❑ Subject – Organic Chemistry

❑ Chapter - Isomerism

ONE SHOT Om Pandey, IIT Delhi

1 Isomer

2 Types of isomerism

3 Structural Isomerism

4 Stereoisomerism

5 Confirmational Isomerism
 Isomers
Compounds with same molecular formula but different physical and chemical property.

CH3 — CH2 — OH CH3 — O — CH3

 Isomers

Structural isomers Stereoisomers

Different arrangement of atoms or Different arrangement of atoms or

groups within the molecule groups in 3D space
1) Chain isomers 1) Optical isomers
2) Position isomers 2) Geometrical isomers
3) Functional isomers 3) Conformational isomers
4) Metamers
5) Tautomers
Structural Isomers
Skeletal isomers, Linkage isomers & Constitutional isomers
Compounds having same molecular formula but different structure
Chain Isomers
Isomers having different size of main carbon chain / side alkyl chain
Same nature of F.G. , M.B. , Substituents

C4H10 C5H12

C6H14
 CH2 — CH3 CH3

C8H10

CH3
Positional Isomers
Compounds having same MF but different position of FG / MB / Substituents

OH

OH

Cl Cl

Cl
 Compounds having same molecular formula but
Functional Isomers
different functional group .

Acid & Ester 1°, 2°, 3° Amines

Alcohol & Ether

Ketone & Aldehyde

1°, 2°, 3° Amides

Alkene & Alkyne

Alcohol attached to sp2 C is chemically

different from alcohol attached to sp3 C .
 Compounds having same nature of functional groups but different
Metamers nature of alkyl groups along polyvalent functional group

Ether 2o Amide

Thio-Ether 3o Amide

2o Amine Ester

3o Amine Ketone
Question

O — CH2 — CH3 O — CH3

and show which type of isomerism?
CH3
 No of Structural Isomers
No of carbon DU = 0 DU = 1

C3

C4

C5
 How many structural isomers are possible for following MF ?
C4H9Cl

C4H9OH Alcohol C4H10O Ether

How many structural isomers are possible in cyclic form for following MF ?
C4H7Cl

C4H8O Cyclic Alcohol C4H8O Cyclic Ether

 Wedge Dash Projection

F
Wedge : Towards Observer
H
Dash : Away from observer
Br
HO
 Stereoisomerism Same structural formula but different orientation in space

CH3 CH3 CH3 H

CH2 CH CH2 CH3 C C C C
H H H CH3

Condition for Geometrical Isomerism :

Two different groups at each restricted point

The groups / atoms showing G.I. must be in same plane. ( 1  2 )

 Stereoisomerism

Configurational Isomerism Confirmational Isomerism

Geometrical Isomerism

Optical Isomerism
Geometrical Isomerism
Conditions Restricted Rotation
Two different groups at each restricted point
The groups / atoms showing G.I. must be in same plane. ( 1  2 )

1. In Double bond system 2. In Ring system

D D D Cl
C C C N
H H H H Cl

N N
H H
 Which will show Geometrical Isomerism ?

H H
H
(1) C C (4)
H
H H

F
D D
(2) H C C (5)
H Cl

I F
(3) C C
Br Cl
Q. AIIMS - 2004 The geometrical isomerism is shown by :–

CH2 CH2

A B

CHCl CHCl

C D
 Cis – Trans Nomenclature

a a a b
C C C C
b b a b

D D
C C
H H

Cl F
C C
Br Cl
Q. AIPMT – 2009

Which of the following compounds will exhibit cis-trans (geometrical) isomerism?

A 1- Butanol

B 2-Butene

C 2-Butanol

D 2-Butyne
 Syn — Anti Nomenclature

R R R
C N C N C N
H G H OH H NH2

R G
C N
H

R
N N N N
R R R
Note : If n is the no. of carbon atoms present in a ring then
(i) n < 8 (ii) n  8
E/Z Nomenclature a b a d
C C C C
c d c b
 CIP Rule [ Sequence Rule ]
1) Group having first atom with higher atomic no. is senior . Cl Br
C C
F I

2) The higher mass isotope is senior. Cl D

C C
F H

3) If first atom of group is identical then second atom is observed for seniority.

