ANILINE

BY:
DR. M. K.Gupta
CAREER POINT SCHOOL OF PHARMACY
CAREER POINT UNIVERSITY, KOTA
 INDEX:

• DESCRIPTION
• ORBITAL STRUCTURE OF ANILINE
• METHODS OF PREPARATION OF ANILINE
• BASICITY OF ANILINE
• EFFECT OF SUBSTITUENTS ON THE BASICITY OF ANILINE
• CHEMICAL REACTIONS OF ANILINE
• IDENTIFICATION TESTS FOR ANILINE
• PHARMACEUTICAL IMPORTANCE OF ANILINE
 DESCRIPTION:

• Aniline is the organic compound in the class of group coming in organic

chemistry which is also called as aminobenzene or phenylamine. This
compound is said to be toxic in nature and also known to be one of the
classes of aromatic amines. It is used in a wide variety of industrial and
known to possess all the characteristics of an aromatic compound.
Aniline has the formula C6H5NH2 wherein the amino group is to be
attached to the benzene ring.
NH2
 Orbital structure:

• Aniline is a slightly pyramidalized molecule, with hybridization of the nitrogen

somewhere between sp3 and sp2. The amine is flatter than an aliphatic amine, owing to
conjugation of the lone pair with the aryl substituent. Thus, the experimental geometry
reflects a balance between the stabilization of lone pairs in orbitals with higher s character
and better stabilization via conjugation with the aryl ring for an orbital of pure p character.
The pyramidalization angle between the C–N bond and the bisector of the H–N–H angle is
142.5°.(For comparison, in more strongly pyramidal methylamine, this value is ~125°,
while a planar nitrogen like that of formamide has an angle of 180°.) The C−N distance is
correspondingly shorter. In aniline, the C−N and C−C distances are close to 1.39 Å,
indicating the π-bonding between N and C. Consistent with these factors, substituted
anilines with electron donating groups are more pyramidalized, while those with electron
withdrawing groups are more planar.
METHODS OF PREPARATION:

1. From reduction of Nitrobenzene:

NO2 NH2

Sn / HCl

/ 2500C

2. From Halobenzene:
Cl NH2

NaNH2

/ 2500C
METHODS OF PREPARATION:

3. From reduction of Nitriles:

CN NH2

2H2 / LiAlH4

ether

4. Hoffmann Bromamide reaction:

O

C NH2 NH2

Br2 / NaOH
 BASICITY OF ANILINE:

• In aniline or other aromatic amines, the lone pair present on nitrogen

atom is delocalized with benzene ring by resonance . Due to the lone
pair present on nitrogen it can easily accept protons & is basic in nature.
EFFECT OF SUBSTITUENTS ON
THE BASICITY OF ANILINE:

1. Any group   present on benzene ring  that has electron withdrawing effect
(– NO2, – CN, – SO3H, – COOH – Cl, C6H5, etc.) decreases basicity of
aniline(Nitroaniline is less basic than aniline as nitro group is electron
withdrawing group (– I group) and aniline is more basic than diphenyl
amine) .(conjugation decreases basic nature)
2. An electron repelling effect (– NH2, – OR, R –, etc.) increases basicity of
aniline. Toluidine is more basic than aniline as – CH3 group is electron
repelling group (+ I group).

3. Aniline is less basic than ammonia & aliphatic amines. This is due to the
phenyl group which exerts –I (inductive) effect, i.e., it withdraws
electrons. This results to the lower availability of electrons on nitrogen
for protonation.
 CHEMICAL REACTONS:

1. REACTIONS DUE TO BENZENE RING:

a) Electrophilic Substitution:
i) Halogenation:
NH2 NH2

Br Br
3Br2
+ 3HBr

Br

2, 4, 6 - tribromoaniline

ii) Sulfonation:
NH2
NH2

H2SO4

/ 1800C

SO3H
p - aminosulf onic acid
Sulf anilic acid
 CHEMICAL REACTIONS:

iii) Nitration:

