Reactions of Arenes:

Electrophilic Aromatic Substitution

d+

+E

d
Y

E
+H

Representative Electrophilic Aromatic

Substitution Reactions of Benzene
H

d+

+E

d
Y

E
+H

d+

+E

+H

Electrophilic aromatic substitutions include:

Nitration
Sulfonation
Halogenation
Friedel-Crafts Alkylation
Friedel-Crafts Acylation

Nitration of Benzene

H
+ HONO2

H2SO4

NO2
+ H2O
Nitrobenzene
(95%)

Sulfonation of Benzene

H
heat
+ HOSO2OH

SO2OH
+ H2O

Benzenesulfonic acid
(100%)

Halogenation of Benzene

H
+ Br2

FeBr3

Br2
+ HBr
Bromobenzene
(65-75%)

Friedel-Crafts Alkylation of Benzene

H
+ (CH3)3CCl

AlCl3

C(CH3)3
+ HCl

tert-Butylbenzene
(60%)

Friedel-Crafts Acylation of Benzene

O

H
AlCl3
+ CH3CH2CCl

CCH2CH3
+ HCl

1-Phenyl-1-propanone
(88%)

Mechanistic Principles
of
Electrophilic Aromatic Substitution

Step 1: attack of electrophile

on p-electron system of aromatic ring

E+
H

H
H

H E

+
H

highly endothermic
carbocation is allylic, but not aromatic

H
H

Step 2: loss of a proton from the carbocation

intermediate

E
H

H E

H+

+
H

highly exothermic
this step restores aromaticity of ring

H
H

The Br2-FeBr3 Complex

Br

Br

Lewis base

+ FeBr3
Lewis acid

Br

Br

FeBr3

Complex

The Br2-FeBr3 complex is more electrophilic

than Br2 alone.

Step 1: attack of Br2-FeBr3 complex

on p-electron system of aromatic ring

Br

H
H

+
Br

FeBr3

H Br

+
H

H
H

+ FeBr4

Step 2: loss of a proton from the carbocation

intermediate

Br
H

H Br

H+

+
H

H
H