Page 1

1.

HOMOLOGOUS SERIES

Organic compounds can be divided into different groups on the basis of similarity in their structure and
properties. The property by which a number of organic compounds form a homologous series is termed as
homology.
The general characteristics of a homologous series are
All compounds in the series have the same functional group.
All compounds in the series can be represented by the same general formula and can be prepared
by the general methods of preparation.
All the homologues show a gradual gradation in their physical and chemical properties.
Successive members of a homologous series differ by CH2 group and by a mass of
14 units.
Table 1a: Homologous series of aliphatic organic compounds
Name of the homologous General formula
series

IUPAC name

Alkanes

CnH2n + 2

(single bond)

Alkanes

Alkenes

CnH2n

Alkenes

Alkynes

CnH2n 2

= (double bond)
(triple bond)

Monohydric alcohols

CnH2n + 1 OH

OH

Alkanols

Aldehydes

CnH2nO

CHO

Alkanals

Ketones

CnH2nO

Monocarboxylic acid

CnH2nO2

COOH

Alkanoic acids

Ethers

CnH2n + 2 O

COC

Alkoxy alkanes

Primary amines

CnH2n + 1 NH2

Amides

CnH2n + 1 CONH2

Esters

CnH2nO2

Cyanides
Nitro compounds

CnH2n + 1CN
CnH2n + 1 NO2

Acid chlorides

2.

Functional group
or substituent

CnH2n + 1 COCl

C=O

Alkynes

Alkanones

NH2

Alkanamines

CONH2

Alkanamides

R COO R

Alkyl alkanoate

CN
O
N
O

Alkane nitriles
Nitroalkanes

COCl

Alkanoyl chlorides

NOMENCLATURE OF ORGANIC COMPOUNDS

Nomenclature implies assigning proper name to a particular organic compound on the basis of certain
standard rules so that the study of these compounds may become systematic. In the IUPAC system, the name
of an organic compound consists of three parts.
(i) Word root (ii) Suffix (iii) Prefix
WORD ROOT
The word root denotes the number of carbon atoms present in the chain. For example,
Chain length

Word root

Chain length

Word root

C1

Meth

C6

Hex

C2

Eth

C7

Hept

C3

Prop

C8

Oct

C4

But

C9

Non

C5

Pent

C10

Dec

SUFFIX
The word root is linked to the suffix, which may be primary, secondary or both.
Primary suffix

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It indicates the nature of linkages between the carbon atoms. For example,

ane for single bonded compounds, CC ;

ene for double bonded compounds, C=C ;
and yne for triple bonded compounds, CC.
Secondary suffix
It indicates the presence of functional group in the organic compound. For example,
Class of organic compound

Functional group

Secondary suffix

Alcohols

OH

ol

Aldehydes

CHO

al
one

C=O

Ketones
Carboxylic acids

COOH

oic acid

Esters

COOR

alkyl..oate

Acid chlorides

COCl

oyl chloride

Acid amides

CONH2

amide

Nitriles

CN

nitrile

Amines

NH2

amine

PREFIXES
There are many groups, which are not regarded as functional groups in the IUPAC naming of the
compounds. These are regarded as substituents or side chains. These are represented as prefixes and are
placed
before
the
word
root
while
naming
a
particular
compound.
For
example,
if a compound contains more than one functional group, then one of the functional group is regarded as
principal functional group and is treated as secondary suffix. The other functional groups are regarded as
substituents and are indicated by prefixes.
Substituent

Prefix

Substituent

Prefix

CnH2n+1

Alkyl

NH2

Amino

Fluoro

NO

Nitroso

Cl

Chloro

N=N

Diazo

Br

Bromo

OCH3

Methoxy

Iodo

OC2H5

Ethoxy

NO2

Nitro

OH

Hydroxy

Thus, a complete IUPAC name of an organic compound may be represented as

Prefix + Word root + Primary suffix + Secondary suffix.

HOW TO NAME ORGANIC COMPOUNDS USING THE IUPAC RULES

In order to name organic compounds you must first memorize a few basic names. These names are
listed within the discussion of naming alkanes. In general, the base part of the name reflects the number of
carbons in what you have assigned to be the parent chain. The suffix of the name reflects the type(s) of
functional group(s) present on (or within) the parent chain. Other groups which are attached to the parent
chain are called substituents.
2.1
RULES FOR NAMING ALKANES SATURATED HYDROCARBONS
The name of straight chain saturated hydrocarbons for up to 12 carbon chain are shown below. The
names of the substituents formed by the removal of one hydrogen from the end of the chain is obtained
by changing the suffix ane to yl.
Number of Carbons
Name
1

methane

ethane

propane

butane

pentane

Page 3

hexane

heptane

octane

nonane

10

decane

11

undecane

12

dodecane

There are a few common branched substituents which you should memorize. These are shown below.

CH3
CH3CH
isopropyl

CH3
CH3CH2CH
sec-butyl

CH3
CH3C
CH3
tert-butyl

CH3
CH3CHCH2
isobutyl

Here is a simple list of rules to follow. Some examples are given at the end of the list.
1.
Identify the longest carbon chain. This chain is called the parent chain.
2.
Identify all of the substituents (groups attached to the parent chain).
3.
Number the carbons of the parent chain from the end that gives the substituents the lowest numbers.
When comparing a series of numbers, the series that is the lowest is the one which contains the
lowest number at the occasion of the first difference. If two or more side chains are in equivalent
positions, assign the lowest number to the one which will come first in the name.
4.
If the same substituent occurs more than once, the location of each point on which the substituent
occurs is given. In addition, the number of times the substituent group occurs is indicated by a prefix
(di, tri, tetra, etc.).
5.
If there are two or more different substituents they are listed in alphabetical order using the base name
(ignore the prefixes). The only prefix which is used when putting the substituents in alphabetical order
is iso as in isopropyl or isobutyl. The prefixes sec and tert are not used in determining alphabetical
order except when compared with each other.
6.
If chains of equal length are competing for selection as the parent chain, then the choice goes in series
to :
(a) the chain which has the greatest number of side chains.
(b) the chain whose substituents have the lowest numbers.
(c) the chain having the greatest number of carbon atoms in the smaller side chain.
(d) the chain having the least branched side chains.
7.
A cyclic (ring) hydrocarbon is designated by the prefix cyclo which appears directly in front of the
base name. In summary, the name of the compound is written out with the substituents in alphabetical
order followed by the base name (derived from the number of carbons in the parent chain). Commas
are used between numbers and dashes are used between letters and numbers. There are no spaces in
the name. Here are some examples:

CH3

CH2CH3

CH3CHCH2CHCH2CH3

CH3CH2 CH3
CH3CH2CH2CHCCH2CH3
CH3

4Ethyl2methylhexane

4Ethyl3,3dimethylheptane

Page 4

CH3CH2CHCHCHCHCH3

CH3

CH

CH2CH2

CH3 CH2 CH3 CH3

CH2

CH3

2,3,5Trimethyl4propylheptane

Methylcyclopropane

(NOT: 2,3dimethyl4secbutylheptane)

CH3

CH3

CH3CHCH2CH2CHCH2CHCH2CH3
1

CH3 CH2

CHCH3
CH2CH3

CH3

5Secbutyl2, 7dimethylnonane

2.2

CH3CH2CHCHCH2CH3

3Ethyl4methylhexane

RULES FOR NAMING ALKENES AND ALKYNES UNSATURATED HYDROCARBONS

Double bonds in hydrocarbons are indicated by replacing the suffix ane with ene. If there is more
than one double bond, the suffix is expanded to include a prefix that indicates the number of double
bonds present (adiene, atriene, etc.). Triple bonds are named in a similar way using the suffix yne.
The position of the multiple bond(s) within the parent chain is(are) indicated by placing the number(s) of
the first carbon of the multiple bond(s) directly in front of the base name.
Here is an important list of rules to follow:
1.
The parent chain is numbered so that the multiple bonds have the lowest numbers (double and
triple bonds have priority over alkyl and halo substituents).
2.
When both double and triple bonds are present, numbers as low as possible are given to
double and triple bonds even though this may at times give yne a lower number than ene.
When there is a choice in numbering, the double bonds are given the lowest number.
3.
When both double and triple bonds are present, the en suffix follows the parent chain directly
and the yne suffix follows the en suffix (notice that the e is left off, en instead of ene). The
location of the double bond(s) is(are) indicated before the parent name as before, and the
location of the triple bond(s) is(are) indicated between the en and yne suffixes.
4.
For a branched unsaturated acyclic hydrocarbon, the parent chain is the longest carbon chain
that contains the maximum number of double and triple bonds. If there are two or more
chains competing for selection as the parent chain (chain with the most multiple bonds), the
choice goes to (1) the chain with the greatest number of carbon atoms, (2) the number of
carbon atoms being equal, the chain containing the maximum number of double bonds.
5.
If there is a choice in numbering not previously covered, the parent chain is numbered to give
the substituents the lowest number at the first point of difference.
Here are some examples:
6

CH3CH=CHCH2CH=CH2

CHCCH=CHCH=CH2

1,4Hexadiene

1,3Hexadien5yne

CH3CH=CHCCH

CH3
1
3
2
5 4
CH3CCH2CH2CH=CH2
CH3

3Penten1yne

5,5Dimethyl1hexene

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CH2CH3
CH2
6

3 2

CHCC=CCH=CH2
1

CH2CH2CH3

1,4,4-Trimethylcyclobutene

3,4Dipropyl1,3hexadien5yne

2.3

RULES FOR NAMING ALKYL HALIDES

The halogen is treated as a substituent on an alkane chain. The halosubstituent is considered of
equal rank with an alkyl substituent in the numbering of the parent chain. The halogens are
represented as
F
fluoro
Cl

chloro

Br

bromo

Iodo

Here are some examples:

CH3
1

CH3 Br

CH3CHCHCH2CH3

CH3CHCHCH3

Cl
3Chloro2methylpentane

2.4

2Bromo3methylbutane

RULES FOR NAMING ALCOHOLS

Alcohols are named by replacing the suffix ane with anol. If there is more than one hydroxyl group
(OH), the suffix is expanded to include a prefix that indicates the number of hydroxyl groups present
(anediol, anetriol, etc.). The position of the hydroxyl group(s) on the parent chain is(are) indicated
by placing the number(s) corresponding to the location(s) on the parent chain directly in front of the
base name (same as alkenes).
Here is an important list of rules to follow:
1.
The hydroxyl group takes precedence over alkyl groups and halogen substituents, as well as
double bonds, in the numbering of the parent chain.
2.
When both double bonds and hydroxyl groups are present, the en suffix follows the parent
chain directly and the ol suffix follows the en suffix (notice that the e is left off, en instead of
ene). The location of the double bond(s) is (are) indicated before the parent name as before,
and the location of the hydroxyl group(s) is(are) indicated between the en and ol suffixes.
Again, the hydroxyl gets priority in the numbering of the parent chain.
3.
If there is a choice in numbering not previously covered, the parent chain is numbered to give
the substituents the lowest number at the first point of difference.
Here are some examples:

OH
1

CH3CHCHCH2CH3

OH

OH OH
1

CH3CHCHCH3

CH3
3Methyl2pentanol

2.5

1
2
3

2,3Butanediol

2Cyclopenten1ol

RULES FOR NAMING ETHERS

The generic IUPAC name of this family is alkoxy alkane in which alkane part contains longer carbon
chain in case of unsymmetrical ethers.
CH3OCH2CH3
Methoxy ethane

CH3CH2OCH2 CH3
Ethoxy ethane

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1
1

CH3OCH2CH2CH3
1Methoxy propane

CH3
2
CH3OCH
3 CH3
2Methoxy propane

2.6
RULES FOR NAMING ALDEHYDES
Aldehydes are named by replacing the suffix ane with anal. If there is more than one
CHO group, the suffix is expanded to include a prefix that indicates the number of CHO groups present (
anedial there should not be more than 2 of these groups on the parent chain as they must occur at the ends).
It is not necessary to indicate the position of the CHO group because this group will be at the end of the
parent chain and its carbon is automatically assigned as C-1.
Here is an important list of rules to follow:
1.
The carbonyl group takes precedence over alkyl groups and halogen substituents, as well as double
bonds, in the numbering of the parent chain.
2.
When both double bonds and carbonyl groups are present, the en suffix follows the parent chain
directly and the al suffix follows the en suffix (notice that the e is left off, en instead ene). The
location of the double bond(s) is(are) indicated before the parent name as before, and the al suffix
follows the en suffix directly. Remember it is not necessary to specify the location of the carbonyl
group because it will automatically be the first carbon. Again, the carbonyl gets priority in the numbering
of the parent chain.
3.
There are a couple of common names which are acceptable as IUPAC names. They are shown in the
examples in parenthesis.
Here are some examples:

O
Propanal

3Methylbutanal 3Methyl3butenal

O
HCH
Methanal
(Common name: Formaldehyde)

O
CH

O
CH3CH
Ethanal
(Common name: Acetaldehyde)

2.7

1.
2.

