Applies the mechanisms and

applications of amination,
Applications of amination
reactions with other
aromatic compounds
Dr. Muhammad Tahir Saddique
Assistant Professor (Chemistry)
Department of Applied Sciences
 Contents
Methods of Preparation
Physical Properties
Basicity of Amines
Chemical Properties
 Methods of Preparation
(1) Reduction of Nitro Compounds:
This is most convenient and widely used method for
preparing aromatic amines. The reduction is carried with (a)
H2 in presence of Ni, Pt or Pd as a catalyst (b) Fe or Sn and
HCl (c) Lithium aluminum hydride. Forexample
H2 / NiorSn/ HCl


C6H5NO2 H C

2 / NiorSn/ HCl

6 H
5 NH2
NO2C6H4-CH3 NH2C6H4-CH3
LiAlH
4 

m-Nitrotoluene m-Toluidine
Selective reduction with ammonium sulphide is used to
 Methods of Preparation
prepare an amino compound such as m-nitroaniline from m-
dinitrobenzene when only one -NO2 group need be reduced.
NO2-C6H4-NO2 NH  -C H -NO
LiAlH 4

2 6 4 2

m-Dinitrobenzene m-Nitroaniline
(2) Ammonolysis of Aryl Chlorides: Aniline is prepared by
trating chlorobenzene with ammonia in presence of cpper
salts at high temperature and pressure.
o
CuCl
 2 , 210 C

C6H5-Cl + 2NH3 C6H5-NH2 + NH4Cl
 Methods of Preparation
This method is useful and canbe carried conveniently under
ordinary condition if a strongly electron-withdrawing group
such as -NO2 is present ortho or para to -Cl.
2,4-Dinitrobenzene +2NH3 2,4-Dinitroaniline + NH4Cl
o
50
C


(3) Hofmann Rearrangement. When treated with bromine

or chlorine in alkaline solution, an aryl amide undergoes
Hofmann rearrangement to yield a primary aromatic amine.
NaOBr

Ar—CONH2 Ar—NH2 + CO2
 Methods of Preparation
(4) Reduction of Azo Compounds. Azo compounds when
reduced with hydrogen in presence of nickel as catalyst, give
arylamines. H , Ni , H , Ni ,
2 
 2 

Ar—N=N—Ar Ar—NH—NH—Ar 2Ar—NH2
Physical Properties of Aromatic Amines. H 2 , Ni , 
 


(1) These are colourless liquids or solids, having

characteristic odour which is not pleasant. hey turn brown in
air owing to oxidation.
(2) On account of their high molecular weights
Physical Properties of Aromatic Amines
and intermolecular hydrogen bonding ability, their boiling points
are relatively high.
(3) They are sparingly soluble in water but dissolve in benzene
and other organic solvents.
(4) They are steam volatile and therefore can be purified by
steam distillation.
(5) They are highly toxic substances. Some of them are
carcinogens (cancer causing).
(6) In UV spectra aniline shows two absorption maxima at 230
and 280 mμ. In IR spectra, primary aromatic amines give bands
Chemical Properties of Aromatic Amines
cm-1 region.
Aromatic amines undergo all the usual reactions of aliphatic
amines. They differ (a) they reaction with nitrous acid (b)
rearrangement reaction (c) oxidations
(d) electrophilic aromatic substitution reactions of the
benzene ring.
(1) Salt Formation. Being basic they form crystalline salts
with strong mineral acids such as HCl or H2SO4.
ArNH2 + HCl → ArN+H3Cl-
Arylammonium Chloride
Chemical Properties of Aromatic Amines
(2) Alkylation. They react with alkyl halide 2o and 3o amines.
The amines so formed react with HX to form salts.These salts
can be treated with aq. NaOH to give free 2o or 3o amines.
R R
‫׀ ׀‬ NaOH
   NaOH
ArNH + RX → Ar—NH + HX → Ar—NH +X-  

2 2

R
‫׀‬
Ar—NH
Chemical Properties of Aromatic Amines
R R R
‫׀׀‬ ‫׀‬
Ar —NH +RX → Ar—N + HX → Ar—NH+X- NaOH


‫׀ ׀‬
R R
R
‫׀‬
Ar—N
‫׀‬
R
 Chemical Properties of Aromatic Amines
(3) Acylation. With acid halides and anhydrides, they form N-
Arylamides.
ArNH2 + CH3COCl → ArNH—CO—CH3 + HCl
ArNH2 + (CH3CO)2Cl →ArNH—CO—CH3+ H3COOH
(4) Reaction with Aldehydes. They react with aldehydes to form
imines
ArNH2 + RCHO → ArN=CH—R + H2O
(5) Carbylamine Reaction. Primary amines react with ethanolic
potassium hydroxide and chloroform
to form carbylamines or isonitriles which have a disagreeble odour.
Chemical Properties of Aromatic Amines
ArNH2 + CHCl3 + 3KOH → ArNC + 3KCl + 3H2O
Carbylamine
(6) Reaction with Nitrous Acid. (a) 1o aromatic amines
undergo diazotization to give diazonium salts.
HCl,05o
ArNH2 + HONO  ArN2 Cl + 2H2O+ - o
 HCl
 ,05


Aliphatic 1o amines do not form diazonium salts.

