Organic Chemistry

ISOMERISM

In One Shot Om Pandey, IIT Delhi

Topics
1 Isomer

2 Types of isomerism

3 Structural Isomerism & No of isomers

4 Stereoisomerism & No of isomers

5 Confirmational Isomerism
12 BOARD
TH
Degree of carbon

Degree of unsaturation

Isomers Compounds with same molecular formula but different

physical and chemical property.
 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) Configurational isomers
2) Position isomers a) Geometrical isomers
3) Functional isomers b) Conformational isomers
4) Metamers
2) Conformational isomers
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 3 isomers

C6H14
5 isomers
QUESTION (04 April, 2024 / Shift-I)

The number of different chain isomers for C7H16 is ______________.

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

OH

OH

Cl Cl

Cl
IIT-JEE 2014

The correct combination of name for isomeric alcohols with molecular formula
C4H10O is/are

A tert-butanol and 2-methylpropane-2-ol

B tert-butanol and 1, 1-dimethylethan-1-ol

C n-butanol and butan-1-ol

D isobutyl alcohol and 2-methylpropane-1-ol

Find no of isomers with MF C8H10 ?

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

Acid & Ester 1°, 2°, 3° Amines

Alcohol & Ether

Ketone & Aldehyde

1°, 2°, 3° Amides

Alkene & Alkyne

Enol and Alcohol

Ring – Chain Isomerism

Cyclic Alkane & Alkene

Cyclic Alkene & Alkyne

 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 (05 April, 2024 / Shift-II)

Match List-I with List-II

List-I List-II
(A) 1-propanol and isopropanol (I) Metamerism
(B) Methoxypropane and ethoxyethane (II) Chain Isomerism
(C) Propanone and propanal (III) Position isomerism
(D) Neopentane and Isopentane (IV) Functional Isomerism

A (A) (II), (B) (I), (C)-(IV), (D)-(III)

B (A)-(III), (B)-(I), (C)-(II), (D)-(IV)

C (A)-(I), (B)-(III), (C)-(IV), (D)-(II)

D (A)-(III), (B)-(I), (C)-(IV), (D)-(II)

JEE Mains-2021

Which one of the following pairs of isomers is an example of metamerism?

CH3

A CH3CH2CH2CH2CH3 , H3C – C – CH3

O CH3

B C6H5 , H5C6 H
O
OH
OH
C H5C6 ,
H5C6
O O
D ,
 No of Structural Isomers
No of carbon DU = 0 DU = 1 ( Cyclic )

C3

C4

C5
How many structural isomers are possible for following MF ?
C4H9Cl Different type of carbon
with atleast 1 H

C4H9OH Alcohol C4H10O Ether

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

C4H8O Cyclic Alcohol C4H8O Cyclic Ether

Ketones & Aldehydes

C4H8O

C5H8O
Cyclic Ketones
JEE Mains - 2021

Compound with molecular formula C3H6O can show :

A Positional isomerism

B Both positional isomerism and metamerism.

C Metamerism.

D Functional group isomerism.

 Wedge Dash Projection
F
Wedge : Towards Observer H
Dash : Away from observer Br
HO

Fischer Projection
OH

F Br
Vertical line : Away from observer
H
Horizontal line : Towards observer
 Stereoisomerism Same structural formula but different orientation
in space

CH3 CH3 CH3 H

C C C C
H H H CH3

Restricted Rotation :
 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 F
(1) C C
H H (4)
Cl

D D
(2) H C C
H

I F
(3) C C
Br Cl
JEE Mains 2020 / 5 Sept/Shift-II

Among the following compounds, geometrical isomerism is exhibited by :

CHCl CHCl

A B
CH3

CH2 CHCl

C D
H3C CH3
Cl
 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
F Cl
 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
JEE Mains 2020 / 6 Sept / Shift-I

Which of the following compounds shows geometrical isomerism ?

