CHE232: LECTURE-10

Section 2: Lecture-3

Mechanism of Electrophilic Aromatic Substitution Reactions

The mechanism of electrophilic aromatic substitution reactions can be
described in three steps.

1. The first step is the generation of electrophile (E+) from the appropriate
reagent.
2. The second step is the reaction between benzene and electrophile forming
benzenonium ion. Benzenonium ion is a carbocation, stabilized by
resonance. The second step of the mechanism is also the slowest step of
the reaction and hence the rate-determining step. After the reaction with
electrophile, see the ring is no more aromatic.
3. The third and final step is aromatization of the ring by elimination of the
proton and regeneration of the catalyst, if used.
 After having an idea about the steps involved in electrophilic substitution of
benzene ring, let’s see the mechanisms of some substitution reactions described
above.

Mechanism of chlorination

Mechanism of nitration

Mechanism of sulfonation
O
O + O
H O S OH
O S O O O S OH

HO3S H SO3H
SO3H -H+
slow fast

Mechanism of Friedel-Crafts alkylation

Mechanism of Friedel-Crafts acylation

Problem: When benzene reacts with propene in the presence of an acid catalyst,
the product is isopropylbenzene instead of n-propyl benzene. Explain.

Thinking: Two carbocations are possible from the reaction of propene with acid.
The one with more hydrogen atoms is less stable. The reaction proceeds through
more stable electrophile (carbocation).

H H+ H2 H
C CH2 C CH2 C
H3C H3C H3C CH3
less stable more stable