3.

Benzaldehyde

RULES FOR NAMING KETONES

Ketones are named by replacing the suffix ane with anone. If there is more than one carbonyl group
(C=O), the suffix is expanded to include a prefix that indicates the number of carbonyl groups present
(anedione, anetrione, etc.). The position of the carbonyl group(s) on the parent chain is(are)
indicated by placing the number(s) corresponding to the location (s) on the parent chain directly in front
of the base name (same as alkenes).
Here is an important list of rules to follow:
The carbonyl group takes precedence over alkyl groups and halogen substituents, as well as double
bonds, in the numbering of the parent chain.
When both double bonds and carbonyl groups are present, the en suffix follows the parent chain
directly and one suffix follows the en suffix (notice that e is left off, en instead of ene). The
location of the double bond(s) is(are) indicated before the parent name as before, and the location of
the carbonyl group(s) is (are) indicated between the en and one suffixes. Again, the carbonyl gets
priority in the numbering of the parent chain.
If there is a choice in numbering not previously covered, the parent chain is numbered to give the
substituents the lowest number at the first point of difference. Here are some examples:
O
O
Propanone
(Common name: Acetone)

3Methyl3buten2one

2Butanone

2,4Pentanedione

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2.8

RULES FOR NAMING CARBOXYLIC ACIDS

Carboxylic acids are named by counting the number of carbons in the longest continuous chain
including the carboxyl group and by replacing the suffix ane of the corresponding alkane with anoic
acid. If there are two COOH groups, the suffix is expanded to include a prefix that indicates the
number of COOH groups present (anedioic acid there should not be more than 2 of these groups
on the parent chain as they must occur at the ends). It is not necessary to indicate the position of the
COOH group because this group will be at the end of the parent chain and its carbon is automatically
assigned as C1.
Here is an important list of rules to follow:
1.
The carboxyl group takes precedence over alkyl groups and halogen substituents, as well as
double bonds, in the numbering of the parent chain.
2.
If the carboxyl group is attached to a ring, the parent ring is named and the suffix
carboxylic acid is added.
3.
When both double bonds and carboxyl groups are present, the en suffix follows the parent
chain directly and the oic acid suffix follows the en suffix (notice that the e is left off, en
instead of ene). The location of the double bond(s) is(are) indicated before the parent name as
before, and the oic acid suffix follows the en suffix directly. Remember it is not necessary to
specify the location of the carboxyl group because it will automatically be the first carbon. Again,
the carboxyl gets priority in the numbering of the parent chain.
4.
There are several common names that are acceptable as IUPAC names. They are shown in
the examples in the parenthesis.
5.
If there is a choice in numbering not previously covered, the parent chain is numbered to give
the substituents the lowest number at the first point of difference.
O

O
CH3COH

HCOH
Methanoic acid
(Common name: Formic acid)

Ethanoic acid
(Common name: Acetic acid)

O
COH

HO
3Methylpentanoic acid

OH

2.9

O O
HOCCOH

COOH
2Hydroxybenzoic acid
(Common name: Salicyclic acid)

Benzoic acid

HO

Ethanedioic acid
(Common name : Oxalic acid)

3Butenoic acid

RULES FOR NAMING ESTERS

Systematic names of esters are based on the name of the corresponding carboxylic acid. Remember
esters look like this:
O
RCOR

acyl group

alkyl group

The alkyl group is named like a substituent using the yl ending. This is followed by a space. The acyl
portion of the name (what is left over) is named by replacing the ic acid suffix of the corresponding
carboxylic acid with ate.
Here are some examples:
O
CH3CH2COCH3
Methyl propanoate

O
COCH2CH3
Ethyl benzoate

O
CH3COC(CH3)3
Tertbutyl acetate
or
Tertbutylethanoate

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2.10

RULES FOR NAMING AMINES

Primary amines (RNH2) are named as alkanamine. If the compound contain double bond along with
amino group, then it is named alkanamine. Alkyl and halo substituents are named as prefix in
alphabetical order.
For example,
CH3CH2CH2NH2

CH3CH2NH2

Propanamine

Ethanamine
3

Cl
1

CH3CHCH2CHNH2

CH2=CHCH2NH2

CH3
2Propenamine

1Chloro2methylbutanamine

Secondary amines (R 2NH) and tertiary amines (R 3 N) are named as Nalkyl alkanamine and
N,Ndialkyl alkanamine.
CH3CH2NHCH3

CH3CH2CH2NHCH2CH3

NMethylethanamine

NEthylpropanamine

CH3CH2NCH3

CH3CH2CH2NCH2CH3
CH3

CH3
N,NDimethylethanamine

2.11

(i)
(ii)
(iii)
(iv)

(v)

NEthylNmethylpropanamine

RULES FOR NAMING ORGANIC COMPOUNDS CONTAINING ONE OR MORE FUNCTIONAL

GROUPS
The rules for naming an organic compound containing functional groups are exactly same as discussed
already for compounds containing double and triple bonds. In this case, the preference of lowest
number is given to carbon atom bearing the functional group. The rules are summarized below:
Select the longest continuous chain containing the carbon atom having functional group(s).
The numbering of atoms in the parent chain is done in such a way that carbon atom bearing the
functional group gets the lowest number.
It two or more same functional groups are present, these are indicated by using di, tri, tetra as prefixed
to the name of the functional group.
If the organic compound contains a functional group, multiple bonds, side chain or substituents, the
following order of preference must be followed,
Functional group > Double bond > Triple bond > Side chain.
When an organic compound contains two or more functional groups, one group is regarded as the
principal functional group and the other group is treated as the secondary functional group, which may
be treated as substituent(s). The following order of preference is used for selecting the principal
functional group,
Carboxylic acids > sulphonic acids > acid anhydrides > esters > acid chlorides > amides > nitriles
>
aldehydes
>
ketones
>
alcohols
>
amines
>
imines
>
ethers
>
alkenes > alkynes.
Different classes of functional groups including multiple bonded compounds and the suffix or prefix
required to name these compounds are given in the preferential decreasing order in the following table.
Class of compounds

1.

Carboxylic acids

Functional group or
substituent

HO

C=O

Suffix

Prefix

Carboxylic acid/oic acid

carboxy

Sulphonic acid

sulfo

oic anhydride

2.

Sulphonic acids

SOH
O

3.

Acid anhydrides

COC

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(R) carboxylate
/(R)oate

alkoxy carbonyl

C=O

Carbonyl halide/oyl
halide

halo carbonyl

C=O

Carboxamide/amide

carbamoyl

Carbonitrile/nitrile

cyano

Carbaldehyde/al

formyl/oxo

C=O

one

keto/oxo

Alcohols

OH

ol

hydroxy

11.

Amines

NH2

amine

amino

12.

Imines

=NH

imine

imino

13.

Ethers

COC

alkoxy

14.

Alkenes

= (double bond)

ene

15.

Alkynes

(triple bond)

yne

4.

Esters

5.

Acid halides

6.

Amides

7.

Cyanides

8.

Aldehydes

9.

Ketones

10.

C=O

RO

NH2

CN
C=O

For those functionalities, which have two prefixes and/or suffixes, the first one is used when carbon
atom of the functional group is not a part of the longest continuous chain and the second one is used, when
carbon atom is counted in the longest chain.
2.12 RULES FOR NAMING AROMATIC COMPOUNDS
(i) When the benzene ring is present as one of the substituent in the carbon chain, it is named as phenyl
group.
(ii) Disubstituted, trisubstituted or tetrasubstituted benzenes are named by using the numbers.
(iii) If different groups are attached to the benzene ring, then the principal functional group is fixed as
number 1. The numbering of the chain is done in any direction (clockwise or anticlockwise), which
gives lowest number to the substituents. The substituents are written in the alphabetical order.
Let us see the application of these IUPAC rules to some organic compounds.
(i) (HOCH2CH2O)2CHCO2H

Bis(2hydroxyethoxy)ethanoic acid

C 2H 5
1

(ii)

1Ethyl4methylcyclohaxane

3
4

CH3
F

CH3CHCH

CH2CH3

(iii) CH3(CH2)4CH2CHCH2CH(CH2)3CH3

7(1,2Difluorobutyl)5ethyltridecane

CO2H
1

(iv)

2
3

4Oxo1,2,3,4tetrahydronaphthalene
1carboxylic acid

Page 10

O
(v) CH3CH2CH2CCH2Cl

1chloropentan2one

(vi)

1,2Didehydrobenzene

(vii) CH3CH2OCH2CH2Cl

1Chloro2ethoxyethane

(viii) OHCCH2CH2CHCH2CHO

3(Formylmethyl)hexanedial

CH2CHO
4

(ix) OHCCH2CH2CHCH2CHO

Butane1,2,4tricarbaldehyde

CHO
(x) CH3CH2CHOCH2CH3

1,1Diethoxypropane

OCH2CH3
(xi) HO2CCH2CH2CHCH2CH2CO2H

Pentane1,3,5tricarboxylic acid.

CO2H
(xii) NCCH2CH2CH2CHCH2CH2CN

Hexane1,3,6tricarbonitrile

CN
O
3

(xiii) OHC

2
1

CO2H

4Formyl2oxocyclohexane1carboxylic acid

(xiv) CH3CSOCOCH2CH3

Propionic thioacetic anhydride

(xv)

Cyclohexanecarboxamide

CONH2
O

(xvi) CH3CCH2CH2CH2CO2H
6

5Oxohexanoic acid

(xvii) CH3CH2CCH2CCH3
4

Hexane2,4dione

(xviii) CH2=CHCH2CH(OH)CH3

Pent4en2ol

NO2
3

(xix)

3Nitrocyclohexene

OH
1

(xx)

Cyclohex2en1ol

3.

ISOMERISM

The existence of different compounds having same molecular formula but different physical and
chemical properties is called isomerism. If the difference in properties is due to difference in their structural
formulae, it is called structural isomerism. And if the difference in properties is due to the arrangement of
atoms or group of atoms in space, it is called stereo isomerism. The different compounds are named as
isomers.
Isomerism is broadly divided into two types,
(i) Structural isomerism and (ii) Stereoisomerism

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3.1

STRUCTURAL ISOMERISM: Two or more compounds with the same molecular formula,
which differ in the arrangement of atoms within the molecule are called structural isomers and the
phenomenon is called structural isomerism. There are different types of structural isomerism.
3.1.1 CHAIN ISOMERISM
The chain isomers have same molecular formula but they differ in the length of carbon chain (straight
or branched). Compounds with four or more carbon atoms can show this kind of isomerism. For example,
(a) C4 H10 has two chain isomers.
CH3CH2CH2CH3

CH3CHCH3

(nButane)

CH3
2Methyl propane
(isobutane)

(b) C5 H12 has three chain isomers.

CH3
CH3CH2CH2CH2CH3

CH3CHCH2CH3

npentane

CH3CCH3

CH3

CH3

2Methyl butane
(isopentane)

2,2Dimethyl propane
(neopentane)

(c) C4 H9OH has two chain isomers.

CH3CH2CH2CH2OH

CH3CHCH2OH

Butan1ol
(nButyl alcohol)

CH3
2Methyl propan1ol
(Isobutyl alcohol)

(d) C4 H8 has two chain isomers.

CH3CH2CH=CH2
CH3C=CH2

But1ene
(Butylene)

CH3
2Methyl propene
(Isobutylene)

3.1.2

POSITION ISOMERISM
The position isomers have same molecular formula but differs in the position of either substituent or
functional group on the same carbon skeleton. For example,
(a) The molecular formula C 4H8 has two position isomers.
CH3CH2CH=CH2

CH3CH=CHCH3

But1ene
(Butylene)

But2ene
(Dimethyl ethylene)

(b) The molecular formula C 4H6 has two position isomers.

