JEE (MAIN+ADVANCED)

STRUCTURAL ISOMERISM
 CONTENT

S.No Pages

1. Structural Isomerism 01 – 6
2. Exercise-1 (Subjective Questions) 07 – 08
3. Exercise-2 (Objective Questions) 09 – 12
4. Exercise-3 13
5. Exercise-4 14
6. Exercise-5 15 – 18
7. Answer Key 19
 STRUCTURAL ISOMERISM

ISOMERISM
INTRODUCTION

(i) The compound which have the same molecular formula but differ in physical and chemical properties are
called as Isomer and the phenomenon is called Isomerism.
(ii) The term ‘isomer’ was given by Berzellius.
(iii) The isomer was derived from Greek word meaning ‘equal or like part’ (isos= equal; meros = parts)

Isomerism

Structural Isomerism Stereoisomerism

Chain isomerism
Position isomerism
Configurational Conformational
Ring chain isomerism
Functional isomerism
Metamerism
Geometrical Optical
Tautomerism Isomerism Isomerism

STRUCTURAL ISOMERISM / CONSTITUTIONAL ISOMERISM

Structural isomers possess the same molecular formula but different connectivity of atoms. The term
constitutional isomerism is a more modern term of structural isomerism. It is sub-classified into
following types.

(i) Chain Isomerism :

The different arrangement of carbon atoms gives rise to chain isomerism. Chain isomers possess different
lengths of carbon chains (straight or branched). Such isomerism is shown by each and every family of
organic compounds.

Butane : C4H10
CH3 – CH2 – CH2 – CH3 n- butane
iso butane

n-butane has the chain of four carbon while isobutane has three in carbon chain. Hence they are
chain isomers.
Butyl alcohol : C4H9OH
CH3 – CH2 – CH2 – CH2OH n-Butyl alcohol
Isobutyl alcohol

These two butyl alcohols are chain isomers.

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 STRUCTURAL ISOMERISM

(ii) Position Isomerism

Position isomerism is shown by the compounds in which there is difference in the position of
functional group, multiple bond or substituent along the same chain length of carbon atoms
To show position isomerism following conditions must be followed
(i) The same molecular formula
(ii) The same length of carbon chain
(iii) The same functional group.

Example :
(a) CH3 – CH2 – CH2Cl and

1- Chloropropane 2- Chloropropane

(b) CH3 – CH2 – CH2OH and

1 - propanol 2 -Propanol

(iii) Ring chain isomerism

Such isomerism arises because of the difference of carbon-chain or ring.
For example :

(i) CH3CH=CH 2
Cyclopropane Propene

Cyclopropane and propene are ring chain isomers.

(ii) CH3 – CH2 – CH = CH2

Cyclobutane
Cyclobutane is the ring-chain isomer of 1-butene.
Note: Acyclic Alkanes do not exhibit ring-chain isomerism.

(iv) Functional group isomerism

Compounds with the same molecular formula but differing in the type of functional group they possess
are classed as functional isomers and isomerism between them is known as functional isomerism. For
example:
CH3 – CH2 – OH and CH3 – O – CH3
Ethyl alcohol Dimethyl ether
(Alcohol) (Ether)

CH3 – CH2 – COOH and

Propanoic acid Methyl acetate
(Acid) (Ester)
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 STRUCTURAL ISOMERISM

OH OH

and

Phenol Alcohol

CH3CH2NH2 , (CH3)2NH , (CH3)3N

(1º – amine) (2º–amine) (3º–amine)

O O O CH3
CH3CH2CH2–C–NH2 , CH3 – CH2–C–NH , CH3 – C – N – CH3
(1º amide) (2º amide) (3º amide)
CH3

CH3CN , CH3NC
(Cyanide) (Isocyanide)

1º, 2º, 3º – alcohols never considered as different functional group isomers but 1º, 2º, 3º-amine and 1º,
2º, 3º amides are considered as functional group isomers.

