C  H2C

H2C


Benzyl radical
 
H2 C CH CH2 H2C CH CH2

Allyl radicals
�
Thus greater the stability easier will be formation of the species. CH3 (Methyl radical) is
sp2 – hydridized (bearing three  CH bonds and singly occupied p – orbital) with HCH angle
1200 and three C  H bonds coplanar. Thus when a methyl radical is formed in the homolytic
cleavage of CH3  X bond, the carbon undergoes a geometric change from tetrahedral to planar
and rehybridisation from sp3 to sp2.
Heterolytic (unsymmetrical) cleavage
When a covalent bond joining two atoms A and B breaks in such a way that both the electrons of
the covalent bond (i.e. shared pair) are taken away by one of the bonded atoms, the mode of
bond cleavage is called heterolytic cleavage. Heterolytic cleavage is usually indicated by a
curved arrow which denotes a two electron displacement. For example

Heterolytic cleavage
A : B A B (When B is more electronegative than A)

Heterolytic cleavage
A : B A B
(When A is more electronegative than B)
As shown above heterolytic fission results in the formation of charged species, i.e. cations and
anions. It usually occurs in polar covalent bonds and is favoured by polar solvents.
In the formation of carbocation, we also find that sp 3 hybridised carbon (in CH3 X) changes to
sp2 hybridised carbon.
An organic ion with a pair of available electrons and a negative charge on the central carbon
atom is called carbanion and stability is in order
CH3

CH3 > CH3CH2 > H3C CH > H3C C

CH3 CH3
Electron attracting group (CN, > C = O) increases stability and electron – releasing group
( CH3 etc) decreases stability of carbanion.
Benzyl carbanion is again stabilized by resonance.

H2 C H2 C H2 C H2 C

Exercise 7.
The greater the s-character in an orbital the ------------ is its energy
(A) Greater (B) Lower
(C) Both (D) None

REACTION INTERMEDIATES
Most of organic reactions occurs through the involvement of certain chemical species. These are
generally short lived (10-6 seconds to a few seconds) and highly reactive and hence can not be
isolated. These short lived highly reactive chemical species. Through which the majority of the
organic reactions occur are called reactive intermediates. These intermediates are detected by
spectroscopic methods or trapped chemically or their presence is confirmed by indirect evidence.
On the other hand, synthetic intermediate are stable products which are prepared isolated and
purified and subsequently used as starting materials in a synthetic sequence.
Carbocations (Earlier Called As Carbonium Ions)
Carbocations are the key intermediates in several reactions and particularly in nucleophilic
substitution reactions and electrophilic addition reaction.
(a) Structure:

Generally in the carbocations the positively charged carbon atom is bonded to three others atoms
and has no nonbonding electrons. It is sp 2 hybridized with a planer structure and bond angles are
+
of about 1200. There is a vacant unhybridised p orbital which (e.g in the case of CH3 ) lies
perpendicular to the plane of C  H bonds.
E
m p
ty

R
1
200

C R

R s
p 2
-h y
brid
ize
dc arbo
norb
ita
l &
s
tructu
reofcarb
oca
tion
s

(b) Stability:
There is an increase in carbocation stability with additional alkyl substitution. Thus one finds that
addition of HX to three typical olefins decreases in the order
(CH3)2C = CH2 > CH3  CH = CH2 > CH2 = CH2
This is due to the relative stabilities of the carbocations formed in the rate determining step which
in turn follows from the fact that the stability is increased by the electron releasing methyl group
(+I), three such groups being more effective than two, and two more effective than one.
Stabilized by three electron releasing groups
CH3

CH3 C > H C
3 CH CH3 > H2 C CH3

CH3
+
Stability of carbocations 30 > 20 > 10 > CH3
Electron release: Disperses charge, stabilizasion.
Further, any structural feature which tends to reduce the electron deficiency at the tricoordinate
carbon stabilizes the carbocation. Thus when the positive carbon is in conjugation with a double
bond. The stability is more. This is so, due to resonance the positive charge is spread over two
atoms instead of being concentrated only on one. This explains the stability associated with the
allylic cations. The benzylic cations are stable, since one can draw canonical forms as for allyl ic.
CH2 CH2 CH2
CH2

The benzyl cation stability is affected by the presence of substituents on the ring. Electron
donating p – methoxy and p – amino group stabilize. The carbocation by 14 and 26 kcal/mole,
respectively. The electron withdrawing groups like e.g, p – nitro destabilize by 20 kcal/mol.
A heteroatom with an unshared pair of electrons when present adjacent to the cationic centre
strongly stabilizes the carbocation. The methoxy methyl cation has been obtained as a stable
+ -
solid CH3 OCH2SbF6 cylopropylmethyl cations are even more stable than the benzyl cations.
This special stability is a result of conjugation between the bent orbitals of the cyclopropyl ring
and the vacant p orbital of the cationic carbon. The carbocations are planar is shown by the fact
these are difficult or impossible to form at bridgeheads, where they can not be planar.
+
The stability order of carbocation is explained by hyperconjugation. In vinyl cations (CH2 = CH) ,
resonance stability lacks completely and therefore are very much less stable.
Stability  hyperconjugated structures  number of a hydrogen.
Exercise 8.
Which of the following carbocations is most stable?
Exercise 9.
Which of the following C – Cl bond is weaker.
Cl
(a) Ph – | – CH3 (b) Ph – CH2 – CH2 – Cl
CH

Exercise 10.
Arrange the following in the increasing order of C – Br bond energy.
Br
|
(a) CH3 – C CH2 – CH3
|
CH3
Br
(b) CH3 – | – CH2 – CH2 – CH3
CH
(c) CH3 – CH2 – CH2 – CH2 – CH2 – Br
(d) CH2 = CH – Br
(e) Ph – CH2 – Br

Exercise 11.
Which of the following C – I bond is weak and why?
(i) CH3 – O – CH2 – I
H
(ii) CH3 – | – CH2 – I
N

Carbanions
Chemical species bearing a negative charge on carbon and possessing eight electrons in its
valence shell are called carbonions. These are produced by heterolylic cleavage of covalent
bonds in which the shared pair of electrons remain with the carbon atom.
(a) Structure:
A carbanion posses an unshared pair of electron and thus represents a base. The best likely
description is that the central carbon atom is sp 3 hybridized with the unshared pair occupying one
apex of the tetrahedron. Carbonions would thus have pyramidal structures similar to those of
amines. It is believed that carbanions undergo a rapid interconversion between two pyramidal
forms.
There is evidence for the sp3 nature of the central carbon and for its tetrahedral structure.
At bridgeheads carbon does not undergo reaction in which it is converted to a carbocation.
However, the reactions which involve carbanions at such centre take place with ease, and stable
bridgehead carbanion are known. In case this structure is correct and if all three R groups on a
carbanion are different, the carbanion should give retention of configuration. However, this never
happens and has been explained due to an umbrella effect as in amines. Thus the unshared pair
and the central carbon rapidly oscillate from one side of the plane to the other.
(b) Stability and Generation:
The Grignard regent is the best known member of a broad class of substances, called
organometallic compounds where carbon is bonded to a metal lithium, potassium sodium, zinc,
mercury, lead, thallium almost any metal known. Whatever the metal it is less electronegative
than carbon and the carbon metal bond like the one in the Grignard reagent is highly polar.
Although the organic group is not a full fledged carbanion an anion in which carbon carries
negative charge, it however, has carbanion character organometallic compounds can serve as a
source form which carbon is readily transferred with its electrons. On treatment with a metal, in RX the direction of the
original dipole moment is reversed (reverse polarization)
d+ d
d d
CH3 CH2  Br Mg CH3CH2 Mg Br

Considerable carbanion character

R C C Also acetylide ion

(c) Properties:
carbanions are nucleophilic and basic and in this behaviour these are similar to amines, since the
carbanion has a negative charge on its carbon, to make it a powerful base and a stronger
nucleophile than an amine. Consequently is enough basic to remove a proton from ammonia.
Illustration 4. Identify the stable carbanion in each pair

(a) CH3 – CH2 – CH2– and CH3 – CH – CH3
 O  O
(b) CH2 – || – CH3 and CH2 – CH2 – || – H
C C
(c) Ph – CH2– and Ph – CH2 – CH2–

Solution: (a) CH3 – CH2 – CH2– (because of inductive effect)

 O
(b) CH2 – || – CH3 (because of mesomeric effect)
C
(c) Ph – CH2– (because of resonance)

Free Radicals
A free radical is a species which has one or more unpaired electrons. In the species where all
electrons are paired the total magnetic moment is zero. In radicals, however, since there are one
or more unpaired electrons. There is a net magnetic moment and the radicals as a result are
paramagnetic. Free radicals are usually defected by electron spin resonance, which is also
termed electron paramagnetic resonance.
Simple alkyl radicals have a planar (trigonal) structure i.e., these have sp 2 bonding with the odd
electron in a p orbital. The pyramidal structure is another possibility when the bonding may be sp 3
and the odd electron is in an sp 3 orbital. The planar structure is in keeping with loss of activity
when a free radical is generated at a chiral centre. Thus, a planar radical will be attacked at either
face after its formation with equal probability to give enantiomers unlike carbocations, the free
radicals can be generated at bridge. This shows that pyramidal geometry for radicals is also possible
and that free radicals need to be planar
H H
H H
p - orbital sp3 - hybridized orbital

C C

H H

Pyramidal structure
Stability

As in the case of carbocation, the stability of free radicals is tertiary > secondary > primary and is
explained on the basis of hyperconjugation. The stabilizing effects in allylic radicals and benzyl
radicals is due to vinyl and phenyl groups in terms of resonance structures. Bond dissociation
energies shows that 19 kcal/mol less energy is needed to form the benzyl radicals from toluene
than the formation of methyl radical from methane. The triphenyl methyl type radicals are no
doubt stalbilized by resonance, however the major cause of their stability is the steric hindrance
to dimerization..
 
C6H5CH3 C6H5CH2 H
H = +85 kcal
Toulene Benzyl radical

+
Ease of formation of alkyl free radicals, benzyl > 30 > 20 > 10 > CH3 > Vinyl

Illustration 5: Alkenes undergo electrophilic addition reaction and benzene undergoes

electrophilic substitution whereas both proceeds through carbocation
intermediate. Explain.
Solution:  electrons are available in case of alkanes whereas they are delocalized in case
of benzene. After attack of electrophile a stable delocalized carboncation is
formed on benzene ring. Whereas a carbocation which can rearrange is formed
by addition of electrophile on alkane.

Exercise 12.
Which of the following statement is correct?
+
(A) Allyl carbonium ion (CH2=CH– CH2 ) is more stable than propyl carbonium ion
(B) Propyl carbonium ion is more stable than allyl carbonium ion
(C) Both are equally stable
(D) None

ELECTRONIC DISPLACEMENT IN COVALENT BONDS

The following four types of electronic effects operates in covalent bonds
(i) Inductive effect (ii) Electromeric effect
(iii) Resonance and mesomeric effect (iv) Hyperconjugation
Inductive Effect (Polar Nature Of Covalent Bonds)

The displacement of an electron (shared) pair along the carbon chain due to the presence of an
electron withdrawing or electron releasing groups in the carbon chain is known as inductive effect
(I – effect).
 It is a permanent effect which is transmitted along the chain.
C……> ……C…>….C……>G (G – Functional group)
 This permanent polarity is due to electron displacement due to difference in
electronegativities.
 This effect weakens steadily with increasing distance from the substitution
(electron – withdrawing or electron – donating group) and actually diminishes down after
three carbon atoms.
There are two types of inductive effect i.e. – I effect and +I effect.
Negative Inductive effect ( I Effect)
If the substituent attached to the end of the carbon chain is electron withdrawing (X). The effect is
called – I effect.
d d
C X
I effect decreases as one goes away from groups (electron attacking)
d d d d
C C C X
3 2 1
C1(d+) > C2(dd+) > C3 (ddd+) and other third carbon charge is negligible.
I effect is in order.
NO2 > F > COOH > Cl > Br > I > OH > C6H5
Due to I effect (electron – with drawing nature) electron density decreases, hence basic nature
is decreased and acidic nature is increased.
Chloroacetic acid is stronger than acetic acid since Cl shows (-I) effect, electron – density is
decreased and O – H bond is weakens causing ionisation of (-COOH) to a greater extent than
CH3COOH.
O O

Cl CH2 C O H CH3 C OH
(-I)
NH3 is a base due to lone pair on nitrogen. Phenyl group is electron – withdrawing. What
happens to electron – density of nitrogen in aniline, Naturally electron – density is decreased.
Hence aniline is weaker base than NH3 .
H N H
H N H

Similarly acidic nature of phenol is greater than H2 O due to electron – withdrawing nature of
phenyl group.
O H
H O H

Positive inductive effect (+I effect):

If the substituent attached to the end of the carbon chain is electron – donating, the effect is
called +I effect.
This is due to electron – releasing (Y). It develops a negative charge on the chain.
d d+
C Y
+I effect also decreases as we go away from group Y (electron – releasing)
ddd dd d d+
C C C C Y
4 3 2 1
C1(d ) > C2 (dd ) > C3 ( ddd)
So +I effect is in the order of
(CH3 )3 C > (CH3 )2 CH > CH3 CH2  > CH3 
Due to electron – releasing group electron density is increased, hence basic nature is also
increased and naturally acidic nature is decreased, thus
-I effect +I effect
Acidic Nature � �
Basic Nature � �

Note:
Inductive effect is a permanent effect operating in the ground state of the organic
molecules and hence is responsible for high melting point, boiling point and dipole
moment of polar compounds.

Illustration 7. Take the following isomerica,b, g chlorobutyric acid

γ

α β
C H2CH2CH2COOH
CH3CH2 C COOH CH3 C HCH2COOH ¯
¯ |
¯ | Cl
| Cl
Cl (II) (III)
(i)

Arrange the acids increasing order of acid strength.

Solution: As we have stated, as we go away from the source, electron - withdrawing

tendency decreases, hence acidic nature also decrease. Thus
(III) < (II) < (I)

Illustration 8. Which of the following carbonyl compound is more acidic?

O O
(a) CH3 – || – CH3 (b) CH3 – || – H
C C

Solution. (b) The acidity of a-hydrogen depends on +ve charge on the carbon atom to
which it is attached. In an aldehyde the carbonyl carbon has more positive
charge and hence more –I effect.

Illustration 9. CH3CO2H is a stronger acid than CH3CH2 – OH. Explain

O
Solution: CH3 – CO2H  CH3 – || – O– + H+
C
CH3 – CH2 – OH CH3 – CH2 – O– + H+
In EtO– the negative charge on O atom is increased by +I effect, whereas in
CH3CO2–, the negative charge on O atom is decreased by delocalisation. Lesser
the charge density on negatively charged atom, weaker is the base.
Electromeric Effect

In presence of an attacking reagent, there is complete transfer of   electrons from one atom to
other to produce temporary polarity on atoms joined by multiple bonds, it is called Electromeric
effect.
 C C ��electrophile
�� ����� ���� ��
added
������
� C C
electrophileremoved

This effect is temporary and takes place only in the presence of a reagent. As soon as the
reagent is removed, the molecule reverts back to its original position. Electromeric effect is of two
types, i.e. +E effect and  E effect.
Positive Electromeric effect (+E effect):

When  electrons transfer takes place C to C (as in alkenes, alkynes etc.), it is called positive
electromeric effect (denoted by + E).
+ 
��electrophile
CH2 = CH2 �� ��� ���� ��
added
������ �
�CH2  CH2
�
electrophile removed
+ 
��electrophile
CH3  CH = CH2 �� ��� ���� � �added
������ �
�CH3  CH  CH2
�
electrophile removed

For example, addition of acids to alkenes

C C + H+  C C

H
(+ E - e ffe c t)

In this, there is also (+I) effect of CH3 group which causes  electron transfer from C2 to C1.
What do you think in the following case:
CH3 CH = CH CH2CH3
(+I) effect of CH3 CH2  is larger than that of CH3 , hence  electron transfer is from C3 to C2 .