CH3CH2CCH

CH3CCHCH3

But1yne
(Crotonylene)

But2yne
(Dimethyl acetylene)

(c) The molecular formula C 4H9 Cl has two position isomers.

CH3CH2CH2CH2Cl

CH3CH2CHCH3

1Chlorobutane

Cl
2Chlorobutane

(d) The molecular formula C 6H6 O3N has three position isomers.
OH

OH

OH

NO2
NO2
orthonitrophenol
(1, 2substitution)

metanitrophenol
(1, 3substitution)

NO2
paranitrophenol
(1, 4substitution)

3.1.3

FUNCTIONAL GROUP ISOMERISM

The isomers having same molecular formula but different functional groups in the molecule are called
functional isomers. The following classes of organic compounds show functional isomerism among
themselves.

Page 12

(a) Alcohols and ethers are functional group isomers.

CH3CH2OH

CH3 OCH3

and

Ethanol
(Ethyl alcohol)
(Functional group OH)

Methoxy methane
(Dimethyl ether)
(Functional groupO)

(b) Aldehydes and ketones are functional isomers. They are also functionally isomeric to unsaturated
ethers, unsaturated alcohols, cyclic ethers and cyclic alcohols.
O
CH3CH2CH2C=O
H
Butanal
(butyraldehyde)
(Functional groupCHO)

CH3CH2CCH3
Butanone
(Functional group

CH2=CHOCH2CH3, CH2=CHCH2CH2OH

C=O)

OH

(c) Carboxylic acids and esters also share functional group isomerism.

O
CH3COH

HCOCH3

Ethanoic acid

Methyl methanoate

(d) Dienes, allenes and alkynes are functional isomers.

CH2=CHCH=CH2
CH2=C=CHCH3
CH3 CH2 CCH
Buta1, 3diene
Buta1, 2diene (An allene)
But1yne
(e) Nitro alkanes and alkyl nitrites are functional group isomers.
CH3CH2NO2
CH3 CH2 ONO
Nitroethane
Ethyl nitrite
(f) 1, 2 and 3 amines share functional group isomerism.
CH3CH2NHCH3
Nmethyl ethanamine
(2 amine)

CH3CH2CH2NH2
Propan1amine
(1 amine)

CH3
CH3NCH3
N, NDimethyl methanamine
(3 amine)

(g) Cyanides and isocyanides are functional group isomers.

CH3CN
CH3 N
C
Ethane nitrile
Methyl isocyanide
(h) Aromatic alcohols, phenols and ethers are also functional isomers.
CH2OH

OCH3

OH
CH3

Benzyl alcohol

Anisole

oCresol

DEGREE OF UNSATURATION

Deficiency of two hydrogen atoms in a molecule is a result of either a pibond or a ring in the structure
of that molecule. The sum of pibonds and rings in the structure of a compound collectively is called
degree of unsaturation or double bond equivalents in that compound. The most general type of
formula for any organic species is (C aHb NcOd). If the compound contains other atoms also, the
tetravalent atoms are replaced by carbon, monovalent atoms are replaced by hydrogen, divalent atoms
are replaced by oxygen and trivalent atoms are replaced by nitrogen. Then all oxygen and all nitrogen
atoms are removed from the formula. However, for the removal of each N atom, one H atom is also
removed from the molecular formula. If the molecular species is charged, H+ are added or removed to
neutralise the charge. As a result of all these operations, we will get a hydrocarbon. Now this
concluded hydrocarbon is compared with saturated alkane containing same number of carbon atoms to
determine the degree of unsaturation or double bond equivalents.
Example 1: C12 H16 N2OCl2

Page 13

C12H16 N2OCl2 will give C12 H18N2O after replacing Cl atoms by H atoms and C 12 H16 after removing O
and N. Corresponding saturated alkane should be C 12 H26 .
Double bond equivalents =

26 16
=5
2

Example 2: C13 H10 BrNS

C13H10 BrNS will give C13 H11 NO after replacing Br by H and S by O atoms. Removal of
O and N gives us C 13H10. The corresponding saturated alkane will be C 13H28.
Double bond equivalents =

28 10
= 9.
2

Example 3: C3 H8N+
C3H8N+ will give C3H7 N after losing one
The corresponding saturated alkane will be C 3H8 .
Double bond equivalents =

H+

ion.

Removal

of

gives

us

C 3H6.

86
= 1.
2

Example 4: C 5H5

C 5H5 will give C5H6 after adding one H+ ion. The corresponding saturated alkane will be C 5H12 . Double
12 6
bond equivalents =
= 3.
2
Catalytic hydrogenation (hydrogenation using H2 in presence of Ni or Pd at room temperature) data is
used to distinguish between the unsaturation due to a bond or unsaturation due to a ring. Compounds
having unsaturation due to bonds absorb 1 mole of H2 for each mole of a bond while compounds having
unsaturation due to rings do not absorb any hydrogen at room temperature.But compounds like cyclopropane
and cyclobutane do absorb 1 mole of H2 at 120C and 200C respectively because these rings are highly
strained and in order to get relieve from strain, they do get cleaved by H2 at elevated temperatures.
Cyclopentane and higher rings to not absorb any H2 at the experimental temperatures (200300C) as such
rings are quite stable.
+ H2

+ H2

Ni at
120C

Ni at
200C

CH3CH2CH3

CH3CH2CH2CH3

3.1.4 METAMERISM
Compounds having same molecular formula but different number of carbon atoms
(or alkyl groups) on either side of the multivalent functional group (i.e. O,S,NH, CO etc.) are called
metamers and the phenomena is called metamerism. Metamerism occurs among the members of the same
family. For example,

(a) CH3CH2COCH2CH3 is a metamer of CH3COCH2CH2CH3 and CH3COCH

Pentan3one

CH3
CH3

Pentan2one

3methyl butanone

The first two compounds are also related as position isomers as the position of
isomers is different.

C=O in the two

1
2

(b) CH3OCH2CH2CH3 is a metamer of CH3CH2OCH2CH3 and CH3OCH

1Methoxy propane
(Methyl npropyl ether)

Ethoxy ethane
(Diethyl ether)

CH3
3

CH3
2methoxy propane

Page 14

(c) CH3CH2NHCH2CH3 is a metamer of CH3NHCH2CH2CH3 and CH3NHCH

Diethyl amine

CH3
CH3

(Methyl npropyl amine)

Methyl isopropyl amine

Draw all possible metamers of CH3CH2NCH2CH2CH3.

CH2CH3
3.1.5

TAUTOMERISM
It is a special type of functional isomerism in which an hydrogen atom is shifted from one position
(atom1) to another (atom3). This shift is referred as 1,3 shift. Such shifts are common between a
carbonyl compound containing an hydrogen atom and its enol form.
R

RC=CR
1
2

RCCR
1
2

H O

HO

Keto form

Enol form

H = ( CH + CC + C=O) ( C=C + CO + OH) = 359 347 = 12 kcal/mol.

Thus, generally keto form is more stable than enol form by 12 kcal. So, in most cases, the equilibrium
lies towards the left.
The term tautomerism is used for isomers that are fairly readily interconvertible and that differ from
each other only (a) in electron distribution and (b) in the position of a relatively mobile atom or group,
The mobile atom is generally hydrogen and the phenomenon is then called as prototropy.
Both acids and bases catalyse such interconversions. Possible limiting mechanisms are those (a) in
which proton removal and proton acceptance (from the solvent) are separate operations and a
carbanion
intermediate
is
involved.
i.e.
an
intermolecular
pathway
and
(b) in which one and the same proton is transferred intramolecularly.

(a)

B:

H
R2CCH=Y

R2CCH=Y
BH

R2C=CHY

H
ROH
RO

R2C=CHY

(Intermolecular)

Carbanion
intermediate

(b)

R2CCH=Y

R2C

H
R2C=CHY

(Intramolecular)

CH
Transition state

1.

Mostly the keto form is more stable than enol form but in certain cases, enol form can become the
predominant form. The enol form is predominant in following cases:
Molecules in which the enolic double bond is in conjugation with another double bond/phenyl ring. In
such cases, sometimes intramolecular hydrogen bonding also stabilizes the enol.
R

CCR

C=CR
HO

H O

Enol form
(Crossconjugation)

Keto form

CH
CH3CCH2COEt
O

Keto form

CH3C
O

COEt
H

Enol form
(Crossconjugation and
intramolecular hydrogen bonding)

Page 15

CH
CH3CCH2CCH3
O

CH3C

Enol form
(Crossconjugation and intramolecular
hydrogen bonding)

Keto form

2.

CCH3

Molecules, which contain two bulky aryl groups.

Ar
CCH
Ar
H O

Ar
C=CH
Ar
HO

Keto form (5%)

Me
where Ar = Me
Me

Enol form (95%)

In the keto form of 2,2dimesitylethanal, the ArCAr bond angle is 109, whereby the bulky aryl
3.

groups experience greater steric repulsion. This steric repulsion eases off when the keto form
transforms to enol form, where the ArCAr bond angle widens to 120.
When the enol is aromatic stabilized.
O

OH

H
H
Enol form

Keto form

The extent of enolization is also affected by the solvent, concentration and temperature. Thus,
acetoacetic ester has an enol content of 0.4% in water and 19.8% in toluene. This is because water
reduces the enol content by hydrogen bonding with the carbonyl group, making this group less
available for intramolecular hydrogen bonding. The effectiveness of intramolecular hydrogenbonding
in stabilizing the enol, with respect to the keto form is seen on varying the solvent and particularly on
transfer to a hydroxylic solvent with MeCOCH2COMe.
Thus, the proportion of enol in the nonpolar solvent
Solvent
% Enol
(hexane) is the same as in the gas phase and higher than in
Gas phase
92
the liquid itself, the latter acting as a polar autosolvent. The
Hexane
92
proportion drops again in the more polar MeCN and more
dramatically in water. What is happening is the increasing
relative stabilization of the keto form by solvation, this being
MeCN
58
particularly marked in water where intermolecular hydrogen
bonding of the keto forms C=O groups can now take place
H2O
15
as an alternative to its enolization.
Also, the enol content of pentan2,4dione (CH3COCH2COCH3 ) is found to be 95% and 45% at 27.5 and
275C respectively. When a strong base is added to a solution of a ketone with hydrogen atom, both the
Liquid

76

enol and keto form can lose a proton. The resulting anion is same in both the cases as they differ only in the
placement of electrons. They are not tautomers but canonical forms.

R
CCR
R
H O
+
+H+ H

R
C=CR
R
HO
+
+H+ H

R ..
CCR
R
O

R
C=CR
R
O

(Carbanion)

(Enolate ion)

Other types of tautomerism

(i) PhenolKeto tautomerism:

Page 16

OH

H
H
Cyclohexadienone

Phenol

In this case, enol form is more stable than keto form because of the aromatic stabilization. (ii)
NitrosoOxime tautomerism:

R
CN
R
H O

R
C=N
R
OH

Nitroso form

Oxime form

This equilibrium lies far to the right and as a rule nitroso compounds are stable only when there is no
hydrogen atom.(iii) NitroAci tautomerism: Aliphatic nitro compounds are in equilibrium with the aci forms.
O
R
CN
R
O
H

O
R
CN
R

O
H

O
R
C=N
R
OH

Aci form

Nitro form

The nitro form is much more stable than the aci form because nitro group has resonance. Aci form of nitro
compounds is also called nitronic acids.
(iv)
ImineEnamine tautomerism / cyanideenimine tautomerism:

R
CCR
R
H NR

R
R C=CR
NHR

Imine form

Enamine form

Imine form predominates generally. Enamines are stable only when there is no hydrogen atom attached to
nitrogen.

