Lecture VII

Nitroaromatic compounds
 I- Preparation of Nitro compounds :
1-Direct nitration (conc. HNO3 - conc. H2SO4)
2- Nitration with acetyl nitrate (CH3COONO2)
 Formed from reacting conc. HNO3 with Ac2O (CH3CO)2O):
 For activated rings, e.g. anisole & acetanilide.
 Gives o-isomer mainly.
 (anisole –OCH3 & acetanilide –NHCOR are moderately activating )
 3- Nitration of Aromatic Amines:
o Aromatic amines highly activated so direct nitration
resulted in decomposition of the ring so nitration of
anilines required modification.
a- Nitration in presence of excess acid:
o Aniline will be converted into amine salt (deactivating
group) & so nitration will occur in m-position.
(aniline to m-nitroaniline)

- NH2 NH3 HSO4 NH3 HSO4 NH2

H2SO4 NaOH
HNO3

NO2 NO2
b- Protection of amino group via acetylation:
The acetamido group is milder activating group than
amino.(aniline to p-nitroaniline)
NH2 NHCOCH3 NHCOCH3 NH2

Ac2O H2 O / H
HNO3 /AcOH

Acetanilide NO2
NO2
 We can synthesize o-nitroaniline, however, through the
reactions that follow:(convert aniline to o-nitroaniline)

NH2 NHCOCH3 NHCOCH3 NH2

NO2 NO2

Ac2O HNO3 /Ac2O H2O / H

(acetyl nitrate)

We can synthesize o-nitroaniline, however, through the reactions that

follow:
We can synthesize o-nitroaniline, however, through the reactions
that follow:(Convert acetanilide to o-nitroaniline)

 A sulfonic acid group can be used as a “blocking group.”

 We can remove the sulfonic acid group by desulfonation at a later stage.
 In this example, the reagent used for desulfonation (dilute H2SO4) also
conveniently removes the acetyl group that we employed to “protect”
the benzene ring from oxidation by nitric acid.
4- Preparation of o- & p-dinitrobenzene:
From oxidation of o- & p-nitroaniline in two steps.

NH2 NO NO2

NO2 NO2 NO2

(NH4)2S2O8 / conc. H2SO4 HNO3/ H2O2

Caro's acid

Caro's acid (peroxysulfuric acid) HO–O–S(O)2–OH

Ammonium persulfate (NH4)2S2O8

II-Chemical Reaction of Aromatic Nitro compounds
1-Electrophilic substitution reactions:
NO2 is deactivating , m-directing group

Friedel-Crafts reaction will not take place on a ring that

bears an NO2 group (or any meta director).
2- Nucleophilic Substitution Reactions (SN2 aromatic)
Nitrobenzene is more activated towards SN2 reactions than benzene
due to:
1. NO2 group has strong –M effect so ↓ electron density in the ring
especially in o- & p- positions.
2. NO2 group stabilizes the intermediate carbanion especially that formed
from o- & p- attacks.
● Presence of good leaving group ( Cl , NO2 ) in o- & p- positions to the
nitro group facilitate the SN2 reactions.
NO2
NO2
OH
NO2

NO2 NaOH / HCl

SNa S
Na 2 CH
3 ON NO2
a
NH3
NO2 OCH3

NH2
3- Reduction of Nitro compounds:
a- In acidic medium:

NO2 NH2

Sn / HCl

aniline
If case of nitrobenzaldyhde SnCl2 used instead of Sn
NH2
NO2

SnCl2 / HCl

CHO
CHO
m-nitrobenzaldehyde
Catalytic reduction can be used in case presence of hydrolysable group
(Capable of undergoing hydrolysis)

NO2 NH2

H2 / Pt

NHCOCH3 NHCOCH3
p-nitroacetanilide
Complete the following equations: