CHAPTER

13 Isomerism

Definition CH3
Compounds having same molecular formula but differ in atleast
CH3 – N – CH3
one physical or chemical or biological properties are called N, N-dimethylmethanamine
isomers and this phenomena is known as isomerism. Metamerism: This type of isomerism occurs when the isomers
Types of Isomerism: (A) Structural isomerism (B) Stereo differ with respect to the nature of alkyl groups around the same
isomerism polyvalent functional group.
e.g. C4H10O: CH3 – O – CH2 – CH2 – CH3
(A) Structural isomerism n-propyl methylether
Structural isomerism is a form of isomerism in which molecules CH3 – CH2 – O – CH2 – CH3
with the same molecular formula have atoms bonded together in diethyl ether
different orders. Ring-Chain isomerism: In this type of isomerism, one isomer is
Types of Structural Isomerism open chain but another is cyclic.
CH2
Chain isomerism: This type of isomerism is due to difference in
the arrangement of carbon atoms constituting the chain. e.g. C3H6: CH3 – CH = CH2 H2C – CH2
Key points: Parent carbon chain or side chain should be different. propene cyclopropane
™ For chain, positional and metamerism, functional group must be
e.g. C5H12: CH3 – CH2 – CH2 – CH2 – CH3 same.
n-pentane ™ Metamerism may also show chain and position isomerism but

CH3 priority is given to metamerism.

Tautomerism: This type of isomerism is due to spontaneous
H3C – CH – CH2 – CH3, H3C – C – CH3 interconversion of two isomeric forms into each other with
different functional groups in dynamic equilibrium.
CH3 CH3 Conditions:
iso-pentane neo-pentane O O
Positional isomerism: It occurs when functional groups or (i) Presence of – C – or – N → O
multiple bonds or substituents are in different positions on the (ii) Presence of atleast one a-H atom which is attached to a
same carbon chain. saturated C-atom.
Key points: Parent carbon chain remain same and substituent, e.g. Acetoacetic ester.
multiple bond and functional group changes its position. O OH
CH3 CH3 CH3
CH3–C–CH2COOC2H5  CH3–C=CHCOOC2H5
CH3 keto form       enol form

