3.

Structural
Isomerism 3

Anupam Gupta
Anupam Gupta
B.Tech & M.Tech - IIT Delhi

10+ Years Total Experience

Mentored JEE, KVPY,

Olympiad Rank Holders

@anupamguptachem
Telegram Channel
livedaily.me/jee
 Unacademy
Subscription

LIVE Class Environment Performance Analysis

LIVE Polls & Leaderboard Weekly Test Series
LIVE Doubt Solving DPPs & Quizzes
LIVE Interaction
 India’s BEST Educators Unacademy Subscription

If you want to be the BEST

“Learn” from the BEST
 Top Results
Bratin Mondal

100 %ile
 11th / 9, 10

12th / Drop

ANUPAMLIVE
 11th / 9, 10

12th / Drop

ANUPAMLIVE
 3.0

Structural
Isomerism 3

Anupam Gupta
 Tautomerism

Definition : Tautomers are two structural isomers (having different functional

groups) which exist in dynamic equilibrium with each other.

Mechanism: The isomers change into each other on shifting of H-atom from one
position to another position in presence of a catalyst.
Keto-enol Tautomerism
Draw enol forms of following carbonyl compounds

i. CH3 - CH = O

ii.

iii.
Which of the following will show tautomerism

A. Me3C -CHO B. Me2CD -CHO

C. D.
Keto-enol tautomerism is not observed in:

A. B.

C. D.
The enolic form of acetone contains:

A. 9 σ bonds, 1 π bond and 2 lone pairs

B. 8 σ bond, 2 π bond and 2 lone pairs
C. 10 σ bond, 1 π bond and 1 lone pairs
D. 9 σ bond, 2 π bond and 1 lone pair
 Stability of Enol form

The Group is more resonance stabilized

An alkene is less resonance stabilized

 Stability of Enol form

In case of monocarbonyl compounds, the compound exists in Keto form (99%).

The enol form is insignificant (less than 1%)
 Stability of Enol form

As stability of alkene increases % enol content increases.

Factors for stabilization of alkene:
1. Alpha-hydrogens leading to hyperconjugation
2. Resonance
 Stability of Enol form

The β-dicarbonyl (or 1, 3-dicarbonyl) compounds have significant enol contents

due to resonance stabilization of enol form
 Stability of Enol form

In phenol (enol form is much more stable due to aromaticity)

 Compare % enol contents

Keto form ⇌ Enol form

I : CH3CH = O ⇌ CH2 = CH - OH

II: CH3 -CH2 - CH = O ⇌ CH3 -CH = CH - OH

III:
Compare % enol contents

I:

II :

III :
The tautomer of I is

A. II
B. III
C. Both II and III
D. None of these
Tautomer of I is

A. II
B. III
C. Both II and III
D. None of these
 Mechanism: Base-catalyzed enolization

Aldehyde or Carbanion enolate ion enol

ketone
(conjugate base of both carbonyl compound and enol)
Mechanism: Base-catalyzed enolization
Mechanism: Acid-catalyzed enolization
Mechanism: Acid-catalyzed enolization
Molecule can be enolised by which hydrogen ?

A. y-H
B. z-H
C. both
D. None of these
 Properties of Keto and enol forms

Polarity Keto form > enol form

Boiling point

The keto form is more polar and the enol form has intramolecular H-bonding
 Properties of Keto and enol forms

Solubility
In polar solvents (like H2O). The more polar keto forms is more soluble in water,
than the less polar enol form. The enol form has intramolecular H-bonding
 Properties of Keto and enol forms

Optical Properties

The carbonyl compounds which have alpha asymmetric carbon (C*) atom and
have α - H hydrogen atom, racemise due to tautomerisation on keeping in
aqueous solution.
Which of the following compounds will racemise on keeping in
aqueous solution

A. B.

C. D.
 Properties of Keto and enol forms

● Chemical properties

The β-dicarbonyl compounds in aqueous solution show chemical properties of

both the forms. The lab tests of following functional groups are positive.

i. ii. C = C ii. -OH

Which among the following compound will give maximum enol
content in solution:

A. B.

C. D.
Arrange the following in decreasing order of percentage enol content.

A. l > ll > lll > lV

B. ll > l > lll > lV

C. ll > lll > l > lV

D. lll > ll > lV > l

Other types of Tautomerism
The number of structural isomers for C6H14 is:

A. 4
[2015]
B. 3
C. 6
D. 5
Which of the following pairs of compounds are positional isomers?

[2015]
A. B.

C. D.
 #JEELiveDaily Schedule

11th

Namo Sir | Physics Ashwani Sir | Chemistry Sameer Sir | Maths

6:00 - 7:30 PM 7:30 - 9:00 PM 9:00 - 10:30 PM

12th

Jayant Sir | Physics Anupam Sir | Chemistry Nishant Sir | Maths

1:30 - 3:00 PM 3:00 - 4:30 PM 4:30 - 6:00 PM
livedaily.me/jee
Telegram Channel
 Unacademy
Subscription

LIVE Class Environment Performance Analysis

LIVE Polls & Leaderboard Weekly Test Series
LIVE Doubt Solving DPPs & Quizzes
LIVE Interaction
 India’s BEST Educators Unacademy Subscription

If you want to be the BEST

“Learn” from the BEST
Step 1 Step 2

INSTALL
 11th / 9, 10

12th / Drop

ANUPAMLIVE
 11th / 9, 10

12th / Drop

ANUPAMLIVE
ANUPAMLIVE
Thank You
@anupamguptachem