(v) Metamers :
This type of Isomerism arises due to unequal distribution of alkyl substituents around a polyvalent
functional group.
Some example of Polyvalent functional groups.
–O– (Ether)  C  (Ketone)
||
O

 N  (tert.amine) –S– (Thioether)

|

O
||
 C  (Thioketone) –C–O– (Ester)
||
S
O
C (acid anhydride)
O
C
O
Example :-
(i) CH 3  C  CH 2  CH 3  CH 2 and CH 3  CH 2  C  CH 2  CH 3
|| ||
O O
(2  Pentanone) (3  Pentanone)
(ii) Diethyl ether and methyl propyl ether
CH3CH2OCH2CH3 (Diethyl ether); CH3OCH2CH2CH3(Methyl propyl ether)
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 STRUCTURAL ISOMERISM

(iii) Diethyl amine and methyl propylamine

CH3CH2 – NH – CH2CH3 (Diethyl amine);
CH3 CH2CH2–NH–CH3(Methyl propyl amine)
O O
OH HO
(iv) C–O and C–O are metamers

(vi) Tautomerism :
(i) Tautomerism is a special type of functional group isomerism which arises due to the transfer of
hydrogen atom as proton from a polyvalent atom to other polyvalent atom.
(ii) Such isomers are directly and readily inter convertible under ordinary conditions, and the isomers
are called tautomers.
(iii) Tautomers exist in dynamic equilibrium.
(iv) The other names of tautomerism are ‘desmotroprism’ or ‘prototropy’.
(v) Tautomerism is thus the property shown by certain compounds exhibiting different
properties, as if they posses different structures and these constitutional isomers are called tautomers.
(vi) If the hydrogen atom oscillates between two polyvalent atoms linked together, the system is called
as Diad.

H–C N C N – H
Hydrocyanic acid isocyanic acid
(vii) Hydrogen atom oscillates in between first and third atoms in a chain, the system is called as triad.
H – O – C N O=C=N–H

(a) Keto - Enol Tautomerism -

(i) When the tautomers exist in the two forms keto & enol then, such type of tautomerism is called
keto-Enol tautomerism'.
(ii) It was discovered by the scientist 'Knorr' in 1911 in acetoacetic ester.
(iii) The Keto means the compound has a Keto group > C = O, and the enol form has both double
bond and OH (hydroxy) group Joined to the same carbon.

H O OH
| || |
–C–C– –C=C–
| |
Keto forms Enol forms
Conditions for tautomerism
(i) Presence of groups like >C = O, –N = O , >C = N– & -H with respect to these groups.
(ii) In order for conversion of a keto form to its enol form it must have an -hydrogen (i.e., hydrogen
attached to the carbon adjacent to the carbonyl group). Thus benzaldehyde,
m-chlorobenzaldehyde (in general, aromatic aldehydes) formaldehyde, trimethylacetaldehyde do
not exist as their enol forms.
O
O ||
|| C–H
|

C–H
|

|
Cl
Benzaldehyde m-Chlorobenzaldehyde
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 STRUCTURAL ISOMERISM

CH3
|
H–C–H CH3–C — C–H
|| | ||
O CH3 O
Methanal Trimethyl-acetaldehyde

(iii) Keto enol tautomerism can occurs both in acidic and basic medium.
Example of Keto enol tautomerism :-
H O
| ||
(i) CH2=C–OH CH3–C–H
Vinyl alcohol Acetaldehyde
Enol form Keto form
O OH
|| |
(ii) CH3–C–CH 3 CH2=C–CH3
Acetone Isopropenyl alcohol
Keto form Enol form

Enol – Contents : It is the % amount of enoL in keto enoL system usually keto content is generally more than
Enol. contents.

Enol contents :  Stabilityof enol

 aromatic in enol
 conjugation in enol
 Hydrogen bonding in enol
 Acid strength of -H of keto form
 Presence of electron withdrawing group

Normally Enol content of cyclic system is greater than corresponding a cyclic system as insertion of -
bond is easier in cyclic system.
O O

eg. >

O O O
O
>

O O O
>

O O O O
>
H H
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 STRUCTURAL ISOMERISM

O O
> OR

O O O

> >

O O O O O O
> >
OR RO OR

O O O O

> >

O OH

O
(Aromatic enol)

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 STRUCTURAL ISOMERISM

EXERCISE-1 (Subjective Questions)

Q.1 How many benzenoid isomer are possible for cresol.

Q.2 Calculate the total number of structural isomers of 3°-amines for the molecular formula C6H15N are?

Q.3 How many cyclopentane structures (excluding stereo isomer) are possible for C7H14.