A pent-2-ene

B 4-methylpent-1-ene

C 4-methylpent-1-ene

D 2-methylpent-1-ene
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 CH2 — H I CH2 — NH2
4) Group having D.B. / T.B. are treated as following.

F
C C
Cl
JEE(Main) 2017 Online

In the following structure, the double bonds are marked as I, II, III and IV
II

III

I IV

Geometrical isomerism is not possible at site (s) :

A I

B III

C I and III

D I and IV
 JEE(Main) 2015

Which of the following compound will exhibit geometrical isomerism?

A 1-Phenyl-2-butene

B 3-Phenyl-1-butene

C 2-Phenyl-1-butene

D 1, 1-Diphenyl-1-propene
 Physical Properties of G.I.

Dipole moment Stability

Boiling point Melting point

Solubility in water

Br H Br Br
C C C C
H Br H H
AIEEE 2002 ( H.W. )

Which of the following does not show geometrical isomerism?

A 1, 2-Dichloro-1-pentene

B 1, 3-Dichloro-2-pentene

C 1, 1-Dichloro-1-pentene

D 1, 4-Dichloro-2-pentene
Polarimeter Experiment
+15°0 –15°
+30° –30°
+45° –45°

 → 0o
Optically Inactive

Polarizer Plane Sample cell Analyzer

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

 → (-) , Anti-clockwise
Leavo-rotatory
compound
 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 / Asymmetric 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)
C2H5 O N
Br
O H
H5C2 D
(d) Si (e) CH3 S C2H5
H3C H
JEE Mains 2022 /29 June/Shift-I

Observe structure of the following compounds

Cl NH2
OH OH
H2N
O O

OH

The total number of structures compounds which possess asymmetric atoms

is ______________.
Chiral Compounds A compound which is non-superimposable on its mirror image
Asymmetric compounds F
H

HO Br

OH

F Br

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

 AIEEE 2004

Amongst the following compounds, the optically active alkane having lowest molecular
mass is

A CH3 – CH2 – CH2 – CH3 B CH3 – CH2 – CH2 – CH3

C CH3 – C D CH3 – CH2 – C  CH

C2H5
AIEEE 2004

Among the following four structures I to IV.

CH3 O CH3 H CH3

C2H5 – CH – C3H7 CH3 – C – CH – C2H5 H – C C2H5 – CH – C2H5

(I) (II) (IV)
H
(III)
It is true that :

A All four are chiral compounds

B Only I and II are chiral compounds

C Only III is a chiral compound

D Only II and IV are chiral compounds

 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

Absolute Configuration
Relative Configuration
R – S Nomenclature
D – L Nomenclature

Standard : Glyceraldehyde

CHO CHO
H OH HO H
CH3 CH3

Note : Applied only in Correct Fischer Projection

 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
O
a
CHO C H
c d H Cl HO H
b H3C
H OH

CH2OH

Odd & Even Exchange

CHO
H Cl
H3C
JEE (Main) 2016
CO2H
H OH
The absolute configuration of is
H Cl

CH3

A (2S, 3R)

B (2S, 3S)

C (2R, 3R)

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

CH3
H
F
Cl

C2H5 C2H5
OH H
H2N H H2N
OH
 Wedge – Dash Projection Fischer Projection

D
H

F
I

D
I
F
H

D
F

H
I
 Find D – L Nomenclature for following ?

CH3
HO H
CHO

COOH
H
H2N CH3
 AIEEE 2008

HO2C CO2H
The absolute configuration of is
H
H OH
OH
A R, R

B R, S

C S, R

D S, S
 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.

H CH3 CH3 HO H
CH3 CH3 HO

H H H OH
H H H OH
 Plane of symmetry & Centre of symmetry

H D
Optically Active
F C Cl C
Acyclic Compounds POS
H H
Cl F
Cyclic Compounds POS
COS

CH3 CH3
CH3 CH3
H OH HO H
H OH H OH
CH3 H D
CH3
 AIEEE 2007

Which of the following molecules is expected to rotate the plane of polarized light?
NH2
H2N COOH CHO
H
(1) H (2) H2N H (3) HO H (4)
Ph Ph H CH2OH
SH
 IIT-JEE-2008

The correct statement(s) about the compound given below is (are).