Cl CH2 — CH3 CH3 CH2 — OH

C C C C
F CH3 I CH2 — NH2
4) Group having D.B. / T.B. are treated as following.

H NH
F C
C C C C
Cl C
 Physical Properties of G.I.

Dipole moment Stability

Melting point
Boiling point

Solubility in water

Cl H Cl Cl
C C C C
H Cl H H
Polarimeter Experiment
+15°0 –15°
+30° –30°
+45° –45°

 → 0o
Optically Inactive

Polarizer Sample cell Analyzer

Plane
Polarised Light  → (+) , Clockwise
Dextro-rotatory
Optical Rotation :

 → (-) , Anti-clockwise
Leavo-rotatory
Specific Rotation []

l → dm
C → gm/ml
 → degree

Specific Rotation is the degree of rotation observed if a 1 dm tube is used and compound
has concn 1gm / ml.
Chiral Centre / Chiral Atom
1. sp3 Hybridisation
2. 4 different groups/atoms

How many chiral atoms are present in following compounds ?

H
H
Cl
+ N
(a) (b) N CH3
(c)
O N
Br
O H
H5C2 D
(d) Si (e) CH3 S Ph
H3C H
 Chiral Compounds
A compound which is non-superimposable on its mirror image
F
H

HO Br

Symmetric compounds

Asymmetric compounds

A compound having only one chiral carbon is Chiral / Optically Active.

 Projection
Wedge – Dash Projection Fischer Projection

D D
H Br Cl
Br H
HO
 Rule for Correct Fischer Projection
On the vertical line , main chain is taken with first carbon at top.

CH2OH CH CHO
OH

CH3 CH COOH
NH2
 Nomenclature

Relative Configuration Absolute Configuration

D – L Nomenclature R – S Nomenclature
Amino Acids / Carbohydrates
Applied only in Correct Fischer Projection

Standard : Glyceraldehyde

COH COH
H OH H OH

CH3 CH3
 D – L Nomenclature

COOH CHO
H2N H HO H
CH3 H OH
CH2OH

COOH CHO
NH2 H OH
H
HO H
CH3 H OH
H OH
CH2OH
 R - S Nomenclature - Fischer Projection
Apply CIP Rule and find priority order . a
c b

Cl CHO
I Br HO CH3
F H
If lowest priority group is at horizontal line then a
c d

CHO O
H Cl C H
H3C HO H
H OH

CH2OH
Q. AIPMT – 2007

CH3 – CHCl – CH2 – CH3 has a chiral centre which one of the following represents its R
configuration.

C2H5 C2H5

A H CH3 B Cl CH3

Cl H

CH3 C2H5

C H Cl D H3C Cl

C2H5 H
 Q. AIIMS - 2005

Correct configuration of the following is :–

CH3
H OH
CH3 OH
H
A 2S, 3S

B 2S, 3R

C 2R, 3S

D 2R, 3R
 R - S Nomenclature in Wedge Dash Projection

CH3 C2H5 C2H5

H OH H
F H2N H H2N
Cl OH

CHO
H Cl
H3C

Odd Exchange

Even Exchange
 Wedge – Dash Projection ↔ Fischer Projection

D
H

F
I
 Find D – L Nomenclature for following ?

COOH
CH3
H
HO H
H2N CH3 CHO

CH3
H NH2
COOH
 Elements of Symmetry
Plane of Symmetry Centre of Symmetry
Imaginary plane which bisects the molecule in COS is a point from which two same
two equal halves, in such a way that each half atom/groups are at same distance.
of the molecule is a mirror image of other half.
 Plane of symmetry & Centre of symmetry

H D Optically Active
Cl POS COS
F C C
H H
Cl F

Optically Active
Acyclic Compounds POS
CH3 CH3
H OH HO H Cyclic Compounds POS
H OH H OH
COS
CH3 CH3
Question Which one of the following is optically inactive ?