(b) 2o amines undergo N-nitrosation.
Chemical Properties of Aromatic Amines
H N=O
‫׀ ׀‬
HCl
Ar—N—R + HONO Ar—N—R

 + H2O
Nitrosoamine
(c) 3o amines undergo C-nitrosation
HCl

C6H5NR2 + HONO NR2— C6H4 —N=O + H2O
(7) Oxidation. Aromatic amines are readily oxidised to give products
depending upon consitions. For example aniline on oxidation with
potassium dichromate and sulphuric acid gives p-benzoquinone.
Chemical Properties of Aromatic Amines
C6H5NH2 O = C6H4 = O

K
2 Cr2 O7 . H
 

Pertrifluoroacetic acid (CF3CO3H) oxidises the -NH2 group to -NO2

group.
CF
3CO
3H
 
Ar —NH2 Ar —NO2
(8) Hofmann-Martius Rearrangement. with N, N -dialkylanilines
in strong acid media at 400 oC, intermolecular migration occurs.
CH3 H H
‫׀‬ ‫׀‬ 300

o
C

‫׀‬ NaOH


H3C—N•HCl H3C—N•HCl→ H—N•HCl

‫׀‬ ‫׀‬ ‫׀‬
Chemical Properties of Aromatic Amines
2,4-Dimethylaniline
(9) Electrophi;ic Aromatic Substitution. Aromatic amines are
highly activated towards substitution in the ring by electrophilic
reagents. The -NH2 group directs the new entrant to the ortho
and para positions.
For axample
Acylation.
Aniline reacts with acid chloride (or acid anhydride) to form
corresponding amides called anilides.
Chemical Properties of Aromatic Amines
O O
ǁ ǁ
C6H5NH2 + CH3―C―Cl → C6H5NH―C―CH3 + HCl
O O O
ǁ ǁ ǁ
C6H5NH2+CH3―C―O―C―CH3→C6H5NH―C―CH3 +

O
ǁ
CH3―C―OH
Chemical Properties of Aromatic Amines
O O
ǁ ǁ
C6H5NH2 +C6H5―C―Cl → C6H5NH―C―C6H5 +
HCl Benzanilide
Benzylamine.
O O
ǁ ǁ
C6H5CH2NH2+C6H5―C―Cl→
C6H5CH2NH―C―CH3 + HCl N-Benzylacetamide
Chemical Properties of Aromatic Amines
Halogenation. Aniline halogenation with bromine or chlorine
is extremely rapid. When bromine water or chlorine water is
added to aniline at room temperature a white precipitate of
2,4,6-tribromo or 2,4,6-trichloaniline is obtained immediately.
C6H5―NH2 + 3 Br2 → 2,4,6-tribromoaniline + 3HBr
Sulphonation. On heating with fuming sulphuric acid, aniline
is sulphonated to form sulphanilic acid (p-
aminobenzenesulphonic acid)
C6H5NH2+H2SO4 (fuming) p-aminobenzenesulphonic acid
o
180
C 
 Basicity of Amines
Basicity of a compound is a measure of a compound's ability
to accept a proton (H+). Aniline accepts a proton as follows:
C6H5N..H2 + H+ → C6H5N+H3
Aniline Anilinium ion
In aliphatic amines, the non-bonding electron pair of N atom
is localized and is fully available for coordination with a
proton. On the other hand, in aromatic amines, the
nonbonding electron pair is delecalized into the benzene ring
by resonance.
 Basicity of Amines
The nonbonding electron pair in the hybrid being
dispersed over the benzene ring as also the N atom, is less
available for protonation. Hence aromatic amines are less
basic than aliphatic amines which show no resonance.
o-Nitroaniline is more weakly baic than aniline because
the electronwithdrawing effect on the ring lowers the
electron density on the N atom, making the electron pair
even less available for protonation.
Diphenylamine is a weaker base than aniline. It contains
two negative phenyl groups instead of one.