CH3 CH CH CH2CH3
1 2 3 4 5

Negative Electromeric effect:

When   electrons transfer takes places to more electronegative atom (O, N, S) joined by
multiple bonds, it is called Negative Electromeric effect (denoted by E).

electrophile added
+ 
C ���
O �� ���� ���� �� �������C  O
electrophile removed

electrophile added
C ���
N �� ���� ���� �� ������� C N
electrophile removed

for example, the addition of cyanide ion to the carbonyl group.

C O CN C O

CN
(-E effect)

Resonance & Mesomeric Effect

There are many organic molecules which can not be represented by a single lewis structure. In
turn, they are assigned more than one structure called canonical forms or contributing of
resonating structures. The phenomenon exhibited by such compounds is called resonance. For
example, 1, 3 – butadiene has following resonance structure.

H2C CH CH CH2 H2C CH CH CH2 H2C CH CH CH2

and canonical forms of vinyl chloride are

H 2C CH Cl H 2C CH Cl

While drawing these canonical forms, the prime thing that has to be kept in mind is that the
relative position of any of the atom should not change while we are allowed to change the relative
positions of  - bonded electron pair or distribution of charge to other atoms. Also remember that
it is not the case that some molecules have one canonical form and some have another form. All
the molecules of the substance have the same structure. That structure is always the same all
the time and is a weighted average of all the canonical forms. In real sense, these canonical
forms have no expect in our imaginations. Now we are in a position to discuss about the
conditions necessary for a compound to show resonance. The two essential conditions are
(a) There must be conjugation in the molecule. Conjugation is defined as the presence of
alternate double and single bonds in the compound like
C C C C

(b) The part of the molecules having conjugation must be essentially planar or nearly planar. The
first condition of conjugation is not only confined to the one mentioned above but some other
systems are also categorized under conjugation. These are
(i) (ii) C C C
(iii) C C C
C C C

O
(iv) C C C (v)
C C N

So, any molecules satisfying both the conditions will show O H

resonance. For example, we consider phenol. The structure of

phenol is

By looking at the structure, it must be clear to you that the compound possesses 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 (sp 2 hybridised) carbon of the ring.
Since, oxygen atom is sp3 hybridized 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, therefore it does show resonance and
its resonance structures are represented as
 O H O H O H O H O H

This has to be borne in mind that resonance always results in different distribution of electron
density than would be the case if there were no resonance. It is a permanent effect, also referred
as mesomeric effect.

Note:
The acidity of phenol can be explained by resonance
O H O

Phenol Penoxide ion

O O O O O O d

d

The above structure shows that the phenoxide ion formed is more resonance stabilised than
phenol. Hence, the acidity of phenol is explained.
Similarly basicity of aniline can be explained.
NH2 NH2 NH2 NH2 NH2

The above structure shows that the lone pair present on N – atom undergoes into resonance and
is not available for donation. Hence, the basicity of aniline decreases and is less than aliphatic
��
amine R  NH .
2

Resonance (mesomeric) effect is of two types.

(i) If the atom or group of atoms is giving electrons through resonance, it is called +R or +M effect. For example,

C C NH2
(+M effect of NH2 group)

Other groups that shows +M effect are NHR, NR2, OH, OR, NHCOR, Cl, Br, I
etc.
(ii) If the atom or group of atoms is withdrawing electrons through resonance, it is called R or
M effect. For example,
 O
C C N (-M effect of NO2 group)

O
Other groups showing M effect are CN, CHO, COR, CO2H, CO2R, CONH2,
SO3H, COCl etc.
Now, let us consider resonance in nitrobenzene and its various canonical structures are
O O O O O O O O O O
N N N N N

The NO2 group in nitrobenzene has M effect. 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.
In drawing the canonical forms and deciding about their relative stabilities, following rules are give
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  butadien.
(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) Structure with formal charges is less stable than uncharged structures. For charged
structure, 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,

CH2 C CH3 CH2 C CH3

O O
(I) (II)]
 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 (expect for hydrogen which have douplet) 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).
Resonance Energy:
The difference in energy between the hybrid and the most stable canonical structure is called as
resonance energy

Illustration10. Why guanidine is basic in nature. Explain the site of protonation and
provide resonating structures.
Solution: + NH2 NH2
NH NH2
H+ C
C  C C +
NH2 NH2 + NH2 H2N NH2
H2N H2N H2N
Guanidine behaves as strong base because it can provide electron pair easily
resulting in three identical resonating structure. Site of protonation is sp 2
hybridised N atom rather than sp3 hybridise N atom resulting in three symmetrical
structures.

Illustration 11. Arrange the various resonating structures of formic acid in order of decreasing stability

Solution: O O O O
+
H C O H > H C O H > H C O H> H C O H

Illustration 12. Explain why phenol is acid while aliphatic alcohols are not.

Solution: After loss of H+ ion from OH group of phenol the remaining part (Phenoxide ion)
stabilizes by resonance, hence it will favour the loss of H + ion and hence acidic in
nature.
    

 OH + OH


3 more R-structure

+
–H (Charge separation is present. Not much stable)
  -    

O 
 

O
  


O

 O 

  
O 


 



(No charge separation, more stabilization by Resonance)

Illustration 13. Why benzyl carbonium ion is more stable than ethyl carbonium ion

Solution: Due to resonance Benzyl carbonium ion is more stable than Ethyl carbonium ion.

Illustration 14. Among orthochlorophenol and orthofluorophenol, which will be a stronger acid
and why?

Solution: The one having a weaker conjugate base will be a stronger acid. If the conjugate
base has to be weak, the negative charge has to be delocalised to a larger
extent.
In o-chlorophenol

Due to the availability of vacant orbitals in chlorine, the negative charge is

delocalised to a larger extent. The same cannot take place in case of F as F
does not have vacant orbitals. So, o-chlorophenol, having a weaker conjugate
base, becomes a stronger acid.

Exercise 13.
Benzylamine is a stronger base than aniline. Explain.

Exercise 14.
Why is always the resonance effect dominating over the inductive effect?

Exercise 15.
Unlike other aromatic amines, why is the following amine strongly basic?

Exercise 16.
Arrange the following alcohols in increasing order of acidity.
(a) CH2 = CH – OH
(b) CH3 – CH2 – OH
Exercise 17.
H3C CH2
(a)
OH
Write resonance structure of the given compound.
(b) Whether this pairs of compound are tautomers

Hyperconjugation
 It is delocalisation of sigma electrons.
 Also known as sigma-pi – conjugation or no bond resonance
 Hyperconjugation is a permanent effect
Occurrence
Alkene, alkynes
Free radicals (saturated type) carbonium ions (saturated type)
Condition
Presence of a–H with respect to double bond, triple bond carbon containing positive charge (in
carbonium ion) or unpaired electron (in free radicals)
Example
H H H
H

H C CH CH2 H C CH CH2 H C CH CH 2 H C CH CH2

H
H H H
Note:
Number of hyperconjugative structures = number of a-Hydrogen. Hence, in above
examples structures i,ii,iii,iv are hyperconjugate structures (4-structures).
Effects of hyperconjugation
Bond Length:
Like resonance, hyperconjugation also affects
bond lengths because during the process the
single bond in a compound acquires some
double bond character and vice-versa. E.g. C
—C bond length in propene is 1.488 Å as
compared to 1.334Å in ethylene.
Dipole moment:
Since hyperconjugation causes these development of charges, it also affects the dipole moment
of the molecule.
Illustration 15. Arrange the following species in increasing order of dipole moment.
Cis  2,3  Dichloro  2  butene Cis  1,2  dichloroethene
(i) , (ii) ,
Cis  1,2  dibromo trans  1,2  dichlorethene
(iii) -1, 2-dichloroethene, (iv)
Solution: H3C Cl H Cl Br Cl Cl H
C C C C

C C C C
H3C I Cl H II Cl Br III Cl H IV Cl
Resultant vector Resultant vector Resultant vector Nonet resultant
vector
In I, there is addition of vector
In II, there will neither be addition nor subtraction of vector
In III, there is subtraction of vector
In IV, the vectors almost cancel each other. So the increasing order of dipole
moment is IV < III < II < I.

Stability of carbonium Ions:

The order of stability of carbonium ions is as follows
Tertiary > Secondary > Primary
Above order of stability can be explained by hyperconjugation. In general greater the number of
hydrogen atoms attached to a-carbon atoms, the more hyperconjugative forms can be written
and thus greater will be the stability of carbonium ions.
CH3 CH2H+

Tertiary carbonium ion H3C—C+ H3C—C

CH3 CH3
(9 equivalent forms)
CH3 CH2H+

Secondary carbonium Ion H3C—C+ H3C—C

H H
(6 equivalent form)
CH3 CH2H+

Primary carbonium Ion H—C+ H—C

H H
(3 equivalent form)

Stability of Free radicals:

Stability of Free radicals can also be explained as that of carbonium ion
� � � �
(CH3 )3 C > (CH3 )2 CH > CH3 CH2 > CH3

Directive influence of methyl group:

The o,p-directing influence of the methyl group in methyl benzene is attributed partly to inductive
and partly to hyperconjugation effect.
CH3
 (orientation influence of the methyl group due to +I effect )

(Orientation influence of methyl group due to hyperconjugation)

The role of hyperconjugation in o,p,-directing influence of methyl group is evidenced by the part
that nitration of p-iso propyl toluene and p-tert-butyl toluene from the product in which —NO 2
group is introduced in the ortho position with respect to methyl group and not to isopropyl or t-
butyl group although the latter groups are more electron donating than Methyl groups
H H

H—C—H H—C—H

H—C—CH3 H3C — C—CH3

CH3 CH3
i.e., The substitution takes place contrary to inductive effect. Actually this constitutes an example
where hyperconjugation overpowers inductive effect.
Illustration 16. Which among the following is most acidic?
Cl
(a)
H3C CH2 CH2 CH COOH
Cl
(b)
H3C CH2 CH CH2COOH
Cl
(c)
H3C CH CH2 CH2 COOH
Cl CH2 CH2 CH2 CH2 COOH
(d)

Solution: As the inductive effect of chlorine decreases with distance (a) will be most acidic
because the carboxylate ion which results after the loss of H + can be stabilized
by electron withdrawing nature of chlorine (I effect) which is strongest in (a)
where chlorine atom is at a - carbon.

Illustration 17. Which among the following is most basic?

(a) CH3CH2NH2
(b) CH3CH = NH
(c) CH3  C  N

Solution: (a) is most basic because here nitrogen is sp 3 hybridized i.e. p – character is
greater than s – character (75% p and 25% s – character), orbital holding lone
 pair is more elongated than spherical, the hold of nitrogen nucleus over these
electrons is less resulting in more basicity.
Illustration 18. Compare the acidic strength of the following
CH3COOH ClCH2COOH Cl2HCCOOH CCl3COOH

Solution: H O H O

CH3COOH < Cl C C O H < Cl C C O H

H Cl

Cl O

< Cl C C O H

Cl
Increasing acidic strength due to increasing number of (I) effect group.

Illustration 19. Explain why aniline is less basic than ammonia.

Solution: The lone pair present at the nitrogen in aniline is delocalized in the ring (by
resonance) and hence, it is not free for protonation, while in ammonia. I t is present
at nitrogen all the time, hence it is readily available for ptrotonation.

Illustration 20. Br
N(CH3)2
Br CH3
—CH3 Br2
AlBr3

Br
–N(CH3)2 and –CH3 both groups are o, p-directing but products are formed
only under direction of –(CH3)2. Explain.

Solution: –N(CH3)2 group as well as –CH3 group are o–, p– directing and if we want to
place both groups, none of the position will be available for S E.
N(CH3)2

—CH3

o–w.r.t CH3
m-w.r.t. N(CH3)2 and so on.
But o, p-directive effect of the stronger donor (–N(CH 3)2) dominates over that of
the weaker donor (–CH 3), hence SE takes place at o-and p-position w.r.t. –N
(CH3)2.
 N(CH3)2
N(CH3)2
—CH3
O Br2 Br —CH3

P Br
Illustration 21. 4- nitrophenol is more acidic than 3,5 - dimethyl –4-nitro-phenol. Explain.
Solution: It is explained in terms of inductive effect and hyperconjugation.
Illustration 22: The order of acidic strength of the following compound is
OH OH
O

C2H5OH H3C OH

(i) (ii) (iv)

NO2
(iii)

Solution: (iv) > (iii) > (i) > (ii)

Illustration 23. Write the following Alkenes in increasing order of their stability with explanation
R2C=CR2, R2C=CHR, R2C=CH2, RCH=CH2, CH2=CH2

Solution Let R= CH3

(a) CH2 = CH2 (no. a-H, no. Hyperconjugation)
H3C H
(b) C=C (3a-H, 3-Hyperconjugative structures)
H
H
H3C H
(c) C=C (6 a-H, 6H–structures)
CH3
H
H3C CH3
(d) C=C (9a–H, 9H–structures)
CH3
H
H3C CH3
(e) C=C (12a–H, 12 H structures)
CH3 CH3
From (a) to (e) number of hyperconjugative structures increases, hence stability
of alkene also increases, hence the correct order is
a< b<c<d<e

Exercise 18.
(i) Which one is more basic?
 O O

H2NH2C C CH3 or H2NH2C C OCH3

(a) (b)
(ii) Why phenol is more acidic than alcohol?
(iii) Why aniline is less basic than aliphatic amines?
(iv) Which among the following is most acidic?
(a) CH3 CH3 (b) CH2 = CH2 (c) HC  CH

Illustration 24. Identify the effects operating in each of the molecule.