R
CC
R
H N

R
C=C
R
NH

Cyano form

Enimine form

Which of the following compound shows tautomerism and also draw their tautomer?
(a) CH3CHO
(b) CH3COCH3 (c) CH3COCH2CH3 (d) C6H5CHO
(f) C6H5COC6H5 (g) O

(e) C6H5COCH3

(h)
O

3.1.6

RINGCHAIN ISOMERISM

Compounds having same molecular formula but possessing open chain and cyclic structures are called
ringchain isomers and the phenomena is called ringchain isomerism.
For example, (a)
C3H6 represents

CH3CH=CH2

and

Propene

Cyclopropane

(b) C4H8 represents

CH3 H
CH3CH2CH=CH2
But1ene

3.2

or

and
Cyclobutane

Methyl cyclopropane

STEREO ISOMERISM
Page 17

Isomers having the same molecular formula and same functional group but differ in their spatial
arrangement or group of atoms in space are called stereoisomers. They are said to have different
configurations or different arrangement of groups in 3D space. Stereoisomerism is of three kinds.
(a) Conformational isomerism (b) Geometrical isomerism and (c) Optical isomerism.
3.2.1 CONFORMATIONAL ISOMERISM
A bond between two carbon atoms is formed by the overlap of sp 3 hybrid orbitals of carbon atom along their
internuclear axis as a result of which the electron distribution within the molecular orbital thus formed is
cylindrically symmetrical along the internuclear axis. Due to this symmetry, rotation about carboncarbon
single bond is almost free,. As a result number of different arrangements of atoms about CC bond results
which are called conformations or rotational isomers or rotamers.
(a) CONFORMATIONS OF ETHANE
In ethane, the two carbon atoms are connected by a bond. If one of the methyl group in ethane molecule is
kept fixed and the other is rotated about the CC bond, infinite number of possible conformations of ethane
result (while counting the total number of isomers for a given molecular formula, the conforms are ignored).
The two extreme conformers are termed as staggered & eclipsed and the conformations lying between them
are termed as gauche or skew conformations. The conformations can be represented by Sawhorse or
Newman projections.
(i) Sawhorse projection
In this projection, the molecule is viewed along the axis of the model from above and right. The central CC
bond is drawn as a straight line, slightly tilted to right for the sake of clarity. The line is drawn some what
longer. The front carbon is shown as the lower left hand carbon whereas the rear carbon is shown as the
upper right hand carbon. Each carbon has three lines corresponding to three atoms/groups (H atoms in the
case of ethane).
H
H

H
H

Eclipsed

H
H

Staggered

Sawhorse projections of ethane

(ii) Newman projection

These projection formulae are obtained by viewing the molecule along the bond joining the two carbon atoms.
The atom near the eye is represented by a point and the three atoms or groups attached to it by three equally
spaced radii. The carbon atom farther from the eye is designated by a circle and the three atoms or groups
attached to it by three equally spaced radical extensions.
H

HH

H
H

H
H

H
H

Eclipsed

Staggered

Newman projections are more widely used to represent conformers. The various conformers of ethane are
shown as:
Ha

Ha Hb
H
60

H
H

H
H
Eclipsed (I)

Ha H

rotation

Ha H

Ha

Hb
60

H
H

Skew or gauche (II)

rotation

60

H
H

H
Hb

60

rotation

rotation

Hb
Eclipsed (III)

Staggered (IV)

Ha
Hb

60

Hb
H

H
H
Eclipsed (V)

rotation

H
Skew or gauche (VI)

Page 18

There are two types of strain among conformers.

(i) Torsional strainStrain due to repulsion between the bonded electron pair of CH or
CC bonds or other types of bonds.
(ii) Vander Waals strain Strain due to repulsion or
crowding between the groups attached to carbon.
Eclipsed form of ethane has both these strains more than in the skew form. Skew form and the
staggered form have similar strains, so they are equally stable.
Thus, stability order of conformers of ethane is
[(I) = (III) = (V)] < [(II) = (IV) = (VI)]Dihedral angle is the angle between HaCC and CCHb
planes in ethane.The energy profile of the conformers of ethane is shown as:
(V)

(III)

(I)

PE

2.9 kcal

(II)

60

120

(I)

(VI)

(IV)

180

300

240

360

Dihedral angle

Eclipsed

Staggered

(2%)

(98%)

Kc = Keq =

[Staggered] 98
=
= 49
2
[Eclipsed]

(b) CONFORMATIONS OF PROPANE

H H H
HC1C2C3H
H H H

Rotation about either C 1C2 bond or C2C3 bond results in the same conformers. If rotation about C2C3 bond
is considered, the conformers of propane can be drawn by replacing Ha of ethane by CH3 group. Everything
else remains same but the energy difference between eclipsed and staggered form will be 3.2 kcal/mol.
(c) CONFORMATIONS OF nBUTANE
In order to examine the conformations of nbutane, it is considered as a derivative of ethane in which one
hydrogen atom of each carbon is replaced by a methyl group. Thus, butane is considered as dimethyl ethane
as shown below,

H H
4
3
CH3CCCH3
H H
1

Rotation about C1 C2 and C3C4 bond results in the same conformers. If rotation about C1C2 or C3C4 bond
is considered, the conformers of nbutane can be drawn by replacing Hb | Ha of ethane by C2H5 group. The
difference in energy between eclipsed and staggered from will be 3.4 kcal/mol.Rotation about C 2C3 bonds
gives six conformers, which are shown as:

rotation
by 60

H
H

H
H

Fully Eclipsed (I)

H3C H

H3C

H3CCH3

CH3

rotation
by 60

H
H

H
Skew or gauche (II)

H
CH3

Partially Eclipsed (III)

rotation
by 60

Page 19

H3C H

H3C
H3C

rotation by
60

H3C
rotation

H3C
H

by 60

H
H

H3C

Skew or gauche (VI)

Staggered (IV)

Partially Eclipsed (V)

Relative stabilities of conformations

Out of the four conformations listed above, anticonformation (IV) is the most stable since in this
conformations the two nonbonded methyl groups (dihedral angle 180) and the four nonbonded hydrogen
atoms are as far apart as possible. The next in order of higher energy come the two gauche conformations ( II
and VI) in which the two nonbonded methyl groups are only 60 apart and hence causing less crowding or
steric strain than eclipsed forms. As a result of this steric strain, the two gauche conformations (II and VI) are
slightly less stable than the anticonformation (IV). However, the two gauche conformations are themselves of
equal energy. Experimentally, it has been found that the gauche conformations are about 0.9 kcal mol 1 less
stable than the anti conformation. Next in order of higher energy fall the two partially eclipsed conformations
(III and V). In these conformations, there are two methylhydrogen eclipsing interactions and one
hydrogenhydrogen eclipsing interaction. Because of methylhydrogen eclipsing interactions partially eclipsed
conformations of nbutane are less stable than anti and gauche conformations. However, the two partially
eclipsed conformations are themselves of equal energy.Experimentally, it was found that partially eclipsed
conformation (III and V) is less stable than gauche conformation (II or VI) by about 2.9 kcal mol1 and than
anti conformation (IV) by about 3.8 kcal mol1. The fully eclipsed conformation (I) is however, the least stable.
This is due to the reason that in this conformation, there is one methylmethyl eclipsing interaction and two
weak hydrogenhydrogen eclipsing interactions. Experimentally, it has been found that fully eclipsed
conformation is about 4.5 kcal mol1 less stable than the most stable anti conformation. Thus, the relative
stabilities of the four distinct conformations of nbutane follow the order,
Anti > Gauche or skew > Partially eclipsed > Fully eclipsed.
(IV)
(II & VI)
(III & V)
(I)
The energy profile for the conformers of nbutane by rotation about C 2C3 bond is
(I )

(I)
(V)

(III)
4.5 kcal

PE

2.9 kcal
3.6 kcal (II)

3.8 kcal

(VI)

0.9 kcal

60

(IV)

120

180

240

300

360

Dihedral angle

It is not always that anti or staggered conformation is more stable than skew or gauche. Sometimes,
the skew or gauche conformer is more stable than anti conformer because of stabilization of skew form by
intramolecular hydrogen bonding. For example, ethylene glycol,2chloro ethanol etc.
O

OH

Cl

>
H
Skew form of
ethylene glycol

3.2.2

>
OH
Staggered form of
ethylene glycol

H
Skew form of
2chloroethanol

Cl
Staggered form of
2chloroethanol

GEOMETRICAL ISOMERISM
Hindered rotation about carboncarbon bond

Page 20

A double bond consists of a bond and a bond. The bond is formed by the sideways overlapping
of unhybridized porbitals of two carbon atoms above and below the plane of carbon atoms. If one of the
carbon
atoms
of
the
double
bond
is
rotated
with
respect
to
the
other,
the
porbitals will no longer overlap and the bond should break, but the breakage of this bond requires 251 kJ
mol1 of energy which is not provided by the collisions of the molecules at room temperature. Consequently,
the rotation about a carboncarbon double bond is not free but is strongly hindered or restricted. In other
words, a bond prevents free rotation of the carbon atoms of the double bond with respect to each other. Due
to this hindered rotation, the relative positions of atoms or groups attached to the carbon atoms of the double
bond get fixed. For example, Ha and Hb cannot exchange their positions by rotations of C1 with respect to C2
without breaking the bond.

Ha

Ha
C

Hb
a

b
C
C

h or

C.
.
C

Hb
a

b
rotation
by 180

C.
.
C

reformation
of bond

b
C
C

(trans isomer)

(cis isomer)

Energy profile for the conversion of cis isomer to trans isomer can be depicted as

Ea
PE
cis

trans

Progress of reaction

Necessary and sufficient conditions for geometrical isomerism

The necessary conditions for a molecule to exhibit geometrical isomerism are
(i)
The molecule must have restricted rotation due to the presence of a C=C, C=N, N=N and cyclic
structure. (ii) Each of the two atoms having restricted rotation must be attached to different substituents.
Thus, alkenes of the type abC=Cab and abC=Cde show geometrical isomerism.

a
b

C=C

a
b

cisisomer (I)

a
b

C=C

b
a

transisomer (II)

Both these isomers have the same structural formulae but differ in the relative spatial arrangement of
groups around the double bond. The isomer I, in which the similar atoms or groups lie on the same
side of the double bond is called the cis isomer whereas the isomer II, in which the similar atoms or
groups lie on the opposite sides of the double bond is called the trans isomer. It is because of this
reason that geometrical isomerism is also called cis trans isomerism.
In the case of cistrans nomenclature, the atoms or groups attached to the Catoms should be similar
but if all the four groups are different, then E, Z nomenclature comes into picture. According to this
nomenclature, if the atoms or groups of higher priority are on the same side of the double bond, the
isomer is designated as Z (zusammen, in German means together) and if the two atoms or groups of
higher priority are on the opposite sides, the isomer is designated as E (Entegegan, in German means
opposite). The priority of a group or atom is based on the atomic number but when atomic numbers are
same (for example, isotopes) then priority is decided by atomic mass.

Page 21

a
b

C=C

C=C

Zisomer

Eisomer

(If groups a and d

have higher priority)

(If groups a and d

have higher priority)

For example, in 1bromo2chloro2fluro1iodo ethene, C1 has two atoms viz. Br and I.

Since I (Z = 53) has higher atomic number than Br (Z = 35), therefore I is assigned priority 1 while Br is
assigned priority 2. Similarly, Cl is assigned priority 1 while F is assigned priority 2 on C 2.

Br(2)
(1) C
I

F(2)

Cl(1)

However, geometrical isomerism is not possible, if one or both the doubly bonded carbon atoms carry two
similar substituents. This is because in such cases, the two possible configurations are, identical as shown
below.

C=C

C=C

d
a
e
a
It is
because
of
this
reason
that
terminal
alkenes
such
as
propene,
1butene,
2methyl propene and alkenes carrying identical substituents on one of the doubly bonded carbon atoms such
as 2methyl 2butene and 2, 3dimethyl 2butene etc. do not show geometrical isomerism. Some other
examples of geometrical isomers are:
H

CO2H

C
CO2H

HO2C

Maleic acid (cis isomer)

CO2H

H3C

H3C

C
C

C2H5

cis2pentene

Fumaric acid
(trans isomer)
1

H
C
C

C2H5

trans2pentene
5

CH3CH=CHCH=CHCH3 (2,4hexadiene).
Let
us
see
the
isomers
of
There
are
3 geometrical isomers of it, namely ciscis, cistrans or transcis and transtrans. It is a symmetrical diene.
H3C
H

C
C

C
C

H3C
H

CH3

C
C

H3C

(ciscis)

H3C

C
C

CH3

(transtrans)

(cistrans or transcis)
2

But CH3CH=CHCH=CHCH2CH3 (2,4heptadiene) shows 4 geometrical isomers, namely ciscis,

cistrans, transcis and transtrans. It is an unsymmetrical diene.

