Anilines are Prepared by

Reduction of the Nitro Group

Anilines are commonly formed by the reduction of the nitro group. The reaction
is accomplished by the reagents shown below. Given that the nitro group is
easily introduced via electrophilic aromatic substitution, the synthetic sequence:
Nitration → reduction → diazotization → substitution
is a powerful route to many substituted arenes.

NO2 NH2

Sn, HCl

NO2 NH2

Pd/C, H2
Substitution Reactions via
Arenediazonium Salts
 Mechanism of Diazotization
[pt] H [pt] H H
O N O H O N O O N O [Eβ] or
sodium nitrous H –H2O [DN]
–H acid –H
nitrite

H
NH2
N O N O
[pt] N N O
nitrosonium ion OR
H [AN] or [AdN] nitrosyl cation
–H H
[pt]
[pt] H H H
–H
N N O N N O N N O
H –H H H [pt]
–H H
H
–H2O
N N N N O
[Eβ] H
 Mechanistic Considerations:
Substitution of Arenediazonium Ions
In these reactions the leaving group leaves before the Nu adds
(compare to electrophilic aromatic substitution mechanism)

H H H
N
H N H H Nu
– N N Nu
[DN] [AN]
H H H H H H
H H H
aryl cation

Although conveniently thought of as proceeding via nucleophilic capture

of the aryl cation via an [AN] step, evidence suggests that many of these
reactions may involve radical chain mechanisms (for example, see: J. Am.
Chem. Soc. 72, 1950, 3013).