Q.4 Mention the specific type of isomerism exhibited by each of the following pairs:
(a) 1,2-dichloro ethane and 1,1-dichloro ethane
(b) Propanoic acid and methyl acetate
(c) Methyl acetate and ethyl formate
(d) o-Nitrophenol and P-nitrophenol
(e) Anisole and o-cresol
(f) Phenol and Cyclohexa-2,4-dien-1-one

Q.5 In each of the following pairs which will have less enol content :
O O
(a) and (b) and

(c) and (d) and

(e) CH 2  CHO and CH 3  CHO

|
Cl
Q.6 In each of the following pairs which will have less enol content :

(a) and (b) and

Q.7 In each of the following sets of compounds write the decreasing order of % enol content.

(a)
O
(II)

(b)

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 STRUCTURAL ISOMERISM

Q.8 In each of the following sets of compounds write the decreasing order of % enol content.
O O
(a)

(I) (III)

O
O
(b) O
N
(II) CH3
(I)
(III)

Q.9 In each of the following sets of compounds write the decreasing order of % enol content.
O O O O O O

O O O
II (III) IV

O O
C C
Q.10 CH3 CH2 CH3
(II)
Among these give ease of enolization.

   OH
O Na O Na O OH
NaOH H+/H2 O +
Q.11 +
H2O (Major) (Minor)
(Minor) (Major)
Explain the observation.

Q.12 Decreasing order of enol content of the following. (along with proper explanation).

(a) (b) (c) (d)

(e)

Q.13 Minimum number of carbon atoms required for an alkane to show any kind of isomerism.

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 STRUCTURAL ISOMERISM

EXERCISE-2 (Objective Questions)

[SINGLE CORRECT CHOICE TYPE]
Q.1 The number of primary, secondary and tertiary amines possible with the molecular formula C3H9N
respectively.
(A) 1, 2, 2 (B) 1, 2, 1 (C) 2, 1, 1 (D) 3, 0, 1

Q.2 C7H7Cl shows how many benzenoid aromatic isomers ?

(A) 4 (B) 3 (C) 5 (D) 6

COOH
OCOH
Q.3 & functional isomer

OMe OEt
Et
& metamers
Me
CH2 – CH2 – OH CH2 – O – CH3

& metamers

Me – N – Me CH2 – NH – CH3

& functional isomers

(A) TFTF (B) FTTF (C) TTFT (D) TFFT

Q.4 How many structural isomeric primary amines are possible for the formula C4H11N?
(A) 2 (B) 3 (C) 4 (D) 5

Q.5 How many structural isomers of C5H10 are possible.

(A) 10 (B) 11 (C) 12 (D) 13

Q.6 How many structural isomer are possible when one of the hydrogen is replaced by a chlorine atom in
anthracene?
(A) 3 (B) 7 (C) 4 (D) 6

Q.7 Tautomer in following is Diad system :

O

(A) CH3COCH3 (B) CH3CH2NO2 (C) (D) HCN

Q.8 Among the following the compounds having the highest enol content :
(A) CH3COOCH3 (B) CH3COCH3
(C) CH 3  C  CH 2 CHO (D) CH3–CO–CH2–CO2CH3
||
O
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 STRUCTURAL ISOMERISM

Q.9 Decreasing order of enol content of the following compounds in liquid phase
O
O O
O
||
CH 3  C  OEt
(1) (3) ( 4)
(A) 2 > 1 > 3 > 4 (B) 1 > 2 > 3 > 4 (C) 4 > 3 > 2 > 1 (D) 3 > 1 > 2 > 4

Q.10 Which of the following cannot be written in an isomeric form?

(A) CH3–CH(OH)–CH2–CH3 (B) CH3–CHO
(C) CH2=CH–Cl (D) Cl–CH2CH2–Cl

Q.11 Molecular formula C3H6Br2 can have structures of

(A) Two gem dibromide (B) Two vic dibromide
(C) Two ter.- dibromo alkane (D) None of these

Q.12 Only two isomeric monochloro derivatives (Structures only) are possible for
(A) n-butane (B) 2, 2-dimethylpentane
(C) benzene (D) neopentane

Q.13 The number of structural isomers of C3H5Br3 is

(A) 4 (B) 5 (C) 6 (D) 7

Q.14 On chlorination of propane number of products of the formula C3H6Cl2 is (Only structural isomers)
(A) 3 (B) 4 (C) 5 (D) 6

Q.15 Which compound can not show tautomerism?