(a) CH3Cl
(b) CH3 – CH = CH2
O
(c) CH3 – CH = CH – || – H
C
(d) CH2 = CH – CH = CH2
Solution: (a) Inductive effect
(b) Inductive and hyperconjugative effects
(c) Inductive, hyperconjugative and mesomeric effects
(d) Mesomeric effect and inductive effect
MECHANISM OF ORGANIC REACTION
A chemical equation is only a symbolic representation of chemical reaction which indicates the
initial reactants and final products involved in a chemical change. Reactants generally consist of
two species.
(a) Substrate: One which is being attacked in a chemical reaction
(b) Reagents: The species which attack the substrate molecule
Substrate + Reagent  Products
Br

CH3—CH—CH3 + OH–  CH3—CH=CH2 + H2O + Br–

substrate Reagent Products
It is important to know not only what happens in a chemical reaction but also how it happens.
Most of the reactions are complex and take place via reactive intermediates which may be or may
not be isolated. The reaction intermediates are generally very reactive which readily react with
other species present in the environment to form the products. The detailed step by step
description of chemical reaction is called its mechanism. Mechanism is only a hypothesis to
explain various facts regarding a chemical reaction.
Substrate  Reactive intermediates –— Products
B
r O
H
  —
CH
—CH
—
CH
—CH
3 –
Br– —
CH—
CH
3OH


3

S
ubs
tra
te In
term
ed
ia
te P
ro
duc
t

By knowing the mechanism we can predict the product of a chemical reaction, adjust the
experimental conditions to improve the yield of the products or even alter the course of reaction
to get the different products.
Most of the attacking reagents carry either positive charge (an electron deficient species) or a
negative charge (electron rich species). The positively charged reagents attack the substrate at
points of high electron density while (-vely) charged reagents attack the point of low electron
density. The organic reactions essentially involve changes in the existing covalent bonds present
in the molecules. These changes may involve electronic displacements in covalent bonds
breaking of some of the existing bonds (bond fission), formation of new bonds as well as energy
change accompanying the bond fission and bond cleavage.
We can understand the mechanism of various organic reactions in terms of following well
established basic concepts.
(i) Electronic displacement in covalent bond
(ii) Fission (cleavage) of covalent bonds
(iii) Nature of attacking reagents
Types of Organic Reactions:
All organic reactions can be broadly classified into four catagories.
(a) Substitution reactions
(b) Addition reactions
(c) Elimination reactions and
(d) Rearrangement reactions
(a) Substitution Reactions
In these an atom or a group of atoms in an organic molecule is replaced by another atom or
group of atoms without any change in the remaining part of the molecule. These reactions may
be initiated by free radical, electrophile or nucleophile.
(i) Free radical substitution reaction:
This substitution reaction is brought about by free radicals. For example chlorination of methane
in presence of diffused sunlight. The mechanism of the reaction is as follows.
Cl : Cl  2Cl Chain initiation
CH4 + Cl� � CH� 3 + HCl
�
�
CH�3 + Cl2 � CH3 Cl + Cl
�
�
� �
�
CH3 Cl + Cl� � CH2Cl + HCl �Chain propagation
               �
�
               �
�
�
Cl�+ Cl� � Cl2 �
�
� �
�Chain termination
CH3 + CH3 � CH3 CH3 �
�
(ii) Nucleophilic substitution reoactions:
These reactions are brought about by nucleophile. The reaction can proceed either via S N1 or
SN2 mechanism.
SN1 mechanism:
Rate determining step involves only the species. For example the reaction.
 CH3 CH3

CH3—C—Br + OH–  CH3—C—OH + Br–

CH3 CH3
takes place as follows
Rate
���� � (CH3 )C + + Br 
1st step: (CH3)3CBr determining step Carbocation
2nd step: Attack by nucleophile
CH3
(CH3)3C+ + OH–  CH3—C—OH
CH3
The stability of carbocation is the controlling factor for this mechanism the formation of 3°
carbocation as an intermediate proceeds via this mechanism. In an optically active compound
substitution at chiral centre through S N1 mechanism produces recemic mixture (No 100%
recemization is observed?).
SN2 mechanism: Rate determining step involves two species and reaction proceeds through
transition state.
CH3 Cl + OH � CH3 OH + Cl
H H H H
Rate
determinin
g
HO– C———Cl  HOd---------C-------Cld– HO—C----H+ Cl–
step
H H
H H
Transition state

Since 1° carbocation is less stable than the transition state formed above, the reaction involving
1° alkyl halides proceed via S N2 mechanism. During reaction configuration of carbon is inverted
which is referred to as Walden inversion.

Points to Remember
 The higher the polarity of solvent greater the tendency for S N1 reaction.
 High concentration of the nucleophile favours SN2 reaction while low concentration
favours SN1 reaction.
 Rearrangement of the carbocation (formed in S N1 reaction) leading to more stable
carbocation is observed in SN1 reaction (discussed latter).
 In general SN2 mechanism is strongly inhibited by increasing steric bulk of the
reagents. In such case SN1 mechanism is favoured.
(iii) Electrophilic substitution reactions:
The reaction initiated by an electrophile is known as electrophilic substitution reaction.
Aromatic substitution reactions are the examples of this type of reaction.
FeCl3 �
C6H6 + Cl2 ���� C6H5Cl + HCl
or AlCl3
 The mechanism of this reaction as follows.
+
Formation of electrophile: Cl : Cl + AlCl3  Cl+ + AlCl4
Electrophile attack:

Elimination of proton:
H Cl
+ Cl 
AlCl


4 +HCl +AlCl3

(b) Addition Reactions

Reactions which involve combination between two molecules to give a single molecule of the
product are called addition reactions. Such reactions are typical of compounds containing
multiple (double or tripe) bonds. Depending upon the nature of the attacking species
(electrophiles, nucleophiles or free radicals) addition reactions are of the following types.
(i) Electrophilic addition reaction:
These reactions are brought about by electrophiles and are typical reactions of alkenes and
alkynes.

C
H —C
H=CH +
slow

C +
3 2+H H
3—C H
— C
H3
2
°carbo
catio
n
Br
Fast
CH3—+CH—CH3 + Br–   CH3—CH—CH3
2-Bromopropane
(ii) Nucleophilic addition reactions:
These reactions are brought about by nucleophiles. The characteristics reaction of aldehyde and
ketone are nucleophilic addition reaction i.e., base catalysed addition of HCN to aldehydes or
ketones.
HO– + HCN  H2O + CN–
R R
R
C –
=O+C
N–

 —
R C
— –
O HCN


R
— C
— O
H

CN

R
N
ucle
oph
ile C
N C
N
K
eto
ne K
eto
nec
yno
hyd
rin
e
(iii) Free radical addition reactions:
Addition reactions brought about by free radicals are called free radical addition reactions for
example addition of HBr to alkenes in presence of peroxides.
Peroxide� CH3  CH2  CH2Br
CH3—CH=CH2+HBr ����� � npropyl hydride
The reaction proceeds through following mechanism.
 2RO°
R  O  O  R ���
RO + HBr  ROH + Br
slow � CH3—CH —CH2—Br
CH3—CH=CH2 + Br ����
HBr
CH3—CH—CH2—Br ���� CH3—CH2CH2—Br + Br
fast
Br + Br  Br2
Illustration 25. Identify the 1, 2- and 1-4 addition products of Free Radical addition of CBrCl 3 to
1, 3-butadiene.

Solution:  CCl
C H 2= C H – C H = C H 2   3  C l 3 C – C H 2 – C H – C H = C H 2

Br (I)

C l3 C – C H 2 – C H – C H = C H 2
Br
1,2 ad d itio n p ro d uc t
C l3 C – C H 2 – C H = C H – C H 2
Br
C l3 C – C H 2 – C H = C H – C H 2 B r
1 ,4 a d ditio n p ro d uc t

Illustration 26. Addition of HCl on 1, 3 butadiene gives two products. Explain.

Solution: Mechanism of addition of HCl on 1, 3-butadiene is as follows
+
H+ + CH2 = CH—CH=CH2CH3—+CH—CH=CH2CH3—CH=CH–CH2
Step:1
An allylic cation equivalent to
CH3—CH— CH—CH2
d+ d+
(Resonance hybrid)
(a)
CH3CH—CH=CH2 1,2 addition
Step:2 ..
CH3—CH— CH—CH2 + :Cl:
.. — Cl (78%)
d+ d+
(b)
CH3CH=CHCH2Cl 1,4 addition (22%)
In step 1 proton adds to one of the terminal cabons of 1, 3 butadiene to form, as
usual, the more stable carbonium ion, in this case a resonance stabilized allylic
cation. Addition of one of the inner carbon atoms would have produced a much
less stable primary cation that could not be stabilized by resonance;
+
CH2=CH—CH=CH2  CH2—CH2—CH=CH2
+
H
In step (2), a chloride ion forms a bond to one of the carbon atoms of the
allylic cation that bears a partial positive charge. Reaction at one carbon atom
results in the 1, 2 – addition product, reaction at the other gives that 1,4 addition
product.

Exercise 19.
Arrange the following in increasing order of reactivity towards H + addition.

(c
(a)
)

(d
(b)
)

(c) Elimination Reactions

An elimination reaction is one which involves the loss of two atoms or groups of atoms from the
same or adjacent atoms of a substrate molecule leading to formation of multiple (double or triple)
bond. These are of two types.
(i) b - elimination reactions. In these reactions, loss of two atoms or groups occurs from the
adjacent atoms of the substrate molecule e.g., acid catalysed dehydration of alcohol and base
catalysed dehydrogenation of alkyl halides.
H

H3C conc.H SO

2 4
H3C CH2 +H O
2
H OH

E1 mechanism
H H
slow
— C— C—     — C — C +— + X –

H
B:
fast 
— C — C +—   C = C + H :B

E2 Mechanism

B: H B H
–
—C——C——slow
—C——C—— C=C +:X +HB

X X
Transitionstate
E1 — CB mechanism

(ii) a - Elimination – In these reactions loss of two atoms or groups occurs from the same atom of
the substrate molecule. E.g., base catalysed dehydrohalogenation of chloroform to form
dichlorocarbene.
Cl
Cl H Cl Cl
C + OH–-  C–  C: + Cl–
Cl Cl –H2O Cl
Cl
Dichlorocarbene is the reactive intermediate involved in carbylamine reaction and
Reimer – Tieman reaction.

(d) Rearrangement Reaction

These reactions involve the migration of an atom or a group of atoms from one atom to another
within the same molecule.
Some reactions involving rearrangement.
AlCl3 � Br
CH3  CH2  CH2  CH2  Br ���� |
575K CH3  CH2  C H  CH3
CH3 CH3
C H OH CH —C—CH —CH
CH3—C—CH2—Br    3 2 3
2 5

CH3 OCH2CH3
CH3Br CH3
Alc
CH3—C—CH2  .KOH
 CH3—C=C—CH3

CH3 CH3
CH3 CH3
HCl
CH3—C—CH=CH2  CH3—C—CH2—CH3
H Cl
O
||
Br
/ KOH
R  C NH2   R—NH2 + K2CO3
2

1° amide 1° amine
1, 2 Hydride shift
C
H3 C
H3 C
H3 C
H3


Br 
Br
C
H—C
—C
3H
—CH
C
H—C
—CH
—CH
CH—
C
3—
CH
—CH
 C
H—C
—CH
—CH 3 3 3 2 3 3 3
 
HB
r H B
r
3
°ca
rb
oc
at
ion
M
ajo
rpr
odu
ct

1, 2 Methyl shift

Illustration 27. Can you think why the below given is order of bases reaction with conc. HCl
(in presence of anhydrous ZnCl2, mixture is called Lucas’s reagent).
CH3

CH3 O H < CH3CH2 OH < CH3 CH OH < CH3 C OH

CH3 CH3

Solution: Naturally the one which is the strongest base, will react faster
ROH+ HCl ��� ZnCl2
� RCl + H2O
base Conc. acid white turbidity
 It is simply a reaction between acid and a base and the strongest base will be
reacting fastest. This is called Luca’s test of making distiction between 1 0, 20 and
30 alcohol.
Illustration 28. Give the mechanism
Me
(i) Me
OH Me
H

Me
CH3
(ii)
Br
CH3
CH3
CH2 HBr

H Me
Solution: (i) Me Me Me Me
O Me
-CH 3 H
H
shift

Me

Me
CH3
(ii)
CH3 CH3
CH3
H

CH3
CH2
Br

H3C Br

CH3

Rearrangement of carbocation through ring expansion.

Exercise 20.
(i) Which of the following intermediate is unstable?

(a) (b)
(ii) Arrange the following carbocation in the order of decreasing stability
 OH
(a) CH3 CH3

CH3
CH3
H3C CH3
H3C
(I)
H3C
OH
(II) OH
(III)
+ +
(b) Why CH3 - O - CH2 is more stable than CH3CH2 CH2 while both are primary
carbocations?

Exercise 21.
Explain the following observations.
OH –
(i) CH3 – I ��� � CH3OH + I
 –
(ii) CF3 – I ���
OH
� CF3H + IO
ISOMERISM
In the study of organic chemistry we come across many cases when two or more compounds are
made of equal number of like atoms. A molecular formula does not tell the nature of organic
compound; sometimes several organic compounds may have same molecular formula. These
compounds possess the same molecular formula but differ from each other in physical or
chemical properties, are called isomers and the phenomenon is termed isomerism (Greek, isos
= equal; meros = parts). Since isomers have the same molecular formula, the difference in their
properties must be due to different modes of the combination or arrangement of atoms within the
molecule. Broadly speaking, isomerism is of two types.
(i) Structural Isomerism
(ii) Stereoisomerism
(i) Structural isomerism: When the isomerism is simply due to difference in the
arrangement of atoms within the molecule without any reference to space, the
phenomenon is termed structural isomerism. In other words, while they have same
molecular formulas they possess different structural formulas. This type of isomerism
which arises from difference in the structure of molecules, includes:
(a) Chain or Nuclear Isomerism;
(b) Positional Isomerism
(c) Functional Isomerism
(d) Metamerism and
(e) Tautomerism
(ii) Stereoisomerism: When isomerism is caused by the different arrangements of atoms or
groups in space, the phenomenon is called Stereoisomerism (Greek, Stereos =
occupying space). The stereoisomers have the same structural formulas but differ in the
spatial arrangement of atoms or groups in the molecule. In other words, stereoisomerism
is exhibited by such compounds which have identical molecular structure but different
configurations.
Stereoisomerism is of two types:
(a) Geometrical or cis-trans isomerism; and
(b) Optical Isomerism.
Thus various types of isomerism could be summarized as follows.
STRUCTURAL ISOMERISM

Chain or Nuclear Isomerism

This type of isomerism arises from the difference in the structure of carbon chain which forms the
nucleus of the molecule. It is, therefore, named as chain, nuclear isomerism or Skeletal
isomerism. For example, there are known two butanes which have the same molecular formula
(C4H10) but differ in the structure of the carbon chains in their molecules.
CH3

CH3
H3C H3C CH3
n - butane isobutane
While n-butane has a continuous chain of four carbon atoms, isobutane has a branched chain.
These chain isomers have somewhat different physical and chemical properties, n-butane boiling
at -0.5o and isobutane at -10.2o. This kind of isomerism is also shown by other classes of
compounds. Thus n-butyl alcohol and isobutyl alcohol having the same molecular formula
C4H9OH are chain isomers.
CH3

H3C OH H3C
n - butyl alcohol
OH
isobutyl alcohol
It may be understood clearly that the molecules of chain isomers differ only in respect of the
linking of the carbon atoms in the alkanes or in the alkyl radicals present in other compounds.
Illustration 29. How many chain isomers does butane have?
CH3
Solution:
CH2
H3C H3C CH2

n - Butylene (1-Butene) Isobutylene (2-Methylpropene)

Illustration 30. How many chain isomers does propyl benzene have?
H3C CH3
Solution: CH2CH2CH3

n - Propylbenzene Isopropylbenzene

Illustration 31. Give the possible chain isomers for ethyl benzene.
 CH2CH3 CH3
Solution:
CH3

Ethylbenzene Xylene (o, m, p)

Positional Isomerism
It is the type of isomerism in which the compounds possessing same molecular formula differ in
their properties due to the difference in their properties due to difference in the position of either
the functional group or the multiple bond or the branched chain attached to the main carbon
chain. For example, n-propyl alcohol and isopropyl alcohol are the positional isomers.
OH
|
CH3–CH2–CH2–OH CH3–CH–CH3
n-propyl alcohol isopropyl alcohol
Butene also has two positional isomers:
CH2=CH–CH2–CH3 CH3–CH=CH–CH3
1-butene 2-butene
1-Chlorobutane and 3-Chlorobutane are also the positional isomers:
CH3  CH2  CH2  CH2Cl CH3 CH2  CHCl  CH3
1Chlorobutane 2Chlorobutane
Methylpentane also has two positional isomers:
CH3—CH2—CH2—CH—CH3 CH3—CH2—CH—CH2—CH3

CH3 CH3
2-Methylpentane 3-Methylpentane
In the aromatic series, the disubstitution products of benzene also exhibit positional isomerism
due to different relative positions occupied by the two substituents on the benzene ring. Thus
xylene, C6H4(CH3)2, exists in the following three forms which are positional isomers.
CH3 CH3 CH3
CH3