H3C
H

C
C

C
C

CH2CH3

(ciscis)

H3C
H

CH3CH2

C
C

C
C

(cistrans)

H
H

C
C

CH3

C
C

CH2CH3

(transcis)

CH3CH2

C
C

CH3
C
C

(transtrans)

Page 22

Draw and give the stereochemical designation for the geometric isomers of
3,5octadiene.
Number of geometrical isomers
(i) The number of geometrical isomers of an unsymmetrical polyene = 2n (where n is the number of
double bonds).(ii)
The number of geometrical isomers of symmetrical polyene containing even
n

number of double bonds = 2n1 + 2 2

.(iii) The number

of geometrical isomers

of symmetrical

n1
2 2

polyene containing odd number of double bonds = 2n1 +

.
Geometrical isomerism is also shown by compounds which contains C=NOH , N=N structural units.
Cyclic compounds also exhibit geometrical isomerism.
Compounds
containing
are
commonly
called
oximes.
Oxime
of
C=NOH units
H
formaldehyde is incapable of showing geometrical isomerism, H C=NOH while oxime of any other aldehyde
(other than formaldehyde) will exhibit geometrical isomerism.

N
OH

HO

(syn isomer)

(anti isomer)

The nomenclature for aldoximes is syn (when H and OH are present on same side of the double bond) and
anti (when H and OH are present on opposite sides of the double bond). Oximes of symmetrical ketones
R C=NOH
R
do not show geometrical isomerism but oximes of unsymmetrical ketones R C=NOH are
R

capable of showing geometrical isomerism.

N
OH

HO
Syn (R)
or anti (R)

Syn (R)
or anti (R)

In this case, syn and anti nomenclature is used but the group with respect to which OH is syn or anti is to be
specified.Diazobenzene also exhibit geometrical isomerism as it fulfills the necessary condition.

Ph

Ph

Ph
N

N
Ph

(cis isomer)

(trans isomer)

Cyclic compounds too have restricted rotation because of the impossibility of rotation around CC single bond
as the conformation of cyclic compound would twist on rotation. Appropriately placed substituents on
cycloalkanes would be capable of showing geometrical isomerism.
X
X

X
X

1,2cis

1,2trans

1,3cis

1,3trans

X
1,4cis

1,4trans

3.2.3

OPTICAL ISOMERISM
Ordinary light has vibrations in all possible planes. In plane polarized light, the vibrations are only in
one plane. The optical isomers differ in the action on plane polarized light. One of the isomer turn the plane of

Page 23

the
polarized
light
to
the
right
(dextro
rotatory),
the
other
turn
it
to
the
left
(laevo rotatory). Optical activity is due to molecular asymmetry. Molecular asymmetry implies that the
compound should not contain any symmetry element (i.e. plane of symmetry and centre of symmetry). A
compound containing a single chiral atom (attached to four different atom or group of atoms) would always be
optically active but compounds with more than one chiral carbon may or may not be optically active.

Conditions for a compound to exhibit optical activity

(a) The compound should be chiral (asymmetrical). The compound should be devoid of any element of
symmetry like plane of symmetry, centre (point) of symmetry etc.
(b) The mirror image of the compound should be nonsuperimposable on it.
A compound or an isomer if fulfills the first condition, the second condition will be automatically fulfilled.
If second condition is seen first and is found to be fulfilled, this means that the first condition would
have been obeyed. So, for a compound/isomer, if it is to be checked that it is optically active or not, any
one of the above condition can be checked.
(i) Plane of symmetry: A plane of symmetry (also called a mirror plane) is a plane passing through the
molecule such that the molecule is divided into 2 equals parts, one part being the mirror image of other
(the plane acting as a mirror). Plane of symmetry can be at the centre of a CC bond or through the
centre of atom. For example,

b
a

plane of symmetry
b
Such an isomer is called meso isomer, which is optically inactive due to the presence of plane of
symmetry. The optical rotation of one half of the molecule is exactly cancelled by the other half. This is
called internal compensation. Meso isomers do not have a mirror image as the mirror image is identical
to the isomer itself.
(ii) Centre of symmetry: A center of symmetry is a imaginary point within the molecule such that a
straight line drawn from any part or element of the molecule to the center and extended an equal
distance on the other side encounters an equal part or element but this should happen in all directions
to be able to qualify as centre of symmetry. If it happens in one or two direction but not in other
directions then such a point is not a centre of symmetry. For example, 2, 4dimethyl cyclobutane1,
3dicarboxylic acid possess a centre of symmetry, which is the centre of the ring. Centre of symmetry
can be at the centre of molecule or over an atom or midway between a bond.
CH3
H

CO2H
H

CO2H

CH3
Another important example of the compound having a centre of symmetry is the trans form of dimethyl
keto piperazine. The compound exists in two formscis and trans. The cis form of the compound exists
in two enantiomeric forms but the trans form has a centre of symmetry and therefore, it is optically
inactive.
H3C

CO

NH

NH

CO

CH3

cisdimethyl ketopiperazine
Optically inactive

H3C

CO

NH

NH

CO

CH3

transdimethyl ketopiperazine
(centre of symmetry)
Optically Active

Similarly, truxillic acid is optically inactive because of the presence of a centre of symmetry.

Page 24

COOH

Ph

COOH

Ph

truxillic acid

It must be noted that only evenmembered rings possess a centre of symmetry. It is not found in
oddmembered rings. Centre of symmetry will never exist in a molecule having only one chiral centre.Organic
compounds
having
atleast
one
chiral
carbon
atom
or
asymmetric
carbon
atom
(a carbon atom attached to 4 different monovalent atom or groups) are always optically active. For example,
lactic acid (2hydroxy propanoic acid) CH3 CH(OH)COOH contains a chiral carbon atom and exhibits optical
activity. Lactic acid exists in two forms, one is the mirror image of the other and the two forms are
nonsuperimposable.

CH3
C
H

These 3dimensional projections of lactic acid can be

represented on 2dimension by Fischer projection
formulas. In drawing Fischer projection formula from
a 3dimensional projection, the group at the back of
the plane (COOH) is pulled to bring on the same line
as that of the CH3 and the groups projecting in the
front (H and OH) will be pushed to bring them on the
same horizontal line. Thus, Fischer projection of lactic
acid would be drawn as

CH3
C
H
CO2H

HO

OH
CO2H
Mirror

CH3
H

CH3
OH

(Note: Fischer projections are drawn only for those

molecules, which have chiral carbon atom).These two
isomers are called enantiomers. The stereoisomers,
which are related as mirror imageobject are called
enantiomers. One isomer and its enantiomer are
mirror images of each other and they are not
superimposable. Which of the two forms drawn is
dextro or laevo, cannot be known by looking at their
structures,

HO

CO2H

CO2H
Mirror

it

can
only
be
determined
experimentally
using
polarimeter.
An equimolar mixture of two enantiomers of lactic acid shows no rotation of plane polarized light, thus it
is optically inactive. It is called racemic form or racemic mixture and is designated as (). The optical
rotation of one enantiomer exactly cancels the optical rotation of other so that the net rotation is zero.
So, racemic mixture is optically inactive due to external compensation. The enantiomers can be
separated from a racemic mixture and the process of separation is called resolution.
Let us see the optical activity of 2butanol.
1

CH3

CH3

OH

HO

CH2CH3

H
4

CH2CH3

Mirror

Structures I and II are mirror images of each other and are not superimposable. They are enantiomers
of 2butanol. A pair of enantiomers is always possible for molecules that contain one tetrahedral carbon atom
with four different groups attached to it. The carbon atom C 2 is called a stereocentre.Let us see the optical
activity of tartaric acid, HO 2CCH(OH)CH(OH)CO 2H.

Page 25

CO2H

CO2H
OH

H
H

OH
H

H
HO

OH
CO2H

CO2H
HO
H

CO2H

(1)
Meso isomer
(does not have mirror image)

H
OH
CO2H

(2)
d or l
Optically active

(3)
l or d
Optically active

Stereoisomers (2) and (3) are enantiomers (mirror image isomers) but those stereoisomers which are
not related as mirror imageobject but have same molecular formula are called diastereomers. Stereoisomers
(1) & (2) and (1) & (3) are related as diastereomers. Let us now see the optical activity in
2,3dibromopentane.2,3dibromopentane has two dissimilar asymmetric carbon atoms. The number of
stereoisomers are shown as
CH3

CH3
Br
Br

H
H

Br

H
H

Br

C2H5
(1)

CH3

CH3
Br
H

H
Br

Br
H

H
Br

C2H5

C2H5

C2H5

(2)

(3)

(4)

Structures (1) and (2) are mirror images of each other and so are enantiomers. Structures (3) and (4)
are also mirror images of each other and they form another set of enantiomers, all stereoisomers 1 to 4 are
optically active. Structures (1) and (3) are called diastereomers. Structures (1) & (4) and (2) & (4) are also
related as diastereomers.

Number of optical isomers

As it has been discussed above, a compound containing two dissimilar carbon atoms can exist in four
optically active forms. Reasoning in the same fashion, we will find that a compound containing three such
asymmetric carbon atoms can exist in eight different configurations, which represent optical isomers. Thus in
general, the number of stereoisomers for a compound with n distinct (different) asymmetric carbon atoms in 2n.
When an organic compound contains two similar asymmetric carbon atoms in its molecule, abdCCabd, the
number of optically active isomers would be less than 2 n. Thus, tartaric acid [HO 2CCH(OH)CH(OH)CO 2H] has
two similar asymmetric carbon atoms and exists in only three forms, of which two are optically active and one
is optically inactive (meso form). Thus, the general formulas for predicting the number of optical isomers is
given as under.
1. When the molecule is unsymmetrical:
Number of d and l isomers (a) = 2n.
Number of meso forms (m) = 0.
Total number of optical isomers (a + m) = 2n.
where n is the number of chiral carbon atom(s).
Common example is CH3CH(Br)CH(Br)COOH.
2. When the molecule is symmetrical and has even number of chiral carbon atoms:
Number of d and l isomers (a) = 2n1 .
n

Number of meso forms (m) = 2 2 .

Total number of optical isomers = (a + m).
Common example is tartaric acid, HOOCCH(OH)CH(OH)COOH.
3. When the molecule is symmetrical and has an odd number of chiral carbon atoms:
n1

Number of d and l forms (a) = 2

n 1
2 2

n 1
2 2

Number of meso forms (m) =

.
Total number of optical isomers = (a + m) = 2n1.

Page 26

Common example is CH3CH(OH)CH(OH)CH(OH)CH3 .

