Lecture No.

38
Electrophilic Aromatic Substitution
At the end of thisReactions
lecture, student will be able
to
Discuss the concept of aromaticity and Huckels
rule
Differentiate aromatic and nonaromatic
compounds
Explain the general mechanism of electrophilic
aromatic substitution reaction
List out examples for EAS reactions

1
Faculty of Pharmacy

M. S. Ramaiah

Structure of Benzene
It contains a six-membered ring and three additional
degrees of unsaturation
It is planar
All C C bond lengths are equal
Resonance
Benzene is conjugated

2
Faculty of Pharmacy

M. S. Ramaiah

Structure of Benzene Contd

Benzenes six -electrons make it electron rich and so

it readily reacts with electrophiles
Overlap of six adjacent p orbitals creates two rings of
electron density
Delocalisation of electrons
Clouds of electrons above and below the plane of
benzene ring
3
Faculty of Pharmacy

M. S. Ramaiah

Nomenclature of Benzene Derivatives

Monosubstituted Benzenes

4
Faculty of Pharmacy

M. S. Ramaiah

Nomenclature of Benzene Derivatives

Disubstituted benzenes

5
Faculty of Pharmacy

M. S. Ramaiah

Nomenclature of Benzene Derivatives

Arrange the substituents in alphabetical order

6
Faculty of Pharmacy

M. S. Ramaiah

Nomenclature of Benzene Derivatives

Polysubstituted benzenes

7
Faculty of Pharmacy

M. S. Ramaiah

Nomenclature of Benzene Derivatives

Phenyl and benzyl group

8
Faculty of Pharmacy

M. S. Ramaiah

Criteria for Aromaticity

A molecule must have uninterrupted cyclic cloud of electrons
For the cloud to be cyclic, the molecule must be cyclic
For the cloud to be uninterrupted, every atom in the ring must have a porbital
For the cloud to form, each p orbital must overlap with the p orbitals on
either side of it
Therefore, the molecule must be planar
Odd number of pairs of electrons
Huckels rule or 4n + 2 rule states that for a planar, cyclic compound to
be aromatic its uninterrupted cloud must contain (4n+2) electrons,
where n is any whole number (0,1,2,)

9
Faculty of Pharmacy

M. S. Ramaiah

Criteria for Aromaticity Contd

Example 1
Benzene 3 pairs of electrons aromatic
Cyclobutadiene & cyclooctatetraene non aromatic

10
Faculty of Pharmacy

M. S. Ramaiah

Criteria for Aromaticity Contd

Example 2

Cyclopropene non aromatic

Cyclopropenyl cation aromatic
Cyclopropenyl anion non aromatic

11
Faculty of Pharmacy

M. S. Ramaiah

Criteria for Aromaticity Contd

Example 3
Naphthalene 5 pairs of electrons aromatic
Phenanthrene 7 pairs of electrons non aromatic

12
Faculty of Pharmacy

M. S. Ramaiah

Electrophilic Aromatic Substitution

Reactions

13
Faculty of Pharmacy

M. S. Ramaiah

Electrophilic Aromatic Substitution

Reactions Contd
Benzene - does not undergo addition reactions
like unsaturated hydrocarbons
Typical reactions of benzene - substitution

14
Faculty of Pharmacy

M. S. Ramaiah

Electrophilic Aromatic Substitution

Reactions Contd

15
Faculty of Pharmacy

M. S. Ramaiah

Electrophilic Aromatic Substitution

Reactions Contd

Mechanism
Step 1
Addition of electrophile to form a carbocation
Rate determining step
Step 2
Loss of a proton to form the substituted product

16
Faculty of Pharmacy

M. S. Ramaiah

Electrophilic Aromatic Substitution

Reactions Contd

How to draw resonance structures for carbocation?

17
Faculty of Pharmacy

M. S. Ramaiah

Summary
Benzene planar and resonance stabilized
Huckels rule states that for a planar, cyclic compound
to be aromatic its uninterrupted cloud must contain
(4n+2) electrons, where n is any whole number
(0,1,2,)
Benzene
undergoes
electrophilic
aromatic
substitution reactions
Sigma complex is formed which is resonance
stabilized
Nitration, sulphonation, halogenation, Friedel Crafts
alkylation and Friedel Crafts acylation of benzene are
electrophilic substitution reactions
18
Faculty of Pharmacy

M. S. Ramaiah