CH3
o - Xylene
m - Xylene CH3
p - Xylene

Illustration 32. C2H4Cl2 can have two position isomers 1, 2- and 1, 1-dichloro ethane. Each is
subjected to following sequence of reactions:
KCN� ���� H3O+
C2 H4Cl 2 ���� � ���
What is the end product in each case?
Solution: CH2Cl
Cl
CH2Cl CH3—CH
Cl
KCN KCN
CN
CH2CN CH3CH
CN
CH2CN
H3O+
H3O+ COOH
CH2COOH CH3—CH
COOH
CH2COOH 

CH3CH2COOH
propanoic acid
CH2CO
O
CH2CO
succinic anhydride (if two—COOH groups are
(if two –COOH groups are at same C-atom heating
at adjacent C-atoms would eliminate CO2)
heating would eliminate
H2O)

Exercise 22.
Nitrophenol, C6H4(OH) (NO2) can have:
(A) No isomer (only a single compound is possible)
(B) Two isomers
(C) Three isomers
(D) Four isomers
Functional Isomerism
When any two compounds have the same molecular formula but possess different functional
groups, they are called functional isomers and the phenomenon is termed functional
isomerism. In other words substances with the same molecular formula but belonging to
different classes of compounds exhibit functional isomerism. Thus,

(1) Diethyl ether and butyl alcohol both have the molecular formula C 4H6O, but contain different
functional groups.
C2H5–O–C2H5 C4H9–OH
diethyl ether butyl alcohol
The functional group in diethyl ether is (–O–), while is butyl alcohol it is (–OH).
(2) Acetone and propionaldehyde both with the molecular formula C 3H6O are functional isomers.
CH3–CO–CH3 CH3–CH2–CHO
acetone Propionaldehyde
In acetone the functional group is (–CO–), while in propionaldehyde it is (–CHO).
(3) Cyanides are isomeric with isocyanides:
RCN RNC
Alkyl cyanide Alkyl isocyanide
(4) Carboxylic acids are isomeric with esters.
CH3CH2COOH CH3 COOCH3
Propanoic acid Methyl ethanoate
(5) Nitroalkanes are isomeric with alkyl nitrites:
 O
R—N R—O—N=O
Alkyl nitrite
O
Nitroalkane
(6) Sometimes a double bond containing compound may be isomeric with a triple bond
containing compound. This also is called as functional isomerism. Thus, butyne is isomeric
with butadiene (molecular formula C4H6).
CH3  CH2C �CH CH2 = CH  CH = CH2
1Butyne 1,3Butadiene
(7) Unsaturated alcohols are isomeric with aldehydes. Thus,
CH2 = CH  OH CH3 CHO
Vinyl alcohol Acetaldehyde

(8) Unsaturated alcohols containing three or more carbon atoms are isomeric to aldehydes as
well as ketones:
CH2 = CH  CH2 OH CH3 CH2 CHO CH3 COCH3
Allyl alcohol Propionaldehyde Acetone
(9) Aromatic alcohols may be isomeric with phenols:
CH2 OH CH 3
OH

Benzyl alcohol o - Cresol

(10)Primary, secondary and tertiary amines of same molecular formula are also the functional
isomers.
CH3 CH2CH2NH2 CH3  NH  C2H5
n  propylamine (1o ) Ethylmethylamine (2o )

CH3—N—CH3

CH3
Trimethylamine(3°)
(11) Alkenes are isomeric with cycloalkanes:
CH3CH2CH=CH2
Butene CH3
Cyclobutane
Methylcyclopropane
Such isomers in which one is cyclic and other is open chain, are called ring-chain isomers.
Alkynes and alkadienes are isomeric with cycloalkenes.
CH3CH2CCH CH2=CH—CH=CH2
1-Butyne 1,3-Butadiene
Cyclobutene
Exercise 23.
The type of isomerism observed in urea molecule is
(A) Chain (B) Position
(C) Geometrical (D) Functional

Metamerism
This type of isomerism is due to the unequal distribution of carbon atoms on either side of the
functional group in the molecule of compounds belonging to the same class. For example, methyl
propyl ether and diethyl ether both have the same molecular formula.
CH3–O–C3H7 C2H5–O–C2H5
methyl propyl ether diethyl ether
In methyl propyl ether the chain is 1 and 3, while in diethyl ether it is 2 and 2. This isomerism
known as Metamerism is shown by members of classes such as ethers, and amines where the
central functional group is flanked by two chains. The individual isomers are known as
Metamers.
Examples:
C2H5—N—C2H5 C3H7—N—CH3 C4H9—N—CH3

C2H5 C2H5 CH3

Triethylamine Ethylmethylpropylamine Butyldimethylamine

Tautomerism
It is the type of isomerism in which two functional isomers exist together in equilibrium. The two
forms existing in equilibrium are called as tautomers. For example, the compound acetoacetic
ester has two tautomers – one has a keto group and other has an enol group:
CH3—C—CH2—COOC2H5 CH3—C=CH—COOC2H5

O OH
Keto-form enol-form
Out of the two tautomeric forms, one is more stable and exists in larger proportion. In above,
normally 93% of the keto form (more stable) and only 7% of the enol form (less stable i.e. labile)
exist.
The equilibrium between the two forms is dynamic, i.e., if one form is somehow removed by
making a reaction, some of the amount of the other form changes into the first form so that similar
equilibrium exists again. Thus, whole of the acetoacetic ester shows the properties of
both ketonic group as well as the enolic group. Thus, it adds on HCN, NaHSO 3 etc. due to the
presence of >C=O group and it decolourises bromine water and gives dark colouration with FeCl 3
due the presence of >C—OH group. Due to the presence of keto and enol form this type of
tautomerism is known as keto-enol tautomerism. It is the most commonly observed type of
tautomerism.
Keto-enol tautomerism is generally observed in those compounds in which either a methyl
 CH 
(CH3—), methylene (—CH2—), or a methyne ( | ) group is present adjacent to a carbonyl
(—CO—) group as in acetoacetic ester above. In other words, it can be said that keto-enol
tautomerism is possible in only those carbonyl compounds in which atleast one a-hydrogen atom
is present so that it may convert the carbonyl group to enol group.
Another example of keto-enol tautomerism is:
O O OH O

CH3—C—CH2—C—CH3 CH3—C=CH—C—CH3
Keto-form 2,4 - Pentanedione
It is found that if the a-hydrogen atoms are present on both the carbons attached to carbonyl
group, more stable is the enol form and hence more its content. Thus, larger the number of a-
hydrogens in a ketone, more is enol content. Also, if number of a-hydrogen containing carbonyl
groups is more, again more is the enol content. Thus the order of enol content is:
CH3CHO < CH3COCH3 < CH3COCH2CHO < CH3COCH2COCH3
CH3COCH2COH3 has about 75% enol content. Moreover, the enol form shows acidic nature due
to the tendency to liberate proton (H +) from the enol ( C—OH) group. This H is the a-hydrogen
in keto – form. Therefore, a-H in carbonyl compound is acidic in nature. More the enol content,
more is the acidic nature of a-hydrogens in a carbonyl compound. Thus above is also the
increasing order of acidity of a-hydrogens.
An interesting observation about the enol content in acetoacetic ester is the fact that above
mentioned percentage ratio (93:7) is in its aqueous solution. In liquid state this ratio is nearly
25 : 75. It is because in liquid state the enol form is much stabilised by intramolecular H-bonding.
CH2
CH
H3C—C O—OC2H5 ���
���H3C—C
� O—OC2H5
O O O H O
enol

In aqueous solution the intermolecular H-bonding with water takes place and it dominates the
intramolecular H-bonding, resulting in lower enol content.
Keto-enol tautomerism exists in cyclic carbonyl compounds also if they fulfil the condition of
presence of a-H. Thus, we have
O —OH

O
—OH O
O
O OH

O OH
O OH
O OH

But the compound O O cannot exist as tautomers since a-H is already at unsaturated carbon.
Tautomerism is also termed as desmotropism (desomo= bond, tropis = turn) because in
tautomers the bonding changes.
O OH
Every compound having skeleton || has its tautomer skeleton | e.g., in the
 C  CH2   C  CH 
O OH
preparation of || a very small amount of enol isomers | also forms
CH3  C  CH3 CH3  C = CH2
which can be isolated. The two exist in equilibrium with each other and can be separated by
suitable methods.
A hydroxy group attached to a carbon which is itself attached to another carbon atom by a double
bond is known as enolic (en for double bond, ol for alcohol). Its nature becomes acidic as in
phenol and unlike OH group in alcohol which is neutral or only very slightly acidic (C 2H5OH + Na
1
 C2H5ONa + H2). In the above two examples migration of a proton from one carbon atom to
2
another takes place with simultaneous shifting of bonds.
Hydrocyanic acid, H – C  N and Isohydrocyanic acid H — N  C are also tautomeric isomers or
tautomers.
Difference between Tautomerism & Resonance
(a) In tautomerism, an atom changes place but resonance involves a change of position of pi-
electrons or unshared electrons.
(b) Tautomers are different compounds and they can be separated by suitable methods but
resonating structures cannot be separated as they are imaginary structures of the same
compound.
(c) Two tautomers have different functional groups but there is same functional group in all
canonical structures of a resonance hybrid.
(d) Two tautomers are in dynamic equilibrium but in resonance only one compound exists.
(e) Resonance in a molecule lowers the energy and thus stabilises a compound and decreases
its reactivity. But no such effects occur in tautomerism.
(f) In resonance, bond length of single bond decreases and that of double bond increases e.g.
all six C—C bonds in benzene are equal and length is in between the length of a single and a
double bond.
(g) Resonance occurs in planar molecule but atoms of tautomers may remain in different planes
as well.
(h) Tautomers are indicated by double arrow in between the two isomers but double
headed single arrow  is put between the canonical (resonating) structures of a
resonating molecule.

Illustration 33. C4H8 can have so many isomers. Write their structures. What are different tests
to make distinction between them?
Solution: C4H8 can have following structures:
(a) CH3—CH2—CH=CH2 1-butene
(b) CH3—CH=CH—CH3 2-butene, (cis and trans)
(c) CH3—C=CH2 2-methyl-1-propene
|
CH3
(d) Cyclobutane
(e) methyl cyclopropane
Distinctions:
(i) Ozonolysis of (a) forms CH3CH2CHO and HCHO or (b) forms CH 3CHO of (c)
forms
CH3
CO and HCHO
CH3
H
(ii)
CH3—C—H CH3—C—OH
+ alkaline KMnO4 
CH3—C—H CH3—C—OH
Cis-2-butene H
Meso-isomer
 H

CH3—C—H CH3—C—OH
+ alkaline KMnO4 
H—C—CH3 HO—C—CH3
trans-2-butene H
d-and l-

Illustration 34. C4H4O4 can have isomers A, B, C and D

(a) is cyclic ester
(b) is dicarboxylic acid giving racemic tartaric and with alkaline KMnO 4
(c) is dicarboxylic acid giving meso tartaric acid with alkaline KMnO 4
(d) is also dicarboxylic acid giving another monobasic acid on heating.
Identify A, B, C and D.

Solution: (a) Cyclic ester is obtained from dicarboxylic acid and diol. Given formula shows
A is cyclic ester of oxalic acid and glycol.
O
O=C CH2
O=C CH2
O
(b), (c) and (d) contain two —COOH groups. Possible structures are
COOH COOH

H—C H—C
COOH
C—H CH2=C
H—C COOH
COOH COOH
(maleic acid) (fumaric acid) gem
(ethene dicarboxylic acid)
On heating d forms another monobasic acid hence d is
COOH
CH2=C 
COOH CH2=CH—COOH
ge m
(ethenedicarboxylicacid)
when alkaline KMnO4 reacts with maleic acid, there is formation of meso-
tartaric acid (by syn addition)
COOH COOH
H—C H—C—OH
H2O + O
alkaline KMnO4
H—C
H—C—OH
COOH
COOH
(C) meso

Hence this represents isomer C

Alkaline KMnO4 converts fumaric acid into a mixture of d- and l-isomers
hence mixture is optically inactive (racemic)
(e) CH3—CH2—C————–––C—CH2CH3

CH2CH3 CH2CH3
 O
O /H O/ Zn ||
� � 3� �2 � ��� 2
CH3  CH2  C  CH2 CH3

STEREOISOMERISM

The isomers which differ only in the orientation of atoms in space are known as stereoisomerism.
It’s of two types.
(a) Geometrical isomerism: Isomers which posses the same molecular and structural formula
but differ in arrangement of atoms or groups in space around the double bonds, are known as
geometrical isomers and the phenomenon is known as geometrical isomerism. Geometrical
isomerism are show by the compounds having the structure.
X X
C=C
Y Y
(i) Cis – trans isomerism: When similar groups are on the same side it is cis and if same
groups are on the opposite side it is trans isomerism.
HOOC COOH HOOC H
C=C C=C
H H H COOH
(Maleic acid) Fumeric acid
(cis fom)
(trans fom)

(ii) Syn - anti

CH3 CH3
H H
C C
N N
OH (aldoxime) OH
(Syn) (anti)

C6H5—N C6H5—N

C6H5—N N— C6H5

(Syn) (anti)

Syn anti isomerism is not possible in ketoxime since only one form is possible two —
CH3 groups are at one C.
CH3
CH3
C
N
OH
(iii) In cyclic compounds:
OH OH

OH OH
Cis trans
Differentiating properties of cis-trans isomerism

(i) Dipolemoment: Usually dipole moment of cis is larger than the trans-isomer.
H Cl H Cl

C C

C C
H Cl Cl H
 = 1.84D =0
(ii) Melting point: The steric repulsion of the group (same) makes the cis isomer less stable than
the trans isomers hence trans form has higher melting point than cis.
(iii) Different chemical properties: Syn-addition makes cis forms into meso and trans into d and l,
anti addition makes cis into d – l and trans into meso.
COOH H COOH COOH
H C OH alc. KMnO 4 C Br water H C Br
  2  

( syn, addn) anti addn. Br C
H C OH C H

COOH H COOH COOH

meso d&l
COOH H COOH COOH
H C OH alc
.KMnO C Br water H C Br

4 
2 

HO C H (syn
,addn) anti
addn. H C
C Br

COOH HOOC H COOH

d&l meso
H
— C— C
O OH H C CO

 O+H
2O
H
— C— COO H
Ma
leica
cid
H C C
O
M
ale
ica
nhy
drid
e
H
—C—
CO
OH


 n
ore
act
ion
H
OOC
—C—
H
E and Z nomenclature of Geometrical Isomerism
If all the four groups/ atoms attached to C = C double bond are different, then Cis and trans
nomenclature fails in such cases and a new nomenclature called E and Z system of
nomenclature replace it.
H I higher priority H I
C C

C C
Br Cl Cl
Br
higher priority higher ranked
E Z
I II
The group / atom attached to carbon - carbon double bond is given to higher rank, whose atomic
weight is higher. If the two higher ranked group are across, it is called E form (E stands for the
German word entgegen meaning thereby opposite) and the two higher ranked groups are on the
same side, they are called Z-form (Z stands for German word Zusammen meaning thereby on the
same side).
In general trans - isomer is more stable then cis isomer because in cis from, there will be more
interaction in between groups.
Besides suitably substituted alkene and cycloalkane, suitably substituted oximes and azo
compounds also exhibit geometrical isomerism.
R R OH
C=N C=N
H OH H
syn-oxime (Aldoxime) Anti-oxime (Aldoxime)

R R OH
C=N C=N
R OH R
R-syn-oxime or R-Syn-oxime or
R-anti-oxime R-anti-oxime

R R
N=N N=N
R
Cis-azo anti-azo

Illustration 35. How will you distinguish between maleic acid and fumaric acid?

Solution. Maleic acid forms an anhydride where as fumaric acid does not.

Exercise 24:
Assign E / Z configuration to each of the following compounds.
(a) H3C CH3 (b) Br CH3

H H H3C CH3
(c) H3C (d) Cl H

Br CH3
Br D

HO CH3

Exercise 25.
Write the isomeric structures of an alkene having m.f. C 4H8. Indicate which is more
stable.

Exercise 26.
 Why does 2-butene exhibit cis-trans isomerism but but-2-yne does not?

Exercise 27.
Geometrical isomerism is possible in:
(A) Butene-2 (B) Ethene
(C) Propane (D) Propene

(b) Optical isomerism: Any substance which rotates the plane polarised light (PPL) is said to be
optically active. If a substance is optically active, it is non - superimposable on its mirror
image. If a molecule of substance is superimposable on its mirror image, it cannot rotate PPL
and hence optically inactive. The property of non-superimposibility on mirror image is called
chirality. The ultimate criterion for optical activity is chirality, i.e., non-superimposibility on its
mirror image.
If a molecule of organic compound contains 'one' chiral carbon, it must be chiral and hence
optically active.

Chiral carbon: If all the four bonds of carbon are satisfied by four different atoms / groups, it is
chiral. Here it should be noted that isotopes are regarded as different atoms / groups) chiral
carbon is designated by an asterisk (*).
Optical isomerism in bromochloroiodomethane:
The structural formula of bromochloroiodomethane is
Br
*
H—C—Cl

I
The molecule has one chiral carbon as designated by star. So molecule is chiral. It is non -
superimposable on its mirror image.
According to Van't Hoff rule,
Total number of optical isomers should be = 2n; when n is number of chiral centre
The Fischer projections of the two isomers are
Br Br

H——— I I——— H
Cl Cl
(i) Mirror (ii)
Stereoisomers which are mirror - image of each other are called enantiomers or enantiomorphs.
(i) and (ii) are enantiomers. All the physical and chemical properties of enantiomers are same
except two:
(i) They rotate PPL to the same extent but in opposite direction. One which rotates PPL in
clockwise direction is called dextro-rotatory (dextro is Latin word meaning thereby right) and
is designated by d or (+). One which rotates PPL in anti-clockwise direction is called laevo
rotatory (means towards left) and designated by  or (–).
(ii) They react with optically active compounds with different rates.

Illustration 36. State whether the following compound is optically active or inactive.
 H

H3C—C—CH2—CH3
2
H
Solution: H H

H3C—C—CH2—CH3 or H3C—C—CH
* 2—CH3

2
H D
The molecule contains one chiral carbon and so must be optically active.
Isotopes are regarded as different atom.
Optical isomerism in compounds having more than one chiral carbons
If an organic molecule contains more than one chiral carbons then the molecule may be chiral or
achiral depending whether it has element of symmetry or not.
Elements of symmetry: If a molecule have either
(a) a plane of symmetry, and / or
(b) centre of symmetry, and / or
(c) n-fold alternating axis of symmetry
If an object is superimposable on its mirror image; it cannot rotate PPL and hence optically
inactive.
If an object can be cut exactly into two equal halves so that half of its become mirror image of
other half, it has plane of symmetry.

superimposable Plane of symmetry

Non-superimposable
Centre of symmetry: It is a point inside a molecule from which on travelling equal distance in
opposite directions one takes equal time.
C A

B B
B B

A C
Thus, if an organic molecule contains more than one chiral carbons but also have any elements
of symmetry, it is superimposable on its mirror - image, cannot rotate PPL and optically inactive. If
the molecule have more than one chiral centres but not have any element of symmetry, it must be
chiral.

Stereoisomerism in 2, 3-dibromopentane
The structural formula of 2, 3-dibromopentane is
H H
* *
H3C—C—C—CH 2—CH3

Br Br
The molecule contains two chiral carbons and hence according to Van't Hoff rule the total number
of optical isomers should be 2n = 22 = 4 and it is. The four optical isomers are.

CH3 H3C CH3 H3C

H———Br Br———H H———Br Br———H

H———Br Br———H Br———H H———Br

CH2CH3 H3CH2C CH2CH3 H3CH2C

(I) (II) (III) (IV)
 Nonsuperimposable  Non -superimposable
 Rotate PPL  Rotate PPL
 Optically active  Optically active
I, II, III and IV are four stereoisomers of 2, 3-dibromopentane.
I and II are enantiomers.
III and IV are also enantiomers
What is relation between I and III; or I and IV; or II and III; or II and IV?
All these pairs are diastereomers, stereoisomers which are not mirror - image of each other are
called diastereomers.
Therefore,
I and III are diastereomers
I and IV are diastereomers
II and III are diastereomers
II and IV are diastereomers
Stereoisomerism in Tartaric Acid
The IUPAC name of tartaric acid is 2, 3 - dihydroxy butandioic acid. The structural formula is
* *
HOOC  CHOH  CHOH  COOH
The molecule contains two chiral carbon and the number of optical isomers should be 2 n=22=4;
but number of optical isomers reduces to 3 because one molecule has plane of symmetry.
Stereoisomers of Tartaric Acid
 HOOC COOH HOOC
COOH

HO———H H———OH HO———H

H———OH ----------------
---------------- Plane of symmetry
H———OH HO———H
HO———H H———OH
HOOC HOOC HOOC
COOH
(i) (ii) (iii) (iv)
 Non - superimposable
 Superimposable
 Can rotate PPL III and IV are same
 Optically active Rotation of IV by 180° yield III.
Superimposability means same in identity
I and II are enantiomers
III is meso-form of tartaric acid
A meso compound is one which is optically inactive although have more than one chiral carbons.
Number of Optical Isomers
Number of possible optical isomers in compounds containing different no. of asymmetric
atoms.
(1) The molecule has no symmetry
The no. of d and l – forms a = 2n
n = no. of asymmetric atoms
The no. of meso l- forms m = 0
Total no. of optical isomers = a + m = 2n
(2) The molecule has symmetry and n is even
The no. of d and l forms a = 2n–1
n
Meso forms m = 2 2 1
Total = a + m
n
= 2n–1 + 2 2 1
Tartaric acid
COOH
H—C—OH
Plane of syn n =2
H—C—OH
COOH
a = 2n–1 = 22–1
n
m = 2 2 1 = 21–1 = 2° = 1
Total = 2 +1 = 3
COOH COOH COOH

H—C—OH HO—C—H H—C—OH

HO—C—H H—C—OH H—C—OH

COOH COOH COOH

I II III
(meso forms)
One of asymmetric centre is rotating plane polarised light towards right other towards left so total
optical rotation is zero.
I & III or II & III which are not mirror image to each other are called diastereomers.
(3) The molecule has symmetry & n is odd
( n 1)
The no. of d and l forms a = 2n–1 - 2 2

( n 1)
Meso forms m = 2 2

Total = a + m
= 2( )
n 1

e.g. Lactic acid

CH3
H—C—OH
COOH
n = 1 no symmetry
d & l forms = 2n = 2
meso form = 0
total = 2
CH3 CH3
Mirror images are also
H—C—OH OH—C—H called as enantiomers
COOH COOH
d-form l-form
Difference between racemic mixture and meso compound
A racemic mixture contains equimolar amounts of enantiomers. It is optically inactive due to
external compensation. It can be resolved into optically active forms. A meso compound is
optically inactive due to internal compensation.
Optically active compounds having no chiral carbon
The presence of chiral carbon is neither a necessary nor a sufficient condition for optical activity,
since optical activity may be present in molecules with no chiral atom and since molecules with
two or more chiral carbon atoms are superimposable on their mirror images and hence inactive.
(i) 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.
16
O

—CH2—S— —CH3

18O

(ii) Atoms with pyramidal bonding might be expected to give rise to optical activity if the atom is
connected to three different groups, since the unshared pair of electron is analogous to a
fourth group.
 Z
N
X Y
Many attempts have been made to resolve such compounds, but until recently all failed
because of umbrella effect, also called pyramidal inversion. The umbrella effect is rapid
oscillation of the unshared pair from one side of XYZ plane to the other.
(iii) Biphenyls, containing four large groups in the ortho position so that there is restricted
rotation, are optically active if the rings are asymmetrical.
If either or both rings are symmetrical, the molecule has plane of symmetry and optically
inactive.
NO2 HOOC Cl COOH O 2N Cl
Cl Cl

'A' 'B' 'B'

NO 2 HOOC COOH O 2N

Mirror
Ring B is symmetrical (having plane of symmetry) superimposable optically inactive.
NO2 HOOC COOH O2N Cl
Cl

NO2 HOOC
COOH O 2N
Non - superimposable
optically active
Allenes, with even number of cumulative double bonds are optically active if both sides are
dissymmetric.
H3C H H CH3
C=C=C C=C=C
H3C H H3C
Inactive H
Active

Specific Rotation
The specific rotation [ a ] l is an inherent physical property of an enantiomer, which varies with the
T

solvent used, temp (in °C) and wavelength of the light used. It is calculated from the observed
rotation a as follows.
a
[ a] l =
T

l �c
Where  = length of tube in decimeters (dm)
C = Concentration in gram cm–3, for a solution density in g cm–3, for a pure liquid.
Illustration 37. The specific rotation of R–2–bromooctane is –36°. What is percentage
composition of a mixture of enantiomers of 2-bromooctane where rotation
is +18°.
Solution: Let X = mole fraction of R,
 (1–X) = mole fraction S.
 X (–36°) + (1–X) 36° = 18°
1
or, X =
4
The mixture has 25% R and 75% S, it is 50% racemic and 50% S.
Nomenclature of Optical Isomers
(1) Absolute and 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.

COOH COOH

H––– C–––OH HO–––C–––H

CH3 CH3
(+)-lactic acid (–)-lactic acid
We know that they differ from one another in the direction in which they rotate the plane
of polarized 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.
(2) 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 + 3.82o 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 - 8.25o
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 absolute configurations as shown
below.
CHO CHO
| |
H––C––OH HO––C––H
| |
 CH2OH CH2OH
(+)-glyceraldehyde (–)-glyceraldehyde
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 a-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 absolute
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
| |
R2 ––C––X X––C––R2
| |
R3 R3
D configuration L configuration
When there are several asymmetric carbon atoms in a molecule, the
configuration at one centre is usually related directly or indirectly to
glyceraldehyde, and the configurations at the natural (+)-glucose there are
four asymmetric centres (marked by asterisk). By convention for sugars, the
configuration of the highest numbered asymmetric carbon is referred to
glyceraldehyde to determine the overall configuration of the molecule. For
glucose, this atom is C–5 and, therefore, OH on it is to the right. Hence the
naturally occurring glucose belongs to the D-series and is named as D-
glucose.

However, the above system of nomenclature based on Fischer projection formulae, has certain
disadvantages. Firstly before a name can be assigned to a compound, we must specify how its
projection formula is oriented.
Secondly, sometimes the two asymmetric carbon atoms having the same kind of arrangements of
substituents are assigned opposite configurational symbols. Thus for (–)-2, 3-butanediol we have

FISCHER PROJECTION
German chemist Emil Fischer, proposed the “Fischer projection” concept to simplify the
displaying of stereo – chemical relationship of carbohydrates.
Fischer projection is the representation of tetrahedral carbon atoms as a two – dimensional
structure on paper. In this projection, molecule arranged with the horizontal bonds along with
chiral centre projecting above the plane of the page. The vertical bonds projecting behind the
page. Main chain of molecule arranged by vertical lines and most important functional group is
placed at the top.
 CHO CHO CHO

CHOH  H C OH  C
CH2OH
CH2OH H
CH2OH OH

CHO

H OH

CH2OH
Projected form
(Fischer projection)

Illustration 38. A racemic mixture of (±) 2phenyl propanoic acid on esterification with
(+) 2butanol gives two esters. Mention the stereochemistry of the two esters produced.
H
Solution. H3C CH3
O

H3C H3C Ph H
H OH O H 5C 2
+ (+) (+ )
Ph H
COOH C 2H 5 H
( ) (+ ) H3C CH3
(Racemic mixture) O

Ph H
O H 5C 2
() (+ )
The bonds attached to the chiral carbon in both the molecules are not broken
during the esterification reaction. (+) Acid reacts with (+) alcohol to give an (++)
ester while (–) acid reacts with (+) alcohol to give (+ –) ester. These two esters
are diastereoisomers.
Illustration 39. Identify each of the following as R or S
CH3 CN
(a) (b)
H C CH2Cl
CH3 C C CH

H3C CH3 CH2OH

CHO COOH
(c) (d)
H C OH NH2 C H

CH2OH CH3

Solution: a – S, b – S, c – R, d – S
Exercise 28.
Which of the following will be a stronger acid and why? Cl 3CH and F3CH

Exercise 29.
HC  C– is a weaker base than CH2 = CH–. Why?

Exercise 30.
Which of the following compounds will exhibit optical isomerism?
(A) 2-butene (B) 2-butyne
(B 2-butanol (D) Butanol

Exercise 31.
Dichloro ethylene shows.
(A) Geometrical isomerism (B) Position isomerism
(C) Both (D) None

Exercise 32.
The compound having molecular formula C4H10O can show
(A) Metamerism (B) Functional isomerism
(C) Positional isomerism (D) All

Exercise 33.
A compound contains 2 dissimilar asymmetric carbon atoms. The number of optical
isomers is:
(A) 2 (B) 3
(C) 4 (D) 5

Exercise 34.
Number of possible isomers of glucose are
(A) 10 (B) 14
(B) 16 (D) 20
 ANSWERS TO EXERCISES

Exercise 1:
1° - six
3° - two
4° - one

Exercise 2:
(i) 2, 3, 5 – tri methyl heptane
(ii) 3, 4, 5, 6 tetra methyl octane
(iii) 3 ethyl 3 propyl heptane

Exercise 3:
(i) 3, 3 – dimethyl but – 1 – ene
(ii) 3- (1, 2 – dimethyl propyl) – 1, 3 – hexadiene
(iii) 4 – cyclopentyl – 2 – butane

Exercise 4:
(i) 2, 2 dimethyl propane
(ii) 3, 3 – diethyl pentane
(iii)) 6 hydroxy 4, 5 – dimethyl hexanoic acid
(iv) 3 chloro 3 hydroxy butanal

Exercise 5:
(i) 3 hydroxy, 3 methyl propanyl chloride
(ii) Benzoic, ethanoic anhydride
(iii) H H H H O

H C C C C C NH2
5 4 3 2
1
H OH Cl O

CH3

3 chloro, 4 - hydroxy, 2 methoxy pentanamide

(iv) H H H O

H3C C C C C Cl
4 3 2 1
5
CH3 OH H

3 hydroxy 4 methyl pentanoyl chloride

Exercise 6:
(i) Cyclo propanol
(ii) 3 cyclo propyl butanoic acid

Exercise 7:
Bond energy order
sp–sp > sp2-sp2 > sp3-sp3
Hence, (A) is correct.

Exercise 8:
(a) is most stable as it is a 3° carbocation as well as allylic.
Exercise 9:
 (a) In this structure if we break C – Cl bond heterolytically we end up with a C + ion; a
benzyl carbocation.

Exercise 10:
e<a<b<c<d
The order depends on carbocation stability

Exercise 11:
In the first case the carbocation generated is stabilized by resonance due to the lone pair
of O. The same happens in the second case, but now due to the lone pair of N. N being
less electronegative can provide electrons easily. Hence the C – I bond in second case is
weak.

Exercise 12:
Allyl carbonium ion undergoes resonance stabilization.
Hence, (A) is correct.