Draw all the stereoisomers of 3chloro2pentanol, CH3CH(OH)CH(Cl)CH2CH3 and

give the stereochemical relationships of the stereoisomers.
Enantiomers:
Physical and chemical properties of enantiomers are as follows:
1. Enantiomers
have
identical
physical
properties
like
boiling
point,
melting
point,
solubility etc.
2. They rotate the plane of polarized light in opposite directions, though in equal amounts. The isomer that
rotates the plane to the left (counterclockwise) is called the laevo isomer and is designated as (), while
the one that rotates the plane to the right (clockwise) is called the dextro isomer and is designated as
(+). Because they differ in this property they are often called optical antipodes.
3. Enantiomers, react at the same rate towards achiral reagents, solvents and catalysts. Towards chiral
reagents, solvents and catalysts, enantiomers react at different rates. The transition states produced
from the chiral reactant and the individual enantiomers are not mirror images. They are diastereomeric

and hence have different enthalpies. The H values are different for the two and hence the rates of
reaction and the amounts of product formed. Their rates may be so far apart that one enantiomer
undergoes the reaction at a convenient rate while the other does not react at all. This is the reason that
many compounds are biologically active while their enantiomers are not.
Although pure compounds are always optically active, if they are composed of chiral molecules,
mixtures of equimolar amounts of enantiomers are optically inactive since the equal and opposite
rotations cancel. Such mixtures are called racemic mixtures or racemates. Their properties are not
always the same as those of the individual enantiomers. The properties in the gaseous or liquid state or
in solution usually are the same, since such a mixture is nearly ideal, but properties involving the solid
state, such as melting points, solubilities and heats of fusion, are often different. Thus, racemic tartaric
acid has a melting point of 204206C and a solubility in water at 20C of 206 g/litre, while for the (+) or
the () enantiomers, the corresponding data are 170C and 1390 g/litre. The separation of a racemic
mixture into its two optically active components is called resolution. The most widely used methods for
the resolution of a racemic mixture is chemical separation.
Chemical Separation: Pasteur was the first investigator to resolve a racemate chemically and his
method is used even today. For example, an optically pure compound, a (+) base, is reacted with a
racemic acid, resulting in two salts: a (+) (+) salt and a () (+) salt. Since these are diastereomers, they
have different solubilities & boiling points and are separable either by fractional crystallization or by
fractional distillation, after which the enantiomers are recovered.
Let us have an enantiomeric pair of CH3CHCO2H. To separate the two isomers of this pair, we treat
C2H5
them with an optically active (chiral) alcohol, CH3CHOH. The reaction can be outlined as:
C2H5
C2H5

C2H5

COH

H3C

C2H5

CH3

HO

(dform)

CH3

CO

H3C

C2H5

(dform)

(d, d ester)
C2H5

C2H5
CH3

HOC
O

H
(lform)

(dform)

C2H5

CH3

HO

H3C

CH3

CO
C2H5 O

(l, d ester)

The esters produced can be seen that they are not enantiomers (mirror image isomers), infact they are
diastereomers. This means that they have different boiling points and thus can be separated by fractional
distillation. d, d and l, d esters are collected as different fractions. Each fraction is separately hydrolysed. Let

Page 27

us say fraction I which have d, d ester, on hydrolysis gives d acid and dalcohol, which are different
compounds having different boiling points, so can be further separated by fractional distillation. On the other
hand, fraction II has l, d ester, which on hydrolysis yield lacid and dalcohol, having quite different boiling
points, so can be separated by fractional distillation. Thus, the enantiomeric acids (d and lform) have been
separated (resolved). The energy profile for the ester formation reaction of enantiomeric acids with optically
active alcohol (dform) can be shown as:
The two enantiomeric acids have same enthalpies but
the diastereomeric esters have different enthalpies,
the transition states for the formation of esters also
have different enthalpies. Thus, the activation energy
for the formation of d, d ester and l, d ester are
different and so, are their rates of reaction. When we

PE

say that a compound is resolvable, it is implied that

the compound is optically active and is comprised of d
and lforms.

POR

But when the compound is nonresolvable, it means that the compound is optically inactive (achiral), which
could be either due to absence of a chiral centre and having a plane of symmetry or due to presence of chiral
centre and having a plane or centre of symmetry.Those stereoisomers, which are not mirror images are called
diastereomers. Diastereomers have different physical properties. e.g. melting and boiling points, refractive
indices, solubilities in different solvents, crystalline structures and specific rotations. Because of their
differences in solubility, they often can be separated from each other by fractional crystallization.
Diastereomers have different chemical properties towards both chiral and achiral reagents. Neither any two
diastereomers nor their transition states are mirror images of each other and so will not necessarily have the

same energies. The H values will be somewhat different and thus the rates of reaction will differ. However,
since the diastereomers have the same functional groups, their chemical properties are not too dissimilar.You
will be astonished to see that the compounds even if they do not have the optically active carbon can still show
optical activity. For example, allenes, biphenyls, spiran etc.By preliminary examination, it seems that the
compound possess plane of symmetry and thus, it should be optically inactive. But on closer observation, it is
revealed that it is optically active due to the following reasons.
R1

C=C=C

R2

R3
R4

If we see the structure, C1, C3 are sp2 hybridised but C2 is sp hybridised. The participation
of orbitals for C1 clearly are (s + px + py), for C2 (s + px) and for C3 (s + px + pz) considering
CCCbond is along Xaxis. Therefore, the orbital picture can be shown as

R3
R1
sp2

R2

sp

sp2

2py
2pz

2pz

R4

XY plane

Therefore, within the molecule two distinct planes

arise and any one or all of them may be plane of
symmetry or may be none. Very clearly none is the
plane of symmetry as R 1, R2, R3, R4 are all different.
If R1 = R2, R3 R4 then XZ plane within the
compound will bisect it into two equal halves. So,
XZ plane will be the plane of symmetry. For the
compounds with cumulative odd number of double
bonds and different terminal groups will never show
optical activity because clearly the terminal carbon
lie in the same plane.

XZ plane

Therefore, the compounds become optically inactive. Draw the orbital picture and see on your own. Such
compounds will show geometrical isomerism.For the biphenyl compounds having all sp 2 hybridised carbon
atoms if the o, osubstituents are very bulky then to release steric strain, the rotation around CC bond axis
takes place causing loss of planarity of the compound. For example,

Page 28

Here as the o, o groups are very bulky, biphenyl

rings change their planarity as shown. Now the bulky
groups are situated at 90 angle apart. Hence, none
of the planes XY or XZ are the planes of symmetry.
So, compound is optically active.

NH2 (CH3)3C

C2H5O (CH3)2CH

NH2

Similar things happen with spiranes having even

number of rings and terminal carbons having different
groups. Such a compound will have no plane or centre
of symmetry, so it is optically active

(CH3)3C

OEt (CH3)2CH
XY plane

R1
R2

XZ plane
R3
(Optically active)
R4

R3
(Geometrically active)
R4

R1
R2

But in the above compound, there is a plane of

symmetry, so it is optically inactive. Such compounds
are capable of showing geometrical isomerism.
Optical rotation for a mixture of optically active
o
isomers is given by obs = i X i

Draw all the stereoisomers of (a) 1, 2dimethyl cyclopropane (b) 1, 2dimethyl

cyclobutane (c) 1, 3dimethyl cyclobutane (d) 1, 3dimethyl cyclopentane.

PROFICIENCY TEST

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

The following 10 questions deal with the basic concepts of this section. Answer the following briefly. Go
to
the
next
section
only
if
your
score
is
greater
than
or
equal
to
8.
Do not consult the study material while attempting the questions.
True/False. CH3CH2CN can show structural isomerism.
True/False. CH3COCH3 can not show tautomerism.
True/False. CHDTMe can show optical isomerism.
True/False. A mixture of 50% d + 50% l isomers is called racemic mixture.
True/False. CH3COCH2COCH3 exists in more enolic form in gaseous phase or nhexane.
True/False. Tartaric acid can have 3 optical variety.
True/False. Dextro compound rotates the plane polarized light towards left.
True/False.Cummulenes with even number of double bonds and each terminal carbon attached to two
different group of atom, is geometrically active.
True/False. Geometrical isomers can be referred as diastereomers.
True/False. CH3COCH3 will have more enol content than CH3COCH2 COCH3 in aqueous solvent.

ANSWERS TO PROFICIENCY TEST

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

True
False
True
True
True
True
False
False
True
False

SOLVED OBJECTIVE EXAMPLES

Page 29

Example 1:
Increasing order of stability among the three main conformations (i.e. Eclipse, Anti, Gauch e) of
2fluoroethanol is
(a) Gauche < Eclipse < Anti
(b) Eclipse < Anti < Gauche
(c) Anti < Gauche < Eclipse
(d) Eclipse < Gauche < Anti

Solution:
Eclipsed form of 2fluoroethanol is least stable due to repulsion between the F and OH groups as well as d ue to
torsional strain. Gauche form is most stable as the torsional as well as vander Waals strain both are considerably
reduced and the intramolecular Hbond further increases the stability. Therefore, the increasing order of stability
is Eclipse < Anti < Gauche.

(b)

Example 2:
The number of structural isomers for C 6H14 is
(a) 3
(b) 4
(c) 5
(d) 6

Solution:
The various isomers possible are:
nhexane, 2methylpentane, 3methylpentane, 2,2dimethylbutane, 2,3dimethylbutane.

(c)

Example 3:
STATEMENT1: Molecules that are not superimposable on their mirror images are chiral.
because
STATEMENT2: All chiral molecules have chiral centres.
(a) Statement1 is True, Statement2 is True; Statement2 is a correct explanation for Statement1.
(b) Statement1 is True, Statement2 is True; Statement2 is NOT a correct explanation for
Statement1.
(c) Statement1 is True. Statement2 is False.
(d) Statement1 is False. Statement2 is True.

Solution:
Statement-1 is correct. Statement-2 is incorrect because compound can be chiral even in the absence of chiral
atoms.

(c)

Example 4
h
CH3 CHCH2CH3 + Cl2
N isomers of C5H11Cl
CH3

The values of N and n are

(a) 6,6
(c) 4, 4

Fractional
distillation

n distilled products

(b) 6, 4
(d) 3, 3

Solution:

CH3CHCH2CH3
CH3

Cl 2/ h

Cl
Cl
CH3CHCH2CH2Cl + CH3CHCHCH3 + CH3CCH2CH3 CH2CHCH2CH3
CH3
CH3 Cl
CH3
CH (d, l)
+

(d, l)

(b)

SOLVED SUBJECTIVE EXAMPLES

Example 1:
Find out whether the given compounds are optically active or not.
SO3H

(i)

SO3H C2H5

(ii)
I

CH3

Page 30

CH3

(iii)

C2H5

C=C=C=C

C3H7
CH3

Solution:
In compounds (i) and (iii), there is plane of symmetry passing through the compound s
(molecular plane). Therefore, they are optically inactive. Compound (ii) does not have any plane of symmetry as
the two phenyl rings are not in the same plane. One of the ring rotates about
CC bond axis because of bulky substituents at o, o positions of two adjacent phenyl rings and the two rings
are perpendicular to each other. So, (ii) is optically active.

Example 2:
Find whether the following compounds are optically active or not.
D
T C H

R3

R1
R2

(i)

R4

CH3

(iii) H
Cl

R3
R4

R1

(ii) R2

Cl

H
H
CH3

Solution:
Compound (i) is optically active because there is no plane of symmetry, which can cut the molecule into two
equal halves. Compound (ii) also does not have plane of symmetry so, it is optic ally active. Compound (iii) is
optically inactive because of the presence of centre of symmetry.

Example 3:
Given that obs = xii , where xi = Mole fraction of the stable conformer and i = Dipole moment of the
stable conformer. Find the dipole moment of gauche conformer of ZCH2CH2Z if obs = 1.0 D and xanti =
0.82. Also draw the stable Newman projections for meso Y CHDCHDY if (i) Y = CH3 and (ii) Y = OH.

Solution:
There are two
ZCH2CH2Z
gauche and anti.

stable

conformers

of

the

compound
viz,

Z
H

x(anti) = 0.82 x(gauche) = 0.18 ;

(anti) = 0

Z
Z

obs = (gauche) x(gauche) + (anti) x(anti)

(gauche)

H
H
Z
(anti)

1 = (gauche) 0.18 + 0 0.82 ; (gauche) = 5.56 D.

The stable conformer of meso form of YCHDCHDY when Y = CH3 is anti because of least repulsion between
methyl groups. When Y = OH, then the Gauche form is more stable because of intramolecular hydrogen bonding.
CH3

CH3
(anti)

H
H
(gauche)

EXERCISE I
1.

2.

AIEEE-SINGLE CHOICE CORRECT

How many pairs of diastereoisomers are possible in the following molecule PhCH(Cl)CH(Cl)Ph?
(a) none
(b) two
(c) four
(d) eight
Which of the following compound will show optical isomerism?
(a) Butanal
(b) 2Chlorobutanol
(c) 2Propanol
(d) 1Butene

Page 31

8.

The total number of optically active and meso forms possible for the compound [HOOC(CH(OH))3
COOH] respectively are
(a) 4, 4
(b) 4, 2
(c) 3, 2
(d) 2, 3
The most stable conformation of chlorohydrin at room temperature is
(a) fully eclipsed
(b) partially eclipsed
(c) gauche
(d) staggered
The dihedral angles between the two CBr bonds in gauche, partially eclipsed, staggered and fully
eclipsed conformations of 1,2dibromoethane respectively are
(a) 60, 120, 180, 0
(b) 0, 60, 120, 180
(c) 120, 60, 180, 0
(d) 60, 0, 180, 120
Which of the following statement is false about cyclopropane1,2dicarboxylic acid?
(a) It has two geometric isomers.
(b) It has three stereoisomers.
(c) All the stereoisomers are optically active.
(d) Only transisomer shows enantiomorphism.
The IUPAC name of Cl3C.CHO is
(a) Trichloroacetaldehyde
(b) 1,1,1Trichloroethanal
(c) 2,2,2Trichloroethanal
(d) Chloral
The name of CH CH is
(b) 3Aminoprop2propenal
(d) 3Amino1oxoprop2ene

9.