+
NH3ONO2- +
NH3ONO2-
NH2

conc.HNO3 conc.HNO3

conc.H2SO4 conc.H2SO4
NO2

NaOH

NH2

NO2

m - nitroaniline
 CHEMICAL REACTIONS:

iv) Friedel Crafts Acylation:

NH2 NH2
NH2

OCOCH3

CH3COCl +
AlCl3

o - aminoacetophenone
COCH3

p - aminoacetophenone

v) Friedel Crafts Alkylation:

NH2 NH2
NH2

CH3

CH3Cl +
AlCl3

o - toludine
CH3

p - toludine
 CHEMICAL REACTIONS:

2. REACTIONS DUE TO “-NH2” GROUP:

a) Formation of salts:
+
NH3.Cl-
NH2

HCl

Aniline Hydrochloride
b) Formation of 20 & 30 amines:
H3C CH3
NHCH3 N
NH2

CH3Cl CH3Cl

-HCl -HCl
N , N - dimethylaniline
N- methylaniline
20 amine 30 amine
 CHEMICAL REACTIONS:

c) Formation of N – substituted amides:

NHCOCH3
NH2

CH3COCl

-HCl
Acetanilide

-HCl COCl

NH C

Benzanilide
 CHEMICAL REACTIONS:

d) Reaction with nitrous acid (Diazotization reaction):

Mechanism:
 CHEMICAL REACTIONS:

e) Formation of Schiff’s Base:

N CHCH3
NH2
O

CH3 C H

NaOH
Schif f s Base
f) Carbylamine reaction:

NC
NH2

CHCl3

KOH
Phenyl isocyanide
(Carbylamine)
 CHEMICAL REACTIONS:

3. MISCELLANEOUS REACTIONS:
a) Oxidation:
i) In the presence of manganese dioxide:
NHOH NO2
NH2

[O] [O]

MnO2 MnO2

Nitrosobenzene Nitrobenzene
ii) In the presence of potassium dichromate & conc.sulphuric acid:

NH2 O

[O]

K2Cr2O7 / H2SO4

O
p - benzoquinone
 CHEMICAL REACTIONS:

b) Reduction:
NH2 NH2

3H2 / Ni

250 atm / 4000C

cyclohexylamine

c) Hofmann Martius Rearrangement: Occurs only with disubstituted aniline:

H3C CH3
N NH2

CH3

4000C

CH3

2, 4 - dimethylaniline
 CHEMICAL REACTIONS:

d) Formation of Phenazine (Wohl – Aue Reaction):

H2N N

+
-2H2O
NO2 N

Phenazine
e) Coupling (Azo dye formation):
 IDENTIFICATION TESTS:

1. SOLUBILITY TEST: Aniline which is basic in nature dissolve in mineral acids

like hydrochloric acid to form ppt. of chloride salts.
2. LITMUS TEST: Aniline is basic in nature. So it turns red litmus paper blue.
3. CARBYLAMINE TEST: This test is also called isocyanide test, because when
aniline is treated with chloroform in the presence of alkali, phenylisocyanide is
formed which is detected by its unpleasant fishy odor.
4. NITROUS ACID TEST: Aniline reacts with nitrous acid forms a diazonium
salt and at higher temperatures the formed diazonium compounds undergoes
decomposition.
5. AZODYE TEST: Aniline forms a diazonium salt when treated with HNO2.
These diazo compounds couple with phenols like β-naphthol to form an orange
azo dye which is insoluble in water.
PHARMACEUTICAL IMPORTANCE:

1. It is used to manufacture Para amino phenol, which is an active

raw material of Paracetamol.

2. It is used to manufacture sulfanilic acid, which is an active

raw material required for sulfonamide synthesis.

3. Azo dyes produced from aniline are used to color clothing.

4. It is used in the preparation of acetanilide which is the precursor for the

synthesis of a large variety of antipyretic drugs.

5. Various aniline derivatives are used as antifungal drugs.

THANK YOU