Exercise 13:
In aniline the lone pair of electrons on N atom are delocalised in the benzene ring and
hence the basicity decreases.

Exercise 14:
Resonance effect operates through the -electrons and inductive effect operates through
the -electrons. -electrons can be easily perturbed and hence that effect is
dominateng.

Exercise 15:
Due to the presence of bulky –NO 2 groups on its ortho positions, the –NMe 2 group goes
outside the plane of resonance to avoid steric repulsion. The C – N bond rotates and
hence the lone pair of N goes perpendicular to the plane of benzene ring. As a result the
resonance is stopped and hence the lone pair is readily available as a base.

Exercise 16.
a>b

The negative charge on ‘O’ atom is delocalized to a larger extent.

CH3 – CH2 – O–, the negative charge on ‘O’ atom is increased by +I effect.

Exercise 17:
(a) H3C CH2 H3C CH2

OH OH
(b) Yes

Exercise 18:
(i) (a)
(ii) Phenoxide ion (C6H5O) which results after loss of H+ from phenol can be
resonance stabilized whereas alkoxide ion (RO ) which results after the loss of
H+ from alcohol can not stabilize it through resonance.
 (iii) Lone pair on nitrogen of aniline are less available for a base because they are
involved in the resonance the ring.
NH2

(iv) (c) is most acidic as triple bonded carbon atom are sp hybridized i.e. orbital
holding bond pairs of C  H bond has 50% s and 50% p – character, the greater
is s – character greater is hold of electrons of carbon nucleus over bon d pair
electrons which makes loss of H+ easier.

Exercise 19.
d>c>a>b
The order depends on the carbocation stability.

Exercise 20.
(i) (a) because for geometrical reasons this carbocation cannot attain planarity.
(ii) (a) I > III > II (I is most stable due to resonance effect of OH group)
(b) In CH3  O  CH2+, positive charge over carbon is stabilized with the
help of lone pair of electrons present in adjacent oxygen atom.
+
CH3  O  CH2+ ��� CH3  O = CH2
��

Exercise 21:
In the first case I is more electronegative than C and hence the positive charge is an the
C atom. So OH– attacks C and displaces I–.
In the second case due to the presence of three F atoms, the electron deficiency of C
increases. Hence it gives a positive charge on I. Hence OH– attacks I and displaces CF3.

Exercise 22:
o-, m- and p-isomers, i.e., position isomers
Hence, (C) is correct.

Exercise 23:
NH4CNO is functional isomer of urea.
Hence, (D) is correct.

Exercise 24:
(a) Z (b) E
(c) Z (d) Z
Exercise 25:

The stability order is I > III > II.

Exercise 26:
Alkynes are all linear molecules and hence there is no chance of exhibiting geometrical
isomerism.

Exercise 27:
H H
C=C
CH3 CH3
If either of the two doubly bonded carbon atoms has same group or atoms attached on it,
it will not show geometrical isomerism.
Hence, (A) is correct.

Exercise 28:
CHCl3 is a stronger acid. Cl3CH  Cl3C– + H+
In this case the negative charge on C is delocalised in the vacant orbitals of Cl, which is
absent in F3C–.

Exercise 29:
HC  C–, in this the negative charge is on a sp hybridised carbon atom which has less
tendency to give electrons.

Exercise 30:
Due to the presence of asymmetric carbon atom.
Hence, (B) is correct.

Exercise 31:
CH2 = CCl2 and CHCl = CHCl are position isomers; CHCl = CHCl also show geometrical
isomerism.
Hence, (C) is correct.

Exercise 32:
Alcohols show position isomerism; Ethers show metamerism; Alcohol and ethers shows
functional isomerism.
Hence, (D) is correct.

Exercise 33:
a = 2n; where n is no. of dissimilar asymmetric carbon atoms.
Hence, (C) is correct.

Exercise 34.
Glucose has four dissimilar asymmetric carbon atoms; a = 24.
Hence, (C) is correct.
 MISCELLANEOUS EXERCISES

Exercise 1: Write the structural formula of 2 – methyl pentan – 1 – ol.

Exercise 2: Write the structural formula of the compound 4 – methyl pent – 2 – ene.

Exercise 3: Write the structural formula of the compound 3 – methyl Butanoic acid.

Exercise 4: Write the structural formula of the compound.

5 - Chloro- 7 - hydroxy - 3 methoxy, oct - 5 - enal

Exercise 5: Write the structural formula of the compound 2 – Bromo butanoyl chloride.

Exercise 6: Explain what is homolytic fission?

Exercise 7: What is inductive effect?

Exercise 8: Why inductive effect is called transmission effect?

Exercise 9: What is difference between a free radical and an ion?

Exercise 10: What is hyper conjugation?

Exercise 11: Why hyperconjugation is called no bond resonance?

Exercise 12: Name the kind of effect that operates to explain the stability of carbocations?

Exercise 13: What is electromeric effect?

Exercise 14: Define and explain the terms chirality. Which of the following molecule are chiral
and which are achiral?
(i) ClCH ( Br ) F
(ii) CH3 CH2  CH ( Cl) CH2CH3
(iii) CH3CHOHCH2CH3
(iv) ClCH2CH2CH2CH3
(v) CH3CH2CHOHCH2CH2CH3

Exercise 15: A compound C4H10O shows optical activity. Identify the compound and write the
possible structures.
 ANSWER TO MISCELLANEOUS EXERCISES

CH3
Exercise 1:
OH

CH3

Exercise 2:
CH3
CH3 O
Exercise 3:
OH
CH3

OH Cl O O
Exercise 4:
H

Exercise 5:
Cl

Br

Exercise 6: In this type of cleavage each fragment formed as the result of cleavage gets one
electron from the shared pair of electrons.
� �
hn
Cl � M �Cl �����
or 523  725K
� Cl + Cl

Exercise 7: Permanent displacement of electrons along a carbon chain when some atom or
group of atoms with different electronegativity than carbon is attached to carbon
chain is called inductive effect.

Exercise 8: Because the effect is carried on from one carbon atom to the next two
consecutive carbon atoms.

Exercise 9: Free radical is electrically neutral form by homolytic cleavage of co-valent bond
but ions are positively & negatively charged species.

Exercise 10: Hyper conjugation is a special kind of resonance in which decolaziation of

electrons takes place through overlap between  bond orbital and  bond orbital
or p orbital.

Exercise 11: Since there is no bond between carbon and hydrogen atoms in hyperconjugation
structures.

Exercise 12: Resonance, inductive effect, hyper conjugation.

Exercise 13: The complete transfer of the shared pair of  - electrons of a multiple bond to one
of the atoms in the presence of the attacking agent is called electromeric effect.

Exercise 14: (i), (iii) & (V)

 SOLVED PROBLEMS

Subjective:

Prob 1. Write the IUPAC name

H3C CH2 CH CH2 CH CH2 CH2 CH3

CH3 H2 C CH3

Sol. 1 2 3 4 5 6 7 8
H3C CH2 CH CH2 CH CH2 CH2 CH3

CH3 H2 C CH3

The longest chain is of 8 carbon atoms. The root word for the chain is oct.
(b) It is a saturated chain. Thus, the primary suffix-ane should be affixed with root word.
Oct + ane = Octane
Root Primary suffix
(c) One methyl group and one ethyl group are present as substituents. The numbering
of the chain is done as indicated above. The names of substituents along with locants
in alphabetical order are written before the root word. Hence, the name of the
compound is

Prob 2. CH3

H3C C CH2 CH2 CH CH2 CH2 CH2 CH3

CH3 H3C C CH3

CH
H3C CH3

Sol. CH3
1 2 3 4 5 6 7 8 9
H3C C CH2 CH2 CH CH2 CH2 CH2 CH3
1'
CH3 H3C C CH3
2'
Branched chain
3' CH
H3C CH3
The compound is a derivative of nonane. It has two methyl groups and one branched
chain as substituents. The branched chain is also numbered. The name of the
branched chain is 1’, 2’, 2’ – trimethylpropyl. Hence, the name of the compound is:
2, 2-Dimethyl-5-(1’, 1’, 2’ – trimethylpropyl) nonane.
Prob 3. H3C CH C C CH3

Cl

Sol. 5 4 3 2 1
H3C CH C C CH3

Cl
It is a derivative of unsaturated hydrocarbon. The parent chain consisting the triple
bond is of five carbon atoms. The numbering is done from R.H.S as it gives lowest
number to triple bond. Cl is a substituent at carbon – 4. Hence, the name of the
compound is:
4 – Chloro pent – 2 – yne

Prob 4. H3C CH2 CH CH CH CH2 CH2 CH3

Cl Br NO2

Sol. 1 2 3 4 5 6 7 8
H3C CH2 CH CH CH CH2 CH2 CH3

Cl Br NO2
The compound is a derivative of octane. All the three groups are subsituents. The
numbering is done from L.H.S as it gives lowest numbers to two subtituents. The
names of the substituents are arranged in alphabetical order. Hence, the name of the
compound is:
4 – Bromo – 3 – chloro – 6 – nitro – octane

Prob 5. Br

H3C CH C C CH3

Sol. Br
5 4 3 2 1
H3C CH C C CH3
The compound is a derivative of an unsaturated hydrocarbon consisting a double bond.
The numbering is done from R.H.S as it gives lowest number to carbon atom linked by
a double bond in the chain. Br is the subtituent at carbon – 4. Hence, the name of the
compound is:
4 – Bromo pent – 2 – ene

Prob 6. H3CH2CHC CHCOOH

Sol. 5 4 3 2 1
H3CH2CHC CHCOOH
The compound consists of two functional groups, COOH group is the principal
functional group. The numbering is thus, done from R.H.S.
Root word = Pent, double bond = 2 – ene, functional group = -oic acid
Thus, the name of the compound is:
2 – Penten – 1 – oic acid
Prob 7. CH2 CH CH2

CN CN CN

Sol. 1 2 3
CH2 CH CH2

CN CN CN
There are three CN groups. All group of one kind which occurs in a single molecule
should be given the same treatment as far as possible (Like Things Alike).
Propane – 1, 2, 3 – tricarbonitrile

Prob 8. C6 H5 O

H3C C CH C CH3

CH3 CHCl

CH3

Sol. C6 H5 O

H3C C CH C CH3
5 4 3 2 1
CH3 CHCl
1'
CH3
The compound is a ketone. Numbering is done at R.H.S as to give lowest number to
the functional group. The substituents are C  3 and C  4.
Root word = Pent, Primary suffix = -ane, functional group = -one, Substituent names =
phenyl, methyl, 1’ – chloroethyl.
Thus, the name of the compound is:
3 – (1’ chloroethyl) – 4 – methyl – 4 – phenylpentan- 2 – one

Prob 9. O O

H3C C CH2 CH2 C OH

Sol. O O
5 3 2 1
4
H3C C CH2 CH2 C OH
Two functional groups are present but COOH group ranks higher in the priority table.
The compound is named as acid. The numbering is done from R.H.S. as to give
minimum number to the functional group carbon. The carbonyl group act as a
substituent.
Root word = pent, primary suffix = -ane, secondary suffix = -oic acid and substituent
= oxo or keto.
Thus, the name of compound is:
4 – Oxo – pentanoic acid.
Prob 10. H 2C CH CH CH2 CH3

H3C CH CH CH2 CH CH2 CH2 COOH

Sol. H2 C CH CH CH2 CH3
5 6 7 8 9
H3C CH CH CH2 CH CH2 CH2 COOH
4 3 2 1
The longest chain in the compound consists 10 carbon atoms and two double bonds
but it does not include the principal functional group, COOH. Hence, the longest
chain of nine carbon bond is selected. The numbering is started from the end of
COOH group as to give minimum number to carbon formatting the COOH group.
Thus, the compound is a derivative of nonene. The compound has a side chain which
is named 2 – butenyl.
Root word = -non, primary suffix = -ene, principal functional group (secondary suffix) =
-oic acid, substituent (prefix) = 2’ – butenyl.
Hence, the name of the compound is:
4 – (2’ – Butenyl) – non – 6 – enoic acid
Prob 11. Arrange the following compounds in the increasing order of basicity
O

N N
N
N H H
H
(I) (II) (III) (IV)

Sol. In (II), (III) and (IV) the lone pair present in sp 3 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 sp 2 orbital which makes it less basic than
(III) and (IV) is less basic (III) due to I effect of oxygen atom. Thus, the increasing
order of basic strength would be II < I < IV < III.

Prob 12. Compare the stabilities of phenyl (C6H5) and cyclohexyl (a) cations and
(b) anions.
Sol. (a) C6H5+ is a vinyl carbocation and is less stable than C6H11+, a 20 carbocation.
(b) In C6H5 :, the electron pair is in an sp 2 hybrid orbital. The carbanion has more
S – character and is more stable than C6H11 : whose unshared electron pair is in an sp3
hybrid orbital.
H
H
sp2 sp3

C 6H 5 C6H11 C6H5 C6H11

Prob 13. Of the ethanol and trifluro ethanol, which is more acidic?
Sol. 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.
Prob 14. Compare the acidic strength of propenoic acid, propanoic acid and propynoic acid.

Sol. HC  C  CO2H > CH2 = CH  CO2H > CH3  CH2  CO2H

Prob 15. Out of phenyl acetic acid and acetic acid, which is stronger?

Sol. Phenylacetic acid is stronger than acetic acid due to I effect of phenyl group.

Prob 16. Give the correct order of acidic strength of O , m  and p  methyl phenols.

Sol. m - methyl phenol > p – methyl phenol > O – methylphenol

Prob 17. Arrange 4 – nitrophenol, 2, 4 - dinitrophenol and 2, 4, 6 – trinitrophenol in the

decreasing order of acid strength.

Sol. 2, 4, 6 – trinitrophenol > 2, 4- dinitrophenol > 4 – nitrophenol

Prob 18. CH3 CH3

is more stable than

Why?

X H X H
(a) (b)

Sol. Here carbocation (a) is stabilized most as the CH 3 group is attached to the carbon
bearing positive charge.

Prob 19. Compare the acidic strength of the following CH 3COOH, ClCH2COOH, Cl2CHCOOH,
CCl3COOH.

Sol. H O H O

CH3COOH < Cl C C O H < Cl C C O H

H
Cl

Cl
O

< Cl C C O H

Cl
Increasing acidic strength due to increasing number of similar (I) groups.

Prob 20. Compare the basic strength of the following NH3, CH3NH2, (CH3)2NH, (CF3)3N.

Sol. The increasing order of basic strength is as follows:

 CH3
CF3 H H
F 3C N < H N < H N < H3 C N

CF3 H H CH3

(I) (II) (III) (IV)

Prob 21. Explain that a - methyl acetyl acetone undergoes enolization to smaller extent than
acetylacetone

Sol. O O H
O O
H3C C CH2 C CH3
C C CH3
CH3 C
Acetyl acetone
H
(Keto - form) Enolization is greater due to less strain
O O H
O O
H3C C CH C CH3
C C CH3
CH3
CH3 C
CH3
a- methyl acetyl acetone Enolization is smaller due to high strain
keto-form

Prob 22. Write the possible isomers of the formula C5H10 O2 .

Sol. (a) Carboxylic acids

(i) H3C CH2 CH2 CH2 COOH (ii) CH3

H3C CH CH2 COOH

(iii) CH3

H3C C COOH

CH3
(b) Esters:
O O
(i) (ii)
H3C CH2 CH2 C OCH3
H3C CH2 C OCH2 CH3
(iii) O
(iv) O
H3C C O CH2 CH2 CH3
H3C C O CH CH3

CH3
And So on.
(c) Hydroxy aldehydes
(d) Hydroxy ketones etc.