O
O O O
(A) (B) (C) (D) N–H
O
H

[MULTIPLE CORRECT CHOICE TYPE]

Q.16 Which of the following compounds have higher enolic content than Keto content?
O O O
|| || O
(A) CH 3  C  C  CH 3 (B)

O O
O
(C) (D)

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 STRUCTURAL ISOMERISM

Q.17 In which of the following pairs first will have higher enol content than second :

(A) and

(B) and

(C) and

(D) and

Q.18 What statement is correct for Keto-enol tautomerism ?

(A) Tautomersim is catalysed by acid and base.
(B) Tautomers are present in dynamic equilibrium state.
(C) Generally keto form is more stable than enol form in mono Ketones.
(D)Atomic arrangements are same in tautomerism

Q.19 Tautomer of following compound is :

O O

C – CH2 – C

(A) C – CH = C (B) C – CH2 – C

O OH OH O

(C) C – CH = C (D) C – CH2 – C

OH OH O OH

Q.20 Which compound will show tautomerism?

O N OH

(A) Ph–NO (B) (C) (D) HCHO

O
Q.21 Which of the following compound has enol content more than keto.
O O O
O O O O
(A) (B) (C) (D) OEt
OEt
N
H
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 STRUCTURAL ISOMERISM

Q.22 Which of the following is/are correct matchings ?

O O
(A) CH3—C—OH and H—C—OCH3 – Metamers

(B) CH3—CH2—C CH and CH3—C C—CH3 – Position isomers

(C) CH3CH2CH2NH2 and CH3—CH—CH3 – Tautomers

NH2
(D) CH3CH2OH and (CH3)2O – Functional isomer

[MATCH THE COLUMN]

Q.23 Match Column I with Column II :

Column I Column II
O O
|| ||
(A) CH 3  C  O  C3H 7 & Et  C  O  Et (P) Chain isomer

(B) & (Q) Positional isomers

(C) & (R) Metamers

(D) CH 3  CH  O  CH 3 & CH3–CH2–CH2–O–CH3 (S) Tautomers

|
CH 3

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 STRUCTURAL ISOMERISM

EXERCISE-3

(JEE ADVANCED Previous Year's Questions)

Q.1 Writestructural formulaefor all theisomeric alcoholshaving themolecular formulaC 4H10O.

[JEE 1984]

Q.2 True or False:

m-chlorobromobenzene is an isomer of m-bromochlorobenzene. [JEE 1985]

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 STRUCTURAL ISOMERISM

EXERCISE-4

(Potential Problems Based on CBSE)

Very Short Answer Type Questions

Q.1 What do you mean by structural isomerism?

Q.2 Butane and 2-methyl propane are which type of isomers?

Q.3 Which type of isomerism is present in CH3CH2OH and CH3OCH3?

Q.4 Which type of isomerism is exhibited by but-1-yne and but--2-yne?

Short Answer Type Questions

Q.5 Draw all the possible structural isomers with the molecular formula C6H14.

Q.6 Draw all the postion isomers of an alcohol with molecular formula C3H8O.

Q.7 What is meant by metamerism? Give an example.

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 STRUCTURAL ISOMERISM

EXERCISE-5 (Rank Booster)

[SINGLE CORRECT CHOICE TYPE]
Q.1 Which of the following has incorrect relation
Me
Pr Pr
(A) & identical
Me

Me Et
(B) & positional isomers
Pr Pr
Et Et
(C) & positional isomers
Pr
Pr
Me
Me
Et
(D) & homologues
Pr

Q.2 Given compound shows which type of isomerism

O O
S—O and S—O
O O
(A) Chain isomerism (B) Positional isomerism
(C) Metamerism (D) Functional group isomerism
O
OD / D 2O
Q.3 Ph (P) final product is ?
(prolonged)

O D O D
C
(A) Ph CD3 (B) Ph CH3
D D
O H O
(C) Ph CD3 (D)
Ph CH3
D

Q.4 Decreasing order of enol content of the following compound in liquid phase
O O O O
|| || || ||
(a) CH 3  C  CH 2  C  O  Et (b) CH 3  C  CH 2  C  CH 3

O O O
|| ||
(c) Ph  C  CH 2  C  Ph (d)

(A) a > b > c > d (B) c > b > a > d (C) c > b > d > a (D) b > c > a > d
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 STRUCTURAL ISOMERISM

O OH
|| | HO


Q.5 CH 3  C  CH  Ph (II)
( I)
(I) isomerizes to (II) on addition on small amount of base structure of (II) is
OH OH O OH
| | || |
(A) CH3  CH — CH  Ph (B) H  C  CH 2  CH  Ph

(C) CH 3  CH  C  Ph (D) CH 3  C — C  Ph
| || || ||
OH O O O

[MULTIPLE CORRECT CHOICE TYPE]

Q.6 Identify the position isomer.