H
Cl
CH3
H3C
Cl H

A The compound is optically active

B The compound possesses centre of symmetry

C The compound possesses plane of symmetry

D The compound possesses axis of symmetry

Enantiomers Br Br
1 or 2 chiral carbon Cl I l CI

Mirror Images F F

Non-superimposable

Diastereomers CH3 CH3

HO H H OH
2 chiral carbon
H OH H OH
Neither mirror images CD3 CD3
Nor-superimposable
 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 ).
JEE Mains 2022 / 29 July/Shift-II
CH3
Statement I : The compound NO2
is optically active. (A)
H

CH3 CH3
O2N
Statement II : The compound is mirror image of above compound A . H CH3

A Both statement-I and Statement-II are correct

B Both statement-I and Statement-II are incorrect

C Statement-I is correct but Statement-II is incorrect

D Statement-I is incorrect but statement-II is correct

 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 rotation of PPL.

(ii) Meso compound and its mirror image are identical.

AIEEE 2004

Which of the following will have a meso-isomer also ?

A 2-Chlorobutane

B 2, 3-Dichlorobutane

C 2, 3-Dichloropentane

D 2-Hydroxypropanoic acid
 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 rotation of PPL .
 Asymmetric Nitrogen : Amine Inversion
Two enantiomers of amines always exist as racemic mixture hence optically inactive.

H
Cl Me

N N — Me
Me
C2H 5 CH3

Nitrogen salts and cyclic amines will not undergo amine inversion.
Geometrical & Optical Isomerism Allenes / Spirans / Cycloalkylidenes

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

Cl l

F Br
JEE Mains 2023/01 Feb/Shift-I

The total number of chiral compound/s from the following is _____________.

Ph

OH
O O Cl
COOH

CH2 OH
COOH
HO OH
OH
OH
HO2C COOH
HO OH
COOH
OH
Biphenyls

O2N F I I I I

I Cl
I l

CI Br

F Br
IIT - JEE 2007

Statement-1 : Molecules that are not superimposable on their mirror images are chiral.
Statement-2 : All chiral molecules have chiral centres .

A Statement-1 is true, statement-2 is true; statement-2 is a correct explanation for

statement-1.

B Statement-1 is true, statement-2 is true; statement-2 is NOT a correct explanation

for statement-1.

C Statement-1 is true, statement-2 is false.

D Statement-1 is false, statement-2 is true.

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

CH3

2 Stereo centre :

CH3 – CH – CH – CH3 CH3 – CH – CH – C2H5 CH3 – CH = CH – CH – OH

OH OH OH OH CH3
2 Stereo centre :
CH3 – CH = CH – CH = CH –CH3 CH3 – CH = CH – CH = CH –C2H5

3 Stereo centre :

H3C(HO)HC – CH = CH – CH(OH)CH3 H5C2(HO)HC – CH = CH – CH(OH)CH3

AIEEE 2009

The number of stereoisomers possible for a compound of the molecular formula

CH3 – CH = CH – CH(OH) – Me is :

A 2

B 4

C 6

D 3
 IIT-JEE 2009

The correct statement(s) about the compound H3C(HO)HC – CH = CH – CH(OH)CH3 (X)

is (are):

A The total number of stereoisomers possible for X is 6.

B The total number of diastereomers possible for X is 3.

C If the stereochemistry about the double bond in X is trans, the number of

enantiomers possible for X is 4.

D If the stereochemistry about the double bond in X is cis, the number of

enantiomers possible for X is 2.
JEE (Advanced) - 2018

For the given compound X, the total number of optically active stereoisomers is …………

HO HO
This type of bond indicates that the configuration at the
specific carbon and the geometry of the double bond is fixed
This type of bond indicates that the configuration at the
HO HO specific carbon and the geometry of the double bond is NOT
X fixed
 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 : Other than Staggered & Eclipsed

 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 .