e.g. C6H4(CH3)2: , ,
Enol content enhance by:
™ Acidity of a-H of keto form.
CH3
o-xylene m-xylene ™ Intra molecular H-Bonding in enol form.
CH3
p-xylene ™ Resonance in enol form.
Functional isomerism: It occurs when compounds have the same ™ Aromatisation in enol form.
molecular formula but different functional groups.
(B) Stereoisomerism
e.g. C3H9N: CH3 – CH2 – CH2 – NH2,
Compounds with the same molecular formula and structural
1-propanamine
formula but having difference in the spatial arrangement of atoms
CH3 – CH2 – NH – CH3, of groups in 3D space are called steroisomers and the phenomenon
N-methylethanamine
is called stereoisomerism.
Types of Stereoisomerism ™ Configuration of optical isomer
Geometrical isomerism: It is due to restricted rotation and is (a) Absolute configuration (R/S system)
observed in following systems. (b) Relative configuration (D/L system)
a a a
C=C C = N–OH N=N ™ Determination of R/S configuration
b b , b , , a a Rule-1 Assign the priority to the four groups attached
a b
to the chiral carbon according to priority rule.
b b
(Ring greater than a Rule-2 If lowest priority 4 is bonded to vertical line
7 member with
double bond)
C
b then moving
CH3 Clockwise
1 → 2 → 3 R
™ Cis-trans isomerism: The cis compound is the one with the Anti clockwise
same groups on the same side of the bond, and the trans has S
the same groups on the opposite sides. Both isomers have Rule-3 If lowest priority 4 is bonded to horizontal
different physical and chemical properties. line then moving
e.g. Clockwise
H H H COOH 1 → 2 → 3 S
C=C C=C Anti clockwise
R
HOOC COOH HOOC H
cis trans
maleic acid fumaric acid
Determination of D/L system
™ General physical properties of geometrical isomer of but-2-ene
™ Reference molecule glyceraldehyde
(i) Stability trans > cis
™ It is used to assign configuration in carbohydrate amino acid
(ii) Dipole moment cis > trans
and similar compounds.
(iii) Boiling point cis > trans
(iv) Melting point trans > cis Rule: Arrange parent carbon chain the vertical line
™ Placed most oxidised carbon on the top or nearest to top.
Calculation of number of geometrical isomers:
™ On highest IUPAC numbered chiral carbon
Unsymmetrical 2n
If OH group on RHS → D
Symmetrical 2n–1 + 2m–1
If OH group on LHS → L
n
m= (If n is even) CHO CHO
2
n +1 H OH HO H
m= (If n is odd) HO H H OH
2 H OH HO H
™ Where n = number of sites where GI is possible. H OH HO H
Optical isomerism: Compounds having similar molecular and CH2–OH CH2–OH
structural formula but differing in the stereo chemical formula and
D-Glucose L-Glucose
behaviour towards plane polarised light are called optical isomers
and this phenomenon is called optical isomersim.
CIP Sequence Rule
Types of optical isomers
The following rules are followed for deciding the precedence
(1) Optically active order of the atoms or groups:-
™ Dextrorotatory (d)
(i) Highest priority is assigned to the atoms of higher atomic
™ Laevorotatory (l)
number attached to asymmetric carbon atom.
(2) Optically inactive
™ Meso (ii) In case of isotopes, isotopes having higher atomic mass is
™ Condition Molecule should be asymmetric or chiral i.e. given priority.
symmetry elements (POS & COS) should be absent. (iii) If the first atom of a group attached to asymmetric carbon
™ The carbon atom linked to four different groups is called atom is same then we consider the atomic number of 2nd
chiral carbon. atom or subsequent atoms in group.
™ Fischer projection An optical isomer can be represented (iv) If there is a double bond or triple bond, both atoms are
by Fischer projection which is planar representation of considered to the duplicated for triplicated.
three dimensional structure. ™ Non-superimposable mirror images are called
Fischer projection representation of lactic acid enantiomers which rotate the plane polarised light up
(2-hydroxypropanoic acid) to same extent but in opposite direction.
COOH COOH
3 2 1
™ Diastereomers are stereoisomers which are not mirror
CH3 – CH – COOH : HO H H OH
images of each other. They have different physical and
CH3 CH3
OH chemical properties.

32 JEE (XI) Module-4 PW

 ™ Meso compounds are those compounds whose Conformational Isomerism
molecules are superimposable on their mirror images
inspite of the presence of asymmetric carbon atom. Newman projection: Here two carbon atoms forming the σ bond
™ An equimolar mixture of the enantiomers (d & l) is
are represented one by circle and other by centre of the circle.
called racemic mixture. The process of converting d- Circle represents rear side C and its centre represents front side
or l- form of an optically active compound into racemic carbon. The C–H bonds of front carbon are depicted from the
form is called racemisation. centre of the circle while C–H bond of the back carbon are drawn
™ The process by which d/l mixture is separated into d from the circumference of the circle.
and l forms with the help of chiral reagents or chiral
catalyst is known as resolution.
™ Compound containing chiral carbon may or may not be
optically active but show optical isomerism.
™ For optical isomer chiral carbon is not the necessary
condition.
Calculation of number of optical isomers
Optically active Optically inactive forms
The compound 4 3 2 1
forms (meso) ™ Conformations of butane: CH3 – CH2 – CH2 – CH3
Unsymmetrical 2n Zero CH3 CH3 CH3 CH3
CH3 H CH3 H H H
Symmetrical n
2(n–1) –1
If n = even 2 2 60°
Rotation
60°
Rotation
60°
Rotation
H H CH3
Symmetrical H H H H H H H H H
2(n–1) – 2(n–1)/2 2(n–1)/2 H CH3
If n = odd Fully eclipsed Gauche Partially Anti Staggered-form
(less stable) (more stable) Eclipsed form (most stable)
* Where n = no. of chiral carbon
™ The order of stability of conformations of n-butane.
The different arrangement of atoms in space that results from the
carbon-carbon single bond free rotation by 0-360° are called Anti staggered > Gauche > Partially eclipsed > Fully eclipsed.
conformations or conformational isomers or rotational isomers ™ Relative stability of various conformation of cyclohexane is
and this phenomenon is called conformational isomers. Chair > twist boat > boat > half chair.

P
W Isomerism 33