CHO NH2
(a) 1Aminoprop2enal
(c) 1Amino2form ylethene
IUPAC name of the compound

(b) 1,1,2Trichloro3bromopropane
(d) None of these

10.

BrCH2CHClCHCl2 is
(a) 1Bromo2,3,3trichloropropane
(c) 3Bromo1,1,2trichloropropane
Indicate the wrongly named compound.
(a) CH3CHCH2CH2CHO

(b)

3.

4.

5.

6.

7.

CH3CHCCCOOH
CH3

CH3
(4Methylpentanal)

(4Methyl2pentynoic acid)

O
(c) CH3CH2CH2CHCOOH

CH3

(d) CH3CH2CH=CHCCH3
(3Hexen2one)

(4Methylpentanoic acid)

11.

12.

13.

14.

Which of the following compound is not chiral?

(a) DCH2CH2CH2Cl
(b) CH3CH(D)CH2Cl
(c) CH3CH(Cl)CH2D
(d) CH3CH2CH(D)Cl
Which of the following compound exhibit geometrical isomerism?
(a) CH2=CClBr
(b) CH3CH=CClBr
(c) CH3CH=CCl2
(d) (CH3)2 C=CClBr
Which of the following compound will show metamerism?
(a) CH3OCOC3H7
(b) CH3SC2 H5
(c) CH3OCH3
(d) CH3OC2 H5
Which one of the following compound will not exhibit optical isomerism?
(a) CH3CH(OH)Br
(b) CH3CH(OH)CH3

Br CH3
(c) CH3CHCHCHCH3
15.

(d) CH3CHCHCH2OH

OH Br
What type of isomerism is shown by the following compounds?

Page 32

O
OH

16.

17.

18.

19.

20.

21.

22.

23.

24.

25.

(a) Metamerism
(b) Positional
(c) Functional
(d) Tautomerism
Which of the following statements regarding the molecule CH2=C=CH2 is not correct?
(a) Both the two bonds are present in the same plane.
(b) The central carbon atom is sp hybridized while the terminal atoms are sp2 hybridized.
(c) The molecule is not planar.
(d) The molecule contains six bonds and two bonds.
If two compounds have the same empirical formula but different molecular formulae they must have
(a) different percentage composition
(b) different molar mass
(c) same viscosity
(d) same vapour density
The IUPAC name of the compound is

CH3
CH3

HO
(a) 1,1dimethyl3hydroxycyclohexane
(b) 3,3dimethyl1hydroxycyclohexane
(c) 3,3dimethyl1cyclohexanol
(d) 1,1dimethyl3cyclohexanol
The compound which is not isomeric with diethyl ether is
(a) npropyl methyl ether
(b) 1butanol
(c) 2methyl2propanol
(d) butanone
The maximum number of isomers for an alkene with the molecular formula C 4H8 is
(a) 2
(b) 3
(c) 4
(d) 5
The number of isomers of dibromoderivative (molar mass 186 g mol 1 ) of an alkene is
(a) two
(b) three
(c) four
(d) six
The number of optically active compounds in the isomers of C 3H5 Br3 is
(a) 1
(b) 2
(c) 3
(d) 4
The enolic form of acetone contains
(a) 9 sigma bonds, 1 pi bond and 2 lone pairs
(b) 8 sigma bonds, 2 pi bond and 2 lone pairs
(c) 10 sigma bonds, 1 pi bond and 1 lone pairs
(d) 9sigma bonds, 2 pi bond and 1lone pairs
A molecule is said to be chiral if it
(a) contains a centre of symmetry
(b) contains a plane of symmetry
(c) cannot be superimposed on its mirror image
(d) exists as cis and transforms
Which of the following statements is not correct?
(a) A m eso compound has chiral centres but exhibits no optical activity.
(b) A meso compound has no chiral centres and thus are optically inactive.
(c) A meso compound has molecules which are superimposable on their mirror images even though
they contain chiral centres.
(d) A meso compound is optically inactive because the rotation caused by any molecule is cancelled
by an equal and opposite rotation caused by another molecule that is the mirror image of the first.

EXERCISE II
1.

IIT-JEE- SINGLE CHOICE CORRECT

1, 2dimethyl cyclohexane has
(a) 2 geometrical isomers and no optical isomers
(b) 2 optical isomers and no geometrical isomers
(c) 3 stereoisomers

Page 33

2.

3.

4.

5.

(d) none of these

The most stable configuration of ethylene glycol is
(a) Anti
(b) Gauche
(c) Partially eclipsed
(d) fully eclipsed
The compound, C2 FClBrI has
(a) 4 geometrical isomers
(b) 6 geometrical isomers
(c) 4 optical isomers
(d) (b) and (c) both
CHOCH(OH)CH(OH)CH2 OH has total
(a) 4 optical isomers
(b) 2 optical isomers
(c) 3 optical isomers
(d) none of these
Total number of optical isomers of COOH(CHOH)2COOH is
(a) 2
(b) 3
(c) 4
(d) 6

6.

For the compound,

total number of optical isomers will be

7.

(a) 2
(b) 4
(c) 8
(d) 16
CH3COCH2COCH3 shows tautomerism, which one of the following will not show?

O
(a)

O
(b)

O
O
(c)
8.

9.

10.

11.

12.

O
CH2CN

(d)

CH3CH2CN and CH3 CH=C=NH are

(a) functional group isomers
(b) geometrical isomers
(c) tautomers
(d) metamers
In which compound, the enol form will be maximum in nhexane?
(a) CH3COCH2 CO2 C2H5
(b) CH3COCH2Cl
(c) CH3COCH2 COCH3
(d) PhCOCH2COCH3
Total number of isomeric alcohols with the molecular formula C4H10O is
(a) 2
(b) 3
(c) 4
(d) 5
(+) Mandelic acid has a specific rotation of +158. What would be the observed specific rotation of the
mixture of 25% () mandelic acid and 75% (+) mandelic acid?
(a) +118.5
(b) 118.5
(c) 79
(d) +79
Which of the following compound can exist in two geometrically isomeric forms?
(a) CH3CCCH3

(b) CH3CHCH=CH2

OH
13.

14.

(c) CH3CH2CH=CHCH3
(d) CH3CH2CH2CH=CH2
The total number of isomers possible for trisubstituted C 6 H3Br2Cl is
(a) Six
(b) Four
(c) Three
(d) Two
In the following sequence of standard stereochemical Fischer formulae, indicate the one that may be
identical with the given compound.

Page 34

NH2
CH3

CO2H

NH2

CO2H
(b) H3C

CH3

(a) H

NH2
H

COOH
COOH
CH3

(c) H2N
15.

(d) H3C

COOH
NH2
Which of the follower stereoisomer exhibits a plane of symmetry?
Br
COOH
(a)

CH3

(b)

CH3

AsMe3 NO2

OH

Ph

COOH

(c)

(d)
HOOC
OH

16.

Which of the Newmann projections shown below represents the most stable conformation about the
C1C2 bond of 1-iodo-2-methylpropane?
H3C I

CH3

(a)

CH3

(b)
H
H

CH3
H

CH3

H3C H

I
(c)

(d)
CH3

17.

18.

19.

I
H

CH3
H

H
Vinyl alcohol and acetaldehyde are
(a) geometrical isomers.
(b) ketoenol tautomers.
(c) chain isomers.
(d) position isomers.
Meso tartaric acid and (+)tartaric acid are
(a) position isomers
(b) diastereomers
(c) enantiomers
(d) racemic mixture
Which of the following compound will form geometrical isomers?
Cl
(a)
(b) CH3CH=NOH

Cl
(c)
20.

(d) all of them

The number of stereoisomers of the following compound is

CH3
C=C
Cl

(CH2)4CH(OH)CH3

Page 35

21.

22.

23.

24.

(a) 8
(b) 4
(c) 6
(d) 2
How many structural isomers of a hydroxy acid of formula C 4H8O3 show optical activity?
(a) 2
(b) 3
(c) 4
(d) 5
Which one of the following compound having molecular formula C 7H16 will show optical isomerism?
(a) 2, 3-dimethyl pentane
(b) 2, 2-dimethyl pentane
(c) 2-methyl hexane
(d) none of these
At room temperature the eclipsed and the staggered forms of ethane cannot be isolated because
(a) both the conformers are equally stable.
(b) they interconvert rapidly.
(c) there is a large energy barrier of rotation about the -bond.
(d) the energy difference between the conformers is large.
The following compound shows

H3C

H
C=C

H3C

H
C
COOH

H3C

25.

(a) optical isomerism only

(b) geometrical isomerism only
(c) optical and geometrical isomerism
(d) tautomerism only
nHeptane on monochlorination gives a number of isomers. How many of them are optically active?
(a) 1
(b) 2
(c) 3
(d) 4

EXERCISE III
1.

MORE THAN ONE CHOICE CORRECT

Which of the following compounds on dichlorination gives 3 different products (may not occur by same
mechanism in all compounds and even low yield products are to be counted).
(a)

(b)

CH3
(c)
2.

(d)

Which of the following pairs represents enantiomers?

NH2
(a) H3C

H , HO2C

CH3

CH3

3.

H
H

(b)

H
CH3
Cl

CH3
NH2

H
OH H3C
Cl , H3C

OH
OH H3C
Cl ,
H

H
H

NH2

CO2H

(c)

CH3

OH
Cl

(d)

H
H

CH3
CO2H CO2H
, HO
OH

H
H

NH2
H
CH3
CH3
Which of the following compounds show position as well as metamerism?
(a) CH3CH2CCH2CH3

(b) CH3OCH2CH2CH3

O
4.

(c) CH3CH2CH2CHO
(d) CH3CH2NH2
Which of the following compounds have gauche conformer less stable than staggered conformer?
(a) CH3CH3
(b) FCH2CH2 OH

Page 36

5.

(c) CH3CH2CH2CH3
(d) CH3COOCH2CH2OCOOH3
Identify among the following, set of functional isomers.
(a) CH3CH2CH2CO2H & CH3CHCH3

(b) CH3CH2CO2H & CH3CO2CH3

CO2H
(c) CH3CH2CH2NH2 & CH3NCH3
6.

CH3
(d) CH3CH2COCH2CH3 & CH3COCH

CH3
CH3
Which of these are isomers for an aromatic compound having molecular formula C 7H8O?
CH2OH

CH3
OH
(a)

(b)

CH2OCH3
(c)
7.

(d)

Which of the following compounds are optically active?

CH3
H
Cl
(a) H
Cl
CH3
COOH
(c) H3C
8.

9.

10.

11.

12.

13.

OCH3

CH2OH
(b) HO

H
CH3

CCl3
H
OH
(d) HO
H
CCl3

CH2Cl
COOH
Keto-enol tautomerism is observed in
(a) C6 H5CHO
(b) C6 H5COCH3
(c) C6 H5COC6 H5
(d) C6 H5COCH2COCH3
Only two structural isomeric monochloro derivatives are possible for
(a) n-Butane
(b) 2,4-Dimethyl pentane
(c) Benzene
(d) 2-Methyl propane
Which of the following compounds are the pair of structural isomers?
(a) (CH3)2CHOC2H5 ; CH3(CH2)2OC2H5
(b) CH3CH2NO2 ; CH2(NH2 )COOH
(c) (CH3)2CH(CH2)2CH3 ; CH3(CH2)2 CH(CH3)2
(d) CH3CH2CO2H ; CH3 CO2 CH3
CH3

CH3CHCH2CH2CH3 on monochlorination with Cl2 in the presence of light at room temperature

(reaction proceeds by free radical mechanism) gives p isomers. The product mixture on fractional
distillation gives q fractions. Which of the following option is correct?
(a) p is 8
(b) p is 7
(c) q is 4
(d) q is 5
Which of the following compounds have anti conformer as the most stable conformer?
(a) CH3CH2CH2CH3 (Rotation about C2C3 bond)
(b) ClCH2 CH2 Br
(c) ClCH2 CH2 OH
(d) HOCH2CH2CH3
Which of the following compounds/isomers have centre of symmetry?

Page 37

NO2 Me3C

CO2Et

(a)

(b)
CMe3

EtO2C

NO2

O
(trans isomer)

CH3

CH3
H
OH
(d)
H
HO

H3C
(c)

CH3

14.