Prob 23. Which among the following is most acidic

 (a) HCOOH (b) CH3COOH
(c) (CH3)2CCOOH (d) (CH3)3CCOOH

Sol. –CH3 group is electron releasing group, it decreases polarity of –OH bond in –COOH
group.
Hence CH3 group decreases the acidic strength of the carboxylic acid.
� �
Prob 24. Why allylic free radical CH2 = CH – CH2 is more stable than CH3– CH2 - CH2 while both
are primary free radicals.

Sol. Allylic free radical is resonance stabilized while propyl free radical is not resonance
stabilized.
� � d� K K d�
CH2 = CH – CH2  CH2 – CH = CH2  CH2  CH  CH2

Prob 25. Though enol form is less stable than keto form, phenol exists in enol form, why?

OH O
Sol.
H
H

Enol form is much more stable than keto form because of great stability associated with
aromatic ring which is absent in keto form.
Objective:

Prob 1. The IUPAC name of the compound

CH3

CH3CH2CH2CH CH CH2CH3

C CH2CH3 is
CH

CH3 CH3 CH2CH3

(A) 3, 3 – diethyl – 4 – methyl – 5 – isopropyl octane

(B) 3, 3 – diethyl – 5 – isopropyl – 4 – methyl octane
(C) 4 – isopropyl – 5 – methyl – 6, 6 – diethyl octane
(D) 6, 6 – diethyl – 4 – isopropyl – 5 – methyl octane

Sol. (B)
Prob 2. The IUPAC name of the compound
CH3CH =CH - CH =CH - C �CCH 3 is
(A) 4, 6 – octadien – 2 – yne (B) 2, 4 – octadien – 6 – yne
(C) 2 – octyn – 4, 6 – diene (D) 6 – octyn – 2, 4 – diene
Sol. (B)

Prob 3. The correct IUPAC name of the compound

O CH3

CH3 CH C CH2 CH is :

CH2 CH3

CH3
(A) 2, 5 – dimethyl heptan – 4 – one
(B) 3, 6 – dimethyl heptan – 4 – one
(C) 2 – ethyl – 5 – methyl hexan – 3 – one
(D) 1, 1 – dimethyl – 4 – ethyl pentan – 3 – one
Sol. (A)
Prob 4. The IUPAC name of CH3 CH CH2 C(CH3)2 is

OH OH
(A) 1, 1 – dimethyl – 1, 3 – butanendiol (B) 2 – methyl – 2, 4 – pentane diol
(C) 1, 3, 3 – trimethyl – 1, 3 – propane diol (D) 4 – methyl – 2, 4 – pentane diol

Sol. (B)
CH3
HO
CH3
Prob 5. The IUPAC name of the compound
is

(A) 1, 1 – dimethyl – 3 – hydroxy cyclohexane

(B) 3, 3 – dimethyl – 1 – hydroxy cyclohexane
(C) 3, 3 – dimethyl cyclohexanol
(D) 1, 1 – dimethyl – 3 – cyclohexanol
Sol. (C)
Prob 6. Which of the following compounds represents 2, 2, 3 – trimethylhexane?
(A) CH3C( CH3 )2 CH 2CH 2CH( CH 3 )2
(B) CH3C( CH 3 )2 CH 2CH( CH3 ) CH 2CH 3
(C) CH3C( CH 3 )2 CH( CH 3 ) CH 2CH 2CH 3
(D) CH 3C( CH 3 )2 CH 2C( CH 3 )2 CH 3

Sol. (C)

Prob 7. The IUPAC name of the compound O OH

CH3 C CH2 C O is
(A) 1 – hydroxy butan – 1, 2 – dione (B) 4 – hydroxy butan – 2, 4 – dione
(C) 3 – oxo butanoic acid (D) 1 – hydroxy – 1, 3 – dioxo butane

Sol. (C)

Prob 8. The IUPAC name of the compound. (CH3)2C CH2COCH3 is

CN
(A) 4 – cyano – 4 – methyl – 2 – oxo pentane
(B) 2 – cyano – 2 – methyl – 4 – oxo pentane
(C) 2, 2 – dimethyl – 4 – oxo pentanenitrile
(D) 4 – cyano – 4 – methyl – 2 – pentanone
Sol. (C)

Prob 9. The IUPAC name of

(C 2H 5)2 N C H 2C H COOH is

Cl
(A) 2 – chloro – 4 – (N – ethyl) pentanone acid
(B) 2 – chloro – 3 – (N, N – diethyl amino) propanoic acid
(C) 2 – chloro – 2 – oxo diethyl amine
(D) 2 – chloro – 2 – carboxy – N – ethyl ethane

Sol. (B)
Prob 10. Which of the following compound contains isopropyl group?
(A) 2 – methyl pentane (B) 2, 2, 3 – tri methyl pentane
(C) 2, 2, 3, 3 – tetra methyl pentane (D) 2, 3 – dimethyl pentane

Sol. (A)

Fill in the blanks

Prob 11. Isomerism which are ………….. and mirror image are known as ……………….. .

Sol. Non super imposable, enantiomeis

Prob 12. Geometrical isomerism is due to ………………….. rotation round a covalent bond.

Sol. Hundred

Prob 13. A meso compound is made up of ……………. molecules that contain ………… centres.
Sol. Achiral, chiral
Prob 14. The (+) and () forms of tartaric acid are …………………….. .

Sol. enentiomersm

Prob 15. Tautomerism is …………………. isomerism.

Sol. dynamic

Prob 16. The possible number of derivatives of propane are …………….. .

Sol. Four

Prob 17. d and l isomers of a compound are mirror image to each other and thus know as
……………. .

Sol. mirror image isomerism

Prob 18. Glucose and fructose are ……………. isomerism.

Sol. Functional

Prob 19. Metamers include ………… class of compounds.

Sol. Same

Prob 20. Dipole moment of trans but -2-ene is ………………………

Sol. zero

State true and false

Prob 21. Homologues can be isomers.

Sol. [F]

Prob 22. Tartaric acid possesses two asymmetric carbon atom in its molecule.

Sol. [T]

Prob 23. A mixture of cis and trans isomers can be separated by fractional distillation.

Sol. [T]

Prob 24. Geometrical isomers must contain a carbon – carbon double bond.

Sol. [F]

Prob 25. A ring can make a molecule rigid and causes geometrical isomers.

Sol. [T]

Prob 26. But-2- ene-1, 4 – dioic acid shows geometrical isomerism.

Sol. [T]
Prob 27. Optical isomers have different physical and chemical properties.

Sol. [F]

Prob 28. cis and trans isomers have different dipole moments.

Sol. [T]

Prob 29. Alkanes show isomerism with alkamines.

Sol. [T]

Prob 30. Only organic compound are optically active.

Sol. [F]
 ASSIGNMENT PROBLEMS

Subjective:

Level – O

1. Explain why the give names in the following are wrong

Give a correct name in each case:
(a) 1 – methylpentane
(b) 2, 3 – dichloropropane
(c) 1 – chloro – 1 – methylpropan – 2 – ol
(d) 1, 1, 2, 2 – tetramethylethane
(e) 2 – keto – pentan – 5 – oic acid

2. Write IUPAC name of tertiary butyl methyl ether.

3. Write structure and IUPAC name of aceto nitrile.

4. Find number of primary, secondary, tertiary and quaternary carbon atom in 2, 2, 4 tri methyl
hexane.

5. Write IUPAC name of

CH 2CHO

CH3

6. What is +E and E effect? Explain with one example in each case.

7. What are free radicals? Discuss the stability order or primary, secondary and tertiary free
radicals?
8. Arrange the different carbanions ions in the decreasing order of stability giving reasons?
9. Explain the stability order of carbocations giving reasons.
10. For each of the following bond cleavages, use curved arrows to describe the electron flow
(a) CH O OCH

3 3 CH
O
3 OCH
3
(b) E
E

(c) CH3
CH3

H3C Br H3C Br

CH3
CH3
(d) O
O

H3C C H 2O
OH
H
11. What is hyper conjugation effect? How does it differ from resonance effect. Briefly discuss the
significance of hyperconjugation effect.

12. D – (+) – glyceral dehyde is oxidised to () glyceric acid, OHCH2.CH(OH)COOH. Give the
D – L designation of the acid.

13. Draw the (a) Newman & (b) Fisher projection for enantiomer of CH 3CHIC2H5.

14. Halogen group attached to benzene nucleus is o – and p – directing but is considered as
deactivating group. Explain.

15. What are end products of the following?

(a) NO2

Fe
Br2

(b) NH2

Fe
Br 2

OH
(C)

AlCl 3
CH3Cl
Level – I

Write IUPAC name of the following compounds:

1.

2.

OH
O
3.
O
OH

4. In which C  C bond of CH3CH2CH2Br, the inductive effect is expected to be the least?

5. Write the resonance structures of (a) CH 3COO and (b) C6H5NH2. Show the movement of
electrons by curved arrows.

6. Give reasons why the following two structures (I and II) can not be the major contributors to
the real structure of CH3COOCH3.
O O

H3C C O CH3 H3C C O CH3

(I) (II)

7. Explain acidic nature of vinyl alcohol.

8. Explain the basic character of following compounds.

NH3, CH3NH2, (CH3)2NH, C6H5NH2

9. Explain the acidic nature of a - hydrogen of aldehydes and ketones.

10. Arrange the following compounds in order of their increasing acidity

COOH COOH COOH

(I)
NO 2 NH2
(II) (III)

11. Arrange the following compounds in order of their increasing acidic characters
CH H2C H3C

COOH COOH COOH

(I) (II) (III)

12. Draw example of (a) a meso alkane having the molecular formula C 8H18 and (b) the simplest
alkane with a chiral carbon.
13. Predict the preferred regiochemistry for the addition of HCl to each of the following
compounds on the basis of carbocation stability.
(a) (b)
CH3
H3C

(c) H3C (d) Ph

CH2

H3C H3C CH3

14. Explain mechanism of 1:4 addition of HBr on 1, 3 – butadiene.

15. Explain which compound is the weaker base:

(a) NH2 NH2

or

NO 2
(b) or
O
(c) O O O O

or HO C C OH
O C C OH
(d) OH OH

CH3 CF3

or
Level – II

Me

1. Me NH2

Me
Me

H2C

2.
H3C

H3C
CH3

3. Which of the following compounds are correctly named?

(A) CH3 CH2CH2 CH(Cl)CO2H; 2  chloropen tanoic acid
(B) CH3 C �CCH(CH3 )CO2H; 2  methyl haxenoic acid  3
(C) CH3CH2CH = CHCOCH3 ; Hex  3  en  2  one
(D) (CH3 )2 CHCH2CH2CHO; 4  methylpen tanal

4. Draw resonance structures for (i) C6H5F and (ii) C6H5NO2 showing which carbon of the ring
bear the partial charge induced in the ring by extended  - bonding.

5. NH2 in benzene is orth-para directing but when passed in acidic solution it becomes meta
directing why?

6. C  O bond length in carbonate ion is longer than C  O bond length in formate ion. Explain
in brief.

7. Math list II with list I

List – I (Statement)
List - II (reason in terms of
effect)
(a) The alkene CH3 CH = CH  CH3 is (a) P - d bonding effect
more stable its isomer
CH3 CH2  CH = CH2
(b) the carbocation CH3  O  H2  (b) Hyper conjugation
+
C
is less stable than its another
canonical form CH3  O+ = CH2
(c) The carbanion: : CCl3 is more stable (c) Fulfillment of octel


than : CF3 .
(d) Phenol is more acidic than alcohol (d) Resonance effect

8. Arrange the following in increasing order of resonance stability.

 (I) (II)
(III)
9. Arrange the following in increasing order of acidic nature.
OH OH OH OH

NO2
(I) (III)
NO2 CH3
(II) (IV)

10. Arrange the following in increasing order of carbocation stability.

CH CH CH C

(I) (II) (III) (IV)

11. Arrange the following in increasing order of carbanion stability.

CH2 CH2 CH2 CH 2

(I) (II) (III)

NO 2
(IV)

12. Arrange the following in increasing order of basic property.

NH2 NMe2 NMe2

Me Me

(I) (II) (III)

13. Write the increasing order of stability of following cations

CF3 , CH2Cl , C6H5CH2 , C6H5

14. Arrange the following in increasing acid strength

 (a) O O O

C OH C OH C OH

C CH3

(I)
(III)
C
O CH3
(II)
(b) OH OH

CH3OH

(V)
(IV)
CN
(VI)
(c) O O O O O

H3C C OH HO C C OH HO C CH2 CH2 C OH

(I) (II)
(III)

15. Rank the following amines in increasing basic nature

(a)

N N

H NH2 NH2
(I) (II)
(III) (IV)
(b) NH2 NH2 NH2 NH2

CH3 NO2

(I) (II) (III) (IV)

(c) NH2 CH2NH2
NH2 NH2
CH3

(I) CH3
(II) (IV)
CH3
(III)
Objective:

Level – I
1. Which one is the wrong statement?
(A) saturated hydrocarbons are called alkenes
(B) open – chain compounds are called aliphatic
(C) unsaturated hydrocarbons contain double or triple bond (bonds) between carbon atoms
(D) aromatic compounds posses a characteristic aroma
2. Which is the correct statement?
(A) the prefix are written before the name of the compound
(B) the suffix are written after the name of the compound
(C) the IUPAC name of a compound is always written as one word
(D) all the above are correct
3. Which of the following statement is wrong?
(A) the IUPAC name of alkenes ends with suffix –ene
(B) the IUPAC name of alkynes ends with suffix –yne
(C) the substituents gets lower number in comparison to functional group
(D) the IUPAC name of acid amides is alkanamide
4. The correct decreasing order of preference of functional groups during the IUPAC
nomenclature of poly functional compounds is
(A) COOH, CHO, OH, NH2 (B) NH2, OH, CHO, COOH
(C) COOH, OH, NH2, CHO (D) COOH, NH2, CHO, OH

5. In which of the following compounds the carbon atom chain has been correctly numbered
7 6 5 4 3 2 1
(A) H3C CH CH CH CH2 CH2 CH3

C 2H 5 CH3
1 2 3
(B) H3C CH2 C CH CH3
4 5
H 2C CH3
5 4 3 2 1
(C) H3C CH2 CH C CH

H 2C CH2 CH3
CH3
(D)
H3C C CH CH CHO
5 4 3 2 1
CH3

6. IUPAC name of CH3 CHO is:

(A) Acetaldehyde (B) Ethanal
(C) Methyl aldehyde (D) Formalin

7. IUPAC name of CH3 CH(OH)CH2CH2COOH is:

(A) 4 – hydroxy pentanoic acid (B) 1 – carboxy – 3 – butanol
(C) 1 – carboxy – 4 – butanol (D) 4 – carboxy – 2 – butanol
8. The IUPAC name of the following compound is:
H2 C CH CH2

CN CN CN
(A) 1, 2, 3 – tricyano propane (B) Propane tricarbylamine
(C) 1, 2, 3 – propane tricarbonitrile (D) 3 – cyanopropane – 1, 5 – dinitrile

9. The structure of 4 – methyl – 2 – penten – 1 – ol is:

(A) (CH3 )2 C = CHCH2 CH2OH (B) (CH3 )2 CHCH = CHCH2 OH
(C) CH 3 CH 2 CH = CHCH 2 OH (D) CH3 CHOHCH = C(CH3 )2

10. The IUPAC name for the following compound is:

OH OH

CH3 C CH2 CH CH3

CH3
(A) 1, 1 – dimethyl – 1, 3 – butandiol
(B) 2 – methyl – 2, 4 – pentandiol
(C) 4 – methyl – 2, 4 – pentandiol
(D) 1, 3, 3 – trimethyl – 1, 3 – propandiol