(A) & (B) &

CN NC
CN NC
O

(C) & (D)

OCH3 O
OCH3
Q.7 Which of the following can tautomerise.

O O O

(A) CD3  C  Ph (B) (C) (D)

|| N
O H

Q.8 Which of the following compounds show tautomerism ?

O S
(A) NH2—C—NH2 (B) NH2—C—NH2

O
(C) HO N O (D) CH3—C—CH3

Q.9 Which compound show tautomerism:

O
OH N OH

(A) (B) (C) (D) None of these

N=O
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 STRUCTURAL ISOMERISM

Q.10 What is relation between (I), (II) and (III) ?

O OH O–
+ +
HN NH N N HN NH
(I) (II) (III)
– +
O N O HO OH O N O
–

H N
H
(A) I and II are tautomers (B) III is conjugate base of II
(C) III is resonance structure of I (D) no relation exists

[MATRIX TYPE]
Q.11 Match the column :
Column I Column II
O OH

(A) (P) Tautomers

O OH

(B) (Q) Structural isomers

OH OH

(C) (R) Position isomers

O CH2

(D) (S) Atleast one of the two structures is enol

OH

[SUBJECTIVE TYPE]

Q.12 Find out the total number of cyclic structural isomers of C6H12.

Q.13 % enol content of acetylacetone in following solvents is found as :

Solvent % enol content
H2 O 15
Liquid state 76
hexane 92
gas phase 92
Explain the observation.

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 STRUCTURAL ISOMERISM

Q.14 In each of the following pairs which is more stable :

(a)  (b) 

(c)  (d) 

(e) 

Q.15 In each of the following pairs which is more stable :

H H
O O O O O O O O
C C C C
(a) CH3 (b)
CH3 CH2 CH3 CH3 CH
(I) (II) (I) (II)

(c)  (d) 

(e) 

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 STRUCTURAL ISOMERISM

ANSWER KEY
EXERCISE-1

Q.1 5 Q.2 7 Q.3 4

Q.4 (a) Positional (b) Functional (c) Metamerism (d) Positional (e) Functional (f) Tautomerim
Q.5 (a) 2; (b) 1; (c) 2; (d) 1; (e) 2 Q.6 (a) 2; (b) 2
Q.7 (a) 2>1; (b) 4>2>1>3; Q.8 (a) 4 > 1 > 3 > 2 ; (b) 2>1>3
Q.9 3>2>4>1 Q.10 2 >1

Q.12 > > > >

(a) (b) (c) (d) (e)

|
(a) Keto form is less stable due to repulsion between  C  O groups so that this exist in enol form. Enol
H
O O

form is also stable due to H-bonding

(b) Active 'H' atom / Acidic 'H' atom so has more enolic content (enol stabilise by resonance & Intra
molecular H–bonding) >
(c) Enolic contents decreases with introduction of e– donator group which causes repulsion in enolic form .
(d) Due to ester group acidic structure of active H decreases & C=C of enol undergoese cross resosnace >
(e) Lowest enolic content because is more stable than Bond
Q.13 4

EXERCISE-2
Q.1 C Q.2 A Q.3 C Q.4 C Q.5 A Q.6 A Q.7 D
Q.8 C Q.9 B Q.10 C Q.11 A Q.12 A Q.13 B Q.14 B
Q.15 B Q.16 BD Q.17 AC Q.18 ABC Q.19 ACD Q.20 C Q.21 D
Q.22 BD Q.23 (A) R, (B) Q, (C) S, (D) Q

EXERCISE-3
Q.1 4 Q.2 False

EXERCISE-5
Q.1 B Q.2 C Q.3 C Q.4 B Q.5 C Q.6 BC Q.7 ABC
Q.8 ABCD Q.9 AC Q.10 AC Q.11 (A) P,Q,S; (B) Q,S; (C) Q,R,S; (D) Q,S
Q.12 12 Q.14 (a) 1; (b) 1; (c) 1; (d) 1; (e) 1 Q.15 (a) 2; (b) 2; (c) 1; (d) 2; (e) 1

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