CH3
CH3
A mixture of racemic C2H5CHCO2H can be resolved by reacting with

CH3
(b) C2H5CHNH2

(a) C2H5CHOH

CH3

CH3
(c) CH3CHNH2
15.

(d) CH3CHOH

CH3
CH3
Which of the following pair represents structural isomers?
(a)

H3C
H

C=C

C2H5
H

and

H3C
H

C=C

C2H5

(b) CH3COC2H5 and CH3CH2CH2COH

(c) CH3CH2OCH2CH2CH3 and CH3OCHCH2CH3

CH3
(d) CH3CH2N=O and CH3CH=NOH

EXERCISE IV
MATCH THE FOLLOWING
1.
Column I

Column II

I.

CH3 (CH2)3CN and (CH3)3 CCN

(A) Position isomers

II.

CH3 CH2 CH2 OCH3 and CH3CH2OCH2CH3

(B) Chain isomers

III. CH3CHOCH3 and CH3CH2CH2OCH3

CH3

IV. CH2=CHCH=CH2 and CH3CCCH3

(C) Functional isomers

(D) Tautomers
(E) Metamers

2.
Column I

I.

H
H

CH3
Br
Br and
C2H5

Br
Br

CH3
H
H
C2H5

Column II

(A) Meso compound

Page 38

II.

H
H

CH3
CH3
Br
Br
H
Br and H
Br
CH3
CH3

(B) Enantiomers

III.

H
H

COOH
OH
OH
COOH

(C) Tautomers

and HO
HO

COOH
H
H
COOH

IV. CH3CH2CHO and CH3CH=CHOH

(D) Diastereomers
(E) Functional isomers

3.
Column I

Column II

I.

2,3,5trihydroxy pentanoic acid

(A) 2 optically active isomers

II.

Lactic acid [CH3CH(OH)CO 2H]

(B) 4 optical isomers

III. 1,2dimethylcyclohexane

(C) No optical isomer

IV. Glycine (NH2CH2CO2H)

(D) 3 stereoisomers
(E) Meso isomer

ASSERTION AND REASON

Direction: Read the following questions and choose

1.

(A) If both Assertion and Reason are true and Reason is the correct explanation of the assertion.
(B) If both Assertion and Reason are true but Reason is not correct explanation of the Assertion.
(C) If Assertion is true but Reason is false.
(D) If Assertion is false but Reason is true.
Assertion: Keto form of acetoacetic ester is more stable than its enolic form.
Reason:

2.

Enolic form of acetoacetic ester is stabilized by intramolecular hydrogen bonding.

(a) (A)
(b) (B)
(c) (C)
Assertion: Extent of enolization depends upon the solvent used.
Reason:

(d) (D)

If the solvent used makes hydrogen bonding with carbonyl group, it decreases the enol
content.

3.

(a) (A)
(b) (B)
(c) (C)
Assertion: Oxime of acetone does not show geometrical isomerism.
Reason:

4.

Both the isomers have different configurations around double bond.

(a) (A)
(b) (B)
(c) (C)
Assertion: Disubstituted biphenyls exhibit optical isomerism.
Reason:

(d) (D)

(d) (D)

If the o,osubstituents are very bulky even then there is no loss of planarity of the biphenyl
rings.

5.

(a) (A)
(b) (B)
(c) (C)
Assertion: Racemic mixture and meso forms are optically inactive.

(d) (D)

Reason:
(a) (A)

These are optically inactive due to external and internal compensation respectively.
(b) (B)
(c) (C)
(d) (D)
PASSAGE BASED PROBLEMS
A bond between two carbon atoms is formed by the overlaping of sp 3 hybrid orbitals of carbon atom
along their internuclear axis. It gives symmetrical electronic distribution along the internuclear axis and thus
rotation about carbon-carbon single bond is almost free. It results in number of spatial arrangements of atoms
called conformations. In any conformation, the angle between CC and CH bonds on adjacent carbon atom

Page 39

is known as dihedral angle. Stability and energy of the conformations depend on the torsional strain and Van
der Waals strain. The order of stability of conformations of nbutane is fully eclipsed < partially eclipsed <
skew or gauche < staggered or anti. But in some cases, skew or gauche is stabilized by intramolecular
hydrogen bonding.Cyclic compounds also follow the same pattern. According to Baeyer strain theory, greater
the deviation from the normal tetrahedral angle, greater is the angular strain and lesser is the stability of
cycloalkane. The most commonly found cyclic compounds usually contain six membered ring. They also show
conformations. The most stable conformation of cyclohexane is chair form which is staggered and free from
any strain.
1.
Dihedral angle in staggered and fully eclipsed conformations of nbutane are
(a) 120, 0
(b) 180, 0
(c) 60, 120
(d) 180, 120
2.
Which of the following molecule has the highest deviation from tetrahedral bond angle?
(a) Cyclopropane
(b) Cyclobutane
(c) Cyclopentane
(d) Cyclohexane
3.
The value of equilibrium constant for the equilibrium
Eclipsed form

4.

5.

Staggered form

of ethane is
(a) 49
(b) 1
(c) 0.02
(d) 4.9
For CH3CHCHCH3, which conformer is the most stable?

Cl OH
(a) Anti or staggered
(b) Fully eclipsed
(c) Gauche or skew
(d) Partially eclipsed
Which of the following statement is correct?
(a) Three membered ring is more stable than a four membered ring.
(b) Six membered ring is more stable than a five membered ring.
(c) Six membered ring has less eclipsing strain than a five membered ring.
(d) All five carbons in cyclopentane are present in the same plane.

EXERCISE V
SUBJECTIVE PROBLEMS
1.

2.

The specific rotation of a pure enantiomer is +12. What will be its observed rotation
if it is isolated from a reaction with (a) 20% racemization and 80% retention and
(b) 80% racemization and 20% inversion?
Find out the total stereoisomers for the following compound,

.
3.

How many optical isomers are possible for the compound,

F
Cl ?
Br

C
H

OH

4.

OH

Is the given isomer,

OH

, optically active or not?

HO
H

H
H

(I)

Page 40

5.

NH2
O cyclises to form one amide linkage. How many optical isomers will be

The compound,

Cl

6.

there for the cyclic product?

One or more of the following compound are in their most stable tautomeric forms. Which are they?

OH
C

(a) H3C

O
C

OCH2CH3

(b)

H
O
H
(c) H
7.
8.

(d) CH3C
OH

CCH3
O

Draw all Newmann projections of FCH2CH2OCH3 and arrange the conformers in their decreasing
order of stability.
Draw sawhorse and Newman projection diagrams of the following structures, which are shown as
Fischer projections. Which compound is optically inactive?

CH3

OH
OH
H

H
(a) HO

H
OH

H3C
H

(b)

CH3

CH3

CHO
OH
OH

H 3C
(c)
H

H
OH

HO
(d)
H

CH3

CH2OH

CO2H
OH
OH

CH3
Br
Br

H
(e) H
9.

CH

H
(f) H

CO2H
CH3
Write the structure of a proton tautomer of each of the following compounds.

(a)

OH

CH3

(b) Ph

(c)

OH
O

N=O

(d) HO

(e)

(f)

H
(g)

(h) CH3NO2

O
(j)
10.

CN

(k) Ph

(i) H3C

NO2

CH3

H
In what stereoisomeric forms would you expect the following compounds to exist?

Page 41

(a) EtCH(CO2H)Me

(b)

O
(c)

(d) Et(Me)C=C=C(Me)Et

Ph

CO2H

(e)

(f)

Ph

CO2H

Br

ANSWERS
EXERCISE I
AIEEE-SINGLE CHOICE CORRECT
1. (b)

2. (b)

3. (b)

4. (c)

5. (a)

6. (c)

7. (c)

8. (b)

9. (c)

10. (c)

11. (a)

12. (b)

13. (a)

14. (b)

15. (c)

16. (a)

17. (b)

18. (c)

19. (d)

20. (c)

21. (b)

22. (a)

23. (a)

24. (c)

25. (b)

EXERCISE II
IIT-JEE-SINGLE CHOICE CORRECT
1. (c)

2. (b)

3. (b)

4. (a)

5. (b)

6. (b)

7. (b)

8. (c)

9. (d)

10. (d)

11. (d)

12. (c)

13. (a)

14. (d)

15. (d)

16. (c)

17. (b)

18. (b)

19. (d)

20. (b)

21. (b)

22. (a)

23. (b)

24. (a)

25. (b)

EXERCISE III
MORE THAN ONE CHOICE CORRECT
1. (a, b)

2. (a, c)

3. (a, b)

4. (c, d)

5. (b, c)

6. (a, b, d)

7. (b, d)

8. (b, d)

9. (a, d)

10. (a, b, d)

11. (a,d)

12. (a,b,d)

13. (b,c)

14. (a,b)

15.(b,c,d)

EXERCISE IV
MATCH THE FOLLOWING
1.

I (B) ; II (E) ; III (A) ; IV (C)

2.

I (B) ; II (D) ; III (A) ; IV (C)

Page 42

I (B) ; II (A) ; III (E) ; IV (C)

3.

ASSERTION AND REASON

1. (d)

2. (a)

3. (c)

4. (d)

5.

(a)

5.

(b)

PASSAGE BASED PROBLEMS

1. (b)

2. (a)

3. (a)

4. (c)

EXERCISE V
SUBJECTIVE PROBLEMS
1.

(a) obs = 0.80 (+12) = +9.6

(b) obs = 0.20 (12) = 2.4

2.

4 geometrical isomers which are (trans, trans), (trans, cis), (cis, cis), (cis, trans) and each geometrical
isomers will have 2 optical isomers. So, a total of 8 stereoisomers will be obtained.

3.

4.

Optically active
*
* NH ,

5.

4 optical isomers

CH

CH
6.

CH3C
O

CH3C

COEt

CCH3
O

(Crossconjugation and intramolecular hydrogen bonding)

OCH3
F

7.

H
H

OCH3
rotation
by 60

H
H

Fully Eclipsed (I)

OCH3
H

rotation
by 60

H
H

H
Skew or gauche (II)

OCH3
rotation H
by 60

H
F

Partially Eclipsed (III)

F
Staggered (IV)

rotation
by 60

OCH3
(I)

rotation
by 60

H
H

Skew or gauche (VI)

OCH3
H

rotation
by 60

F
H

H
H

Partially Eclipsed (V)

Decreasing order of stability of conformers:

(IV) > [(II) = (VI)] > [(III) = (V)] > (I).

Page 43

8.
Sawhorse
representation

CH3

H OH

OH
H

H
HO

(a)

OH H
CH3

CH3

CH3

OH

H OH

Me
H

(b)

H
OH

Me

H
(c)

H OH

H OH
CH2OH
CHO

(e)

H Br
Me

H
H

(f)

9.

H OH
COOH
COOH

(a)

HO H

H
OH

Optically
active

HOH2C

HH

HH

H OH

COOH

Optically
active

Br
Br

Optically
inactive

MeMe

Me

COOH
OH
OH

OH
OH

H Br

Me

Optically
inactive

CHO

Me
Br
Br

Me H

OH H

CH2OH

H
H

H
OH

MeH

CHO
(d)

Me H

Me
H

H
OH

Optically
active

H3CCH3

Me OH

Me

HO
H

OH
H

Optical
activity

MeOH

OH

OH
OH

H OH

Me H

Me
Me
H

Newman
representation

OH
OH

Optically
inactive

HOOCCOOH

N O

OH
H
O

CH3

PhC

(b) Ph

O
C=CH2

O
(c)

OH

N=O

(d) HO

O
OH

NOH

OH

(e)

OH

Page 44

(f)

OH

H
N

(g)

OH
(h) CH3NO2

CH2=N
O
OH

(i) H3C

NO2

CH2

CN

(j)

O
(k)

Ph

C NH

OH

CH3

PhC=NCH3

H
COOH

10.

COOH
Me

Me

(a) H
Et

Me

and

H
O

CH3

Me

Et
C=C=C

Me

(e) Ph H

CH3

Me

C=C=C

Ph

Me

Et
(d)

Me

CH3

(b)

H
Et

Me
(c)

CH3

Et

Et

COOH

COOH

Ph

Me
COOH

Ph

COOH

Br

Br

(f)

Page 45