11. What is the decreasing order of stability of the ions?

+ + +
(I) CH3  CH CH3 (II) CH3  CH OCH3 (III) CH3  CH COCH3
(A) I > II > III (B) II > III > I
(C) III > I > II (D) II > I > III

12. The C  H bon distance is longest in

(A) C2H2 (B) C2H4
(C) C2H6 (D) C2H2Br2
13. The most stable free radical among the following
� �

(A) C6H5 CH2 CH2 (B) C6H5 C HCH3

� �

(C) CH3 C H2 (D) CH3 C HCH3

14. Theorder of decreasing stability of the carbanions
(CH3)3C (I) ; (CH3)2CH (II); CH3CH2 (III); C6H5CH2 (IV) is
(A) I > II > III > IV (B) IV > III > II > I
(C) IV > I > II > III (D) I > II > IV > III
15. The most stable carbanion among the following is
(A) H 2C CH2 (B) CH2
 (C) CH2 (D) CH2

OCH3
NO 2
16. Among the following alkene: 1 – butene (I), cis 2- butene (II), trans 2 – butene (III), the
decreasing order of stability is
(A) III > II > I (B) III > I > II
(C) I > II > III (D) II > I > III

17. The arrangement of (CH3)3C-, (CH3)2CH-, CH3CH2- when attached to benzene or unsaturated
group in increasing order of activating effect is
(A) (CH3)3C < (CH3)2CH  < CH3CH2 
(B) CH3CH2  < (CH3)2CH  < (CH3)3C 
(C) (CH3)2CH < (CH3)3C  < CH3CH2 
(D) (CH3)3C < CH3CH2  < (CH3)2CH 

18. Decreasing I power of given groups is

(1) CN (2) NO2 (3) NH3 (4) F
(A) 2 > 1 > 4 > 3 (B) 2 > 3 > 4 > 1
(C) 3 > 2 > 4 > 1 (D) 3 > 2 > 1 > 4

19. A free radical is

(A) neutral is character (B) shortly lived
(C) paramagnetic (D) all the above

20. Which amongst the following will be most stable?

+ +
(A) CH3 CH2 (B) ( CH3 ) 2 CH
+ +
(C) ( CH3 ) 3 CCH2 (D) ( CH3 ) 3 C

21. The most stable carbocation amongst the following is

+ +
(A) ( CH3 ) 2 CH (B) Ph3 C
+ +
(C) CH3 CH2 (D) CH2 = CH  CH2

22. Which of the following exerts +I effect?

(A) CH3  (B) Cl
(C) NH2 (D) NO2

23. Which of the following species has/have electron releasing effect?

(A) CHO (B) NO2
(C) CH3 (D) C6H5

24. +R power of the given groups

(1) (2) NH2 (3) OH
O
(4) NHCOCH3 in decreasing order is
(A) 1 > 2 > 3 > 4 (B) 4 > 3 > 2 > 1
(C) 1 > 3 > 2 > 4 (D) 1 > 4 > 3 > 2
25. Which statement is correct for inductive effect?
(A) it is a permanent effect
(B) it is the property of single bond
(C) it causes permanent polarization in the molecule
(D) all are correct
Level – II

1. The IUPAC name of Cl3 CCH2 CHO is

(A) Chloral (B) 3, 3, 3 – trichloropropanal
(C) 1, 1, 1 – trichloropropanal (D) 2, 2, 2 – trichloropropanal
2. The formula of propanenitrile is
(A) CH3 CN (B) C2H5 CN
(C) C3H7 CN (D) C2H5NC
3. The correct name of CH3 CH2 CH2 is :

C C CH
(A) 3 – hexyn – 5 – ene (B) 5 – hexen – 3 – yne
(C) 3 – hexyn – 1 – ene (D) 1 – hexen – 3 – yne
4. Which compound is 2, 2, 3 – trimethylhexane
CH3 CH3 CH3 CH3
(A) (B)
CH3 C CH CH2 CH3 CH3 C CH2 CH CH3

CH3 CH3
CH3 CH3 CH3
(C) (D)
CH3 CH CH2 CH2 C CH3 CH3 C CH CH2 CH2 CH3

CH3 CH3 CH3

5. IUPAC name of H3C CH CH2 CH CH2Cl is :

C 2H 5 OH
(A) 1 – chloro – 4 – methyl – 2 – hexanol
(B) 1 – chloro – 4 – methyl – hexanal – 2
(C) 1 – chloro – 4 – ethyl – 2 – pentanol
(D) 1 – chloro – 2 – hydroxy – 4 – methyl hexane
6. In which class of compounds will the following compound be named?
ClCH2 CH CH2 C CH2NO2

OH O
(A) Nitro compounds (B) Alcohols
(C) Alkyl halides (D) Ketones
7. Which one of the following IUPAC names is incorrect?
(A) Ethanoic acid (B) Ethanal
(C) pent – 3 – ene (D) 3 – methyl – pentan – 2 – ol
8. The IUPAC name of the compound CH3 CONHBr is:
(A) 1 – bromoacetamide (B) ethanoyl bromide
(C) N – bromoethanamide (D) None of these
CH2 CH3

9. The IUPAC name of C2 H5 C CH2 CHNH2 is :

(A) 4 – amino – 2 – ethyl – 1 – pentene (B) 2 – ethyl – 4 – pentanamine
(C) amino – 4 – pentene (D) 4 – ethyl – 4 – penten – 2 – amine
 O

C2H5 C

10. The IUPAC name of O is :

CH3 C

O
(A) ethoxy methanone (B) ethyl – 2 – methyl propanoate
(C) ethanoic propanoic anhydride (D) 2 – methyl ethoxy propanone

11. Which statement is correct for electromeric effect?

(A) it is a temporary effect
(B) it is the property of  bond
(C) it takes place in presence of reagent, i.e. electropile or nucleophile
(D) all are correct

12. Which one of the following is most acidic?

(A) phenol (B) 2 – chlorophenol
(C) 3 – chlorophenol (D) 4 – chlorophenol

13. Which one of the following is most – acidic?

(A) 2 – propanol (B) 2 – methyl – 2 – propanol
(C) ethanol (D) methanol

14. Consider the following carbanions

(1) H3C CH2 (2) H2C CH (3) HC C

Correct order of stability of these carbanions in decreasing order is
(A) 1 > 2 > 3 (B) 2 > 1 > 3
(C) 3 > 2 > 1 (D) 3 > 1 > 2

15. Consider the following carbocations

H3C CH2 H2C CH H2 C CH CH2

(1) (2) (3)

(4) C6H5CH2
Stability of these carbocation in decreasing order is
(A) 4 > 3 > 1 > 2 (B) 4 > 3 > 2 > 1
(C) 3 > 4 > 2 > 1 (D) 3 > 4 > 1 > 2
16. Which among the following carboncations is most stable?
(A) (B)
C C6 H5 CH2

(C) (D)
C6 H5 CH C6 H5 H3 C C CH3

CH3
17. Arrange basicity of the given compounds in decreasing order
(1) CH3  CH2  NH2 (2) CH2 = CH  NH2
(3) CH  C  NH2
(A) 1 > 2 > 3 (B) 1 >3 > 2
(C) 3 > 2 > 1 (D) 2 > 3 > 1

18. Arrange the following groups in order of decreasing deactivating effect

(1) NO2 (2) SO3H
(3 CF3 (4) CHO
(A) 1 > 3 > 2 > 4 (B) 1 > 2 > 3 > 4
(C) 1 > 4 > 3 > 2 (D) 4 > 3 > 2 > 1

19. Consider the following compounds

NH2 NH2 NH2 NH2

(I) NO 2 CN CH3
(II) (III) (IV)

Arrange these compounds in deceasing order of their basicity

(A) 1 > 2 > 3 > 4 (B) 2 > 3 > 1 > 4
(C) 4 > 1 > 3 > 2 (D) 4 > 1 > 2 > 3

20. Which one of the following is vinyl carbocation

(A) (B)
H5 C6 CH2 CH2 CH CH2
(C) (D) All of these
H2 C CH

21. Which one of the following is most basic?

NH2 NH2
(A) (B)
CH3

NH2 NH2
(C) (D)
H3C CH3

H3C CH3

22. Which of these species are electrophiles?

(A) FeCl3 (B) BF3
(C) AlCl3 (D) all of these
23. Arrange given compounds in order of decreasing acicity
(1) CH3  NO2 (2) NO2  CH2  NO2 (3) CH3  CH2  NO2
NO 2
(4)
O 2N CH NO 2
(A) 4 > 2 > 1 > 3 (B) 4 > 2 > 3 > 1
(C) 3 > 1 > 2 > 4 (D) 3 > 1 > 4 > 2

24. Which one of the following has the highest nucleophilicity?

(A) F (B) OH
(C) CH3 (D) NH2

25. The stability of given free radical in decreasing order is

(1) H3C CH2 (2) H3C CH CH3 (3) H3C C CH3

CH3
(4) CH3
(A) 3 > 4 > 1 > 2 (B) 1 > 2 > 3 > 4
(C) 3 > 2 > 4 > 1 (D) 3 > 2 > 1 > 4
 ANSWERS TO ASSIGNMENT PROBLEMS

Subjective:

Level - O
CH3 H H H H

1. (a) H C C C C C H Hexane

H H H H H
H H H
(b)
H C C C Cl 1, 2 dichloro propane

H Cl H
H H CH3
(c)
H C C C Cl 3 chloro butan - 2 - ol

H OH H
CH3 CH3
(d)
H3C C C CH3 2, 3 dimethyl butane

H H
H H H
(e)
H C C C C COOH 4 keto pentanoic acid

H O H H

CH3
2.
H3C C O CH3 2 methoxy 2 methyl propane

CH3

H
3.
H C CN Ethane nitrile

4. 1° - five, 2° - two, 3° - one, 4 – one

5. 2 (2- methyl) phenyl ethanal
12. Oxidation of D – (+) – aldehyde does not affect any of the double bonds to the chiral C. The
acid has the same configuration even through the sign of rotation is changed.
CHO COOH

H C OH H C OH

CH2OH CH2OH
D-( )-glyceraldehyde D-(-)-glyceric acid
13. CH3 CH3
CH3 CH3

I H H I

I H I
H
C 2H 5 C 2H 5 C2H5
C2H5

14. The high electron negativity of a halogen polarizes a C  X bond so that Cl d 

carbon bears partial positive. This leaves the ring electron deficient and +d
makes electrophilic attach difficult. The inductive deactivation is greater
at the ortho – than at the para – position because its influence decrease E
with distance from the electronegative halogen atom

15. NO2 group is m – directing while NH2 and OH groups are O  and p  directing.
(a) NO 2 (b) NH2

Br

m - bromonitrobenzene

Br
O - (also p-) bromoaniline
(c) OH

CH3

O - (also p-) cresol

Level – I
1. Cyclo dodecane

2. 4 – ethyl – 2 – cyclopropyl – 1 – hexene

3. 1, 2 – ethanedioic acid

4. The magnitude of inductive effect decreases with distance and hence the effect is least in C 2
C3 bond
3 2 1
H3C CH2 CH2 Br

5. (a) O
O
H3C C
H3C C
O
O

(b) NH 2 NH 2 NH 2 NH2 NH2

6. Both these structures involve sepetration of charge and hence do not contribute substanitially
towards the resonance hybrid. Further, the contribution of I is lower than that of structure II
since C atom has only a sextet of electrons.

7. (a)
H2 C CH OH H 2C CH OH

-H less stable due to charge seperation.

H 2C CH O H 2C CH O

More stable due to absence of charge seperation

After loss of H+ ion vinyl alcohol stabilizes by resonance, hence it will favour loss of H + and
hence acidic in nature.
8. Order of basic strength is as follows:

9. H3C C R CH2 C R CH2 C R

-H
O
O O
Since after the loss of a - H remaining part of alhehyde, or ketone stabilizes by resonance,
hence, it will favaour the loss of H+ ions hence it is acidic in nature.
10. III < I < II
The conjugate bases of the 3 compounds are stabilized by equivalent resonance as shown
below
O O O O O O O O
O O O O

-M M

N NH2 NH2
N
(I) O O
O O (III)
(II)

11. III < II < I

As we go from I  II  III S character of the hybridized orbital of
a - c decreases (sp  sp2  sp3) hence the acidic character decreases.
12. (a) CH3 CH3

CH3CH2C C CH2CH3 3, 4 dimethy hexane

H
 (b) The chiral C in this alkane must be attached to the four simplest alkyl group.
CH3

H2CH3C C H

CH2

CH2

CH3
3 methyl hexane

13. (a)
HCl

Cl
( 1, 4 - addition product)
(b) CH3 CH3 Cl

CH3 HCl CH3 CH3

Cl
H3C H3C H3C
H3C
(c) H3C
H3C H3C
CH2 HCl Cl
CH3 H3C Cl
H3C H3C
H3C
(d) Ph
Ph Ph
HCl Cl
Cl

H3C CH3 H3C CH3 H3C CH3

14.
H2C CHCH CH2
H 2C CH CHCH2 HCH2C CHCH2
Due to mesomeric effect, there is polarity on C 1 and C4 resulting in the 1, 4 addition at these
sites. This type of behaviours is generally obtained in conjugated systems.
H
H2C CH CH CH2 H2C CH CH CH3
Alkyl carbocation (resonance stabilized)

Br
H2C CH CH CH3 BrH2C CH CH CH3
1, 4 - addtion product
NH2
15. (a) (b)

NO2

(c) O O (d) OH

CH3
HOC COH
Level – II

1. 1 amino 4, 5 diethyl 2 methyl non – 3 - ene

2. 3 ethyl 3 methyl pentene

3. A, C & D

4. (a)
d

or
d d
F F
F F F

(b) O O O O O O O O O O
N N N N N

d d
or

d
In each case the para and two ortho positions bear some of the charge (ve charge in
fluorobenzene and +ve charge in nitrobenzene)

5. Because the nitrogen atom of NH2 contains lone pairs of NH3

electrons it donates electron density to the benzene ring,
so it is ortho para directing but when it is passed in acidic
medium then it converts into. Which is meta – directing? (anilinium ion)

6. CO32 ion is a resonance hybrid of the following three resonating structure of equal stability.
O O O O 2

O O O O O O O
O

HCOO- is a resonance hybrid of only two resonating structure of (as shown below) of equal
stability.
O O O

H O H O H O

Thus is the resonance hybrid of carbonate ions each C  O bond has 2/3rd signal bond
character and 1/3rd doubled bond character while HCOO  ion each C  O bond has half
single bond and half doubled bond character. Greater the single bond character of any bond
larger that bond.

7. List – I List – II
(a) (b)
(b) (c)
(c) (a)
(d) (d)
8. II < I < III
9. IV < I < II < II

10. IV < I < II < III

11. II < III < I < IV

12. I < II < III

13.
C6H5 < CF 3 < CH2Cl < C6H5CH2

14. (a) I < III < II (Intramolecular H – bonding in III makes it less acidic than p – isomer)
(b) II < I < III
(c) I < III < II

15. (a) IV < II < III < I

(b) III < I < II < IV
(c) II < III < I < IV
Objective:

Level - I

1. A 2. D 3. C
4. A 5. D 6. B
7. A 8. C 9. B
10. B 11. D 12. C
13. B 14. B 15. D
16. A 17. A 18. A
19. D 20. D 21. B
22. A 23. C 24. A
25. D

Level - II

1. B 2. B 3. D
4. D 5. A 6. D
7. C 8. C 9. D
10. C 11. D 12. B
13. D 14. C 15. A
16. A 17. A 18. A
19. C 20. C 21. C
22. D 23. A 24. C
25. D