CH3 H
H Cl (ii) CH3 — CH2 — C — CH3
(i)
Cl H
CH3 D

H
CH3 CH3 HO
(iii) (iv) OH
H H H
Enantiomers Diastereomers
1 or 2 chiral carbon 2 chiral carbon
Mirror Images Neither mirror images

Non-superimposable Nor-superimposable

CH3 CH3
Br Br H OH
HO H
Cl I l CI H OH
H OH
F F CD3 CD3
 Physical Properties of Enantiomer & Diastereomer

CH3 CH3 CH3 CH3

HO H H OH D I D I
H OH HO H Br Cl Cl Br
CH3 CH3 F F

CH3 CH3 CH3 H

C C C C
H H H CH3

Enantiomers have similar physical properties except the opposite sign of specific rotation .
Diastereomers have different physical properties ( melting points, boiling points,
densities, solubilities, refractive indices, dielectric constants and specific rotations ).
Q. AIIMS - 2010

Which of the following is optically active : –

OH OH
CH3
A B

OH
OH CH3

C D
Question
Br Br
F F
If optical rotation for is 111° then find optical rotation of
I CI
Cl l
 Meso Compound
Min. 2 chiral carbon Opposite configuration Same connectivity

CH3
H C2H5
H C2H5
CH3

Properties of Meso compound

(i) Meso compounds are optically inactive due to internal compensation of PPL.
(ii) Meso compound and its mirror image are identical.
 Racemic Mixture
Equi-molar mixture of enantiomers

Br Br
Cl I l CI
F F

Note : Racemic mixture is optically inactive due to external compensation of PPL .

 Geometrical & Optical Isomerism
Allenes / Spirans / Cycloalkylidenes

Br F Cl H
H H
C C C C H Cl
I D D D

Cl l

F Br
 Biphenyls

O2N F I I I I

I Cl I l

CI Br

F Br
 No of stereoisomers
1 Stereo centre :
D – CH – CH2 – CH3 CH3 – CH = CH – CH3

CH3

2 Stereo centre :
AIIMS - 2017

CH3 – CH – CH2 – CH – CH2 – CH3 CH3 – CH = CH – CH – CH2 – CH3

CD3 CH3 CH3

2 Stereo centre : CH3 – CH – CH – CH3

OH OH
 Conformational isomerism
Free rotation

Sawhorse Projection Newman Projection

Conformations :
Different arrangements of atoms that can be converted into one another by rotation
about single bonds are called conformations .
 Dihedral Angle
The angle between C – X and C – Y in X – CH2 – CH2 – Y

X X Y
Y

Staggered conformation

Eclipsed conformation

Skew conformation
 Factors affecting stability of conformations

Torsional Strain : Any deviation from the X

staggered conformation X
Y Y
Pitzer strain or Eclipsing strain

Vander Waals Strain : It is due to steric-crowding .

Angle strain : Any deviation from “normal” bond angles

 Conformational Analysis of Ethane

Energy Profile of Ethane

POTENTIAL ENERGY

12.5
kJ/mol

0° 60° 120° 180° 240° 300° 360°

DIHEDRAL ANGLE
Conformational Analysis of Butane
 Conformational Analysis of Butane

POTENTIAL ENERGY

19 kJ
/mol 16 kJ
/mol
3.8 kJ/mol

0° 60° 120° 180° 240° 300° 360°

DIHEDRAL ANGLE

n-Butane exists as 3 conformers one anti (IV) and two gauche (II & VI).
 Case of Intramolecular Hydrogen Bonding

G – CH2 – CH2 – OH where G = – OH , – NH2 , – F , – NR2 , – NO2 , – COOH ,–CHO

2-Flouroethanol

Gauche form is more stable than the anti-form due to intra molecular hydrogen
bonding.
Q. AIPMT – 2010

Which of the following conformers for ethylene glycol is most stable :

OH OH
OH H

A B
H H HO H
H H H H

OH OH
H OH H H

C D
H H H H
H OH
Q. NEET (UG) 2017

With respect to the conformers of ethane, which of the following statements is true?

A Bond angle changes but bond length remains same

B Both bond angle and bond length change

C Both bond angles and bond length remains same

D Bond angle remains same but bond length changes

Q. AIIMS 2016

Which of the following statement is incorrect?

A It is possible to separate eclipsed and staggered form of ethane at

room temprature.

B Eclipsed form has torsional strain.

C Ethane has infinite number of confomer.

D Energy difference between staggered form and eclipsed form of

ethane is 12.5 kJ /mole.
Conformation Dihedral angle () Torsional strain Vander Waal strain
of n-butane

Anti

Gauche

Fully Eclipsed