 Conformational Analysis of Ethane

Energy Profile of Ethane

POTENTIAL ENERGY

12.5
kJ/mol

0° 60° 120° 180° 240° 300° 360°

DIHEDRAL ANGLE
JEE Mains-2022

Staggered and eclipsed conformers of ethane are :

A Polymers

B Rotamers

C Enantiomers

D Mirror images
Conformational Analysis of Butane
 Conformational Analysis of Butane

POTENTIAL ENERGY

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

0° 60° 120° 180° 240° 300° 360°

DIHEDRAL ANGLE

n-Butane exists as 3 conformers one anti and two gauche .

JEE Mains-2022

Arrange the following conformational isomers of n-butane in order of their increasing

potential energy
CH3 CH3 CH3 HH
H CH3 H
H CH3
I II III IV
H H H H
H H H H H H HC CH
3 3
CH3 H

A II < IV < III < I

B I < III < IV < II

C II < III < IV < I

D I < IV < III < II

 IIT – JEE 2010

In the Newman projection for 2, 2-Dimethylbutane

X
H3C CH3

H H

Y
X and Y can respectively be:

A H&H

B H & C2H5

C C2H5 & H

D CH3 & CH3

 IIT-JEE 2004

Newman projection of Butane is given, C-2 is rotated by 120° along C-2 & C-3 bond in
anticlockwise direction the conformation formed is :
CH
4 3
H H
3 2
H H
1
CH3
A Anti

B Fully eclipsed

C Gauche

D Partially eclipsed
Conformational Enantiomers CH3 CH3
H CH3 CH3 H
The gauche conformers of butane
are mirror images of each other. H H H H
H H

Conformational Diastereomers CH3 CH3

H CH3 H
Gauche conformations and anti conformation H
of butane are not mirror images of each other.
H H H H
H CH3
 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.
AIEEE 2006

Increasing order of stability among the three main conformations (i.e. eclipse, anti,
gauche) of 2-fluoroethanol is

A eclipse, gauche, anti

B gauche, eclipse, anti

C eclipse, anti, gauche

D anti, gauche, esclipse

AIEEE / JEE AD

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
IIT-JEE 2012 Which of the given statement(s) about N, O, P and Q with
respect to M is (are) correct ?

Cl CH3 CH3
HO H HO H
H H OH HO H
OH
HO Cl H CH3 HO
H OH H
HO H HO H
CH3 Cl CH3
Cl Cl
A M and N are non-mirror image stereoisomers.

B M and O are identical

C M and P are enantiomers

D M and Q are identical

JEE ( Advanced ) - 2014

The total number(s) of stable conformers with non-zero dipole moment for the
following compound is (are) :

Cl
Br CH3
Br Cl

CH3
JEE Adv. 2019
Total number of isomers considering both structural and stereoisomers, of cyclic
ethers with the molecular formula C4H8O is ____________
O
O O O
O
(S)
CH3 * CH3 CH3 (R)
CH3
(1 isomer)
(1 isomer) (2 isomers)

O O O O
CH3 * (S) (R)
CH3 CH3 CH3
CH3
(1 isomer) (2 isomers)

O O O O
(R) (R) (S)
(S) (R) (S)
H3C * * CH3 H3C CH3 H3C CH3 H3C CH3
(3 isomers)
JEE Mains 2022 / 27 June / Shift-I

Total number of possible stereoisomers of dimethyl cyclopentane is ________________.

CH3 CH3 CH3

R R S
CH3 CH3 CH3
S R S

CH3 CH3 CH3

R R S

S R S
CH3 CH3 CH3

Out of six isomers, two are meso compounds and are optically inactive
Therefore, only 4 isomers will be optically active.
QUESTION (30 Jan, 2024 / Shift-II)

Number of geometrical isomers possible for the given structure is/ are _______________.
D
H H