By

Mr. Pise V. J.
Assistant Professor

Department of Pharmaceutical Chemistry

Arvind Gavali College of Pharmacy,

Jaitapur, Satara.
 Aromatic Amines
Learning Outcomes;
ü Define aromatic amines, explain types and assign
nomenclature to aromatic amines.
ü Explain preparation methods for aromatic
amines.
ü Explain physicochemical properties of aromatic
amines (like basicity).
ü Describe factors affecting on basicity of aromatic
amines.
ü Write and explain chemical reactions of aromatic
amines.
ü Describe diazonium salts and their applications.
 Aromatic Amines
These are the derivatives of aromatic hydrocarbons
in which a hydrogen of the benzene ring has been
replaced by an amino group, -NH2.

All such compounds in which an amino or

substituted amino group is bonded directly to an
aromatic ring are termed as aromatic amines.
 Aromatic Amines
Aromatic amines can be named as primary,
secondary and tertiary amines.

The derivatives of arenes in which –NH2 is

bonded to a side chain are to be regarded as aryl
substituted aliphatic amines.
 Aromatic Amines
Nomenclature:
NH2 NH2 NH2 NH2 HN CH3

CH3 OCH3

NO2
m-Toluidine m-Anisidine N-Methylaniline
Aniline p-Nitroaniline 3-Methylaniline 3-Methoxyaniline
 Methods of preparation of Aromatic Amines:

1. Reduction of Nitro Compounds: This is a very

convenient and widely used method. The
reduction is carried with Hydrogen in the
presence of Ni, Pd or Pt as catalyst or Sn or Fe
and HCl or Lithium aluminium hydride.
 Methods of preparation of Aromatic Amines:

CH3 CH3

NO2 NH2
Fe
HCl

NO2 NH2

2, 4-Dinitrotoluene 2, 4-Diaminotoluene
 Methods of preparation of Aromatic Amines:
2. Ammonolysis of Aryl Chlorides: Aniline is
prepared by treating chlorobenzene with
ammonia in the presence of copper salts at high
temperature and pressure.
 Methods of preparation of Aromatic Amines:
3. Hofmann Rearrangement: When aromatic
amides are treated with hypohalites or Bromine
and alkali yields aromatic amines.
O
N OB
NaOBr
Ar C NH2 Ar NH2 + CO2
(Br2+NaOH)
 Methods of preparation of Aromatic Amines:

4. Reduction of Azo compounds: Azo compounds

when reduced with hydrogen in presence of
nickel as catalyst, give aryl amines.
 Aromatic Amines
Resonance Structures
 Physicochemical Properties of Aromatic Amines
Basicity of aromatic amines:

Definition of base: A base is a substance that can

accept protons or donate a pair of valence
electrons to form a bond.
To compare the basicity of alkyl amines and aryl
amines, we must consider availability of the lone
pair of electrons on nitrogen.
Aromatic Amines
 Aromatic Amines
Aryl amines are less basic than alkyl amines
because the lone pair on N is delocalised.
Substituted anilines are more or less basic than
aniline depending on the nature of the
substituent.
 Aromatic Amines
Effect of substituent on Basicity:
1. Electron donating groups add electron density
on the benzene ring, making the aryl amine
more basic than aniline.
 Aromatic Amines
Effect of substituent on Basicity:
2. Electron withdrawing groups remove electron
density from benzene ring making the aryl
amines less basic than aniline.
 Aromatic Amines
Comparison in Basicity:
p-Nitro aniline is less basic than aniline:
 Aromatic Amines
Comparison in Basicity:
p-Nitro aniline is less basic than aniline: This is
because the –NO2, group is electron
withdrawing. It makes the –NH2 group of aniline.
Thus the lone pair of electrons on nitrogen in p-
Nitro aniline is less available for donation to H+.
It is therefore, less basic.
 Aromatic Amines
Comparison in Basicity:
p-Methyl aniline is more basic than aniline:
 Aromatic Amines
Comparison in Basicity:
p-Methyl aniline is more basic than aniline: This
is because the methyl group is electron-
donating. It makes the –NH2 group of p-methyl
aniline more electron rich than –NH2 group in of
aniline. Thus the lone pair of electrons on
nitrogen in –methyl aniline is more available for
donation to H+. it is therefore, more basic.
 Aromatic Amines
Comparison in Basicity:
Diphenylamine is less basic than aniline:

More available Less available

.. ..
NH2 NH
 Aromatic Amines
Comparison in Basicity:
Diphenylamine is less basic than aniline: The
lone pair of electrons on nitrogen in
diphenylamine can overlap with the π electron
system of both the aromatic rings. This cause
greater delocalization of the lone pair of
electrons than that occurs in aniline. Thus the
lone pair of electrons on nitrogen in
diphenylamine is less available for donation to
H+. It is therefore, less basic.
 Aromatic Amines
Chemical Reactions:
1. Salt Formation: Because of basic in nature
these forms the crystalline salts with strong
mineral acids like HCl or H2SO4.
 Aromatic Amines
Chemical Reactions:
2. Alkylation: Aromatic amines react with alkyl
halides to form sec and tert amines. The amines
so formed react with HX to form salts. These
salts can be treated with aq. NaOH to give free
sec and tert amines.
 Aromatic Amines
Chemical Reactions:
 Aromatic Amines
Chemical Reactions:
3. Acylation: With acid halides and anhydrides,
they form N-Aryl amides.
 Aromatic Amines
Chemical Reactions:
4. Reaction with Aldehydes: Aromatic amines
react with aldehydes to form imines (Schiff’s
base)
 Aromatic Amines
Chemical Reactions:
5. Carbylamine Reaction: Primary aromatic
amines react with ethanolic potassium hydroxide
and chloroform to form carbylamines or
isonitriles which have a disagreeable odor.
 Aromatic Amines
Chemical Reactions:
6. Reaction with Nitrous Acid:
a. Primary aromatic amines undergo
diazotization to give diazonium salts.
 Aromatic Amines
Chemical Reactions:
6. Reaction with Nitrous Acid:
b. Sec. Aromatic amines undergo N-nitrosation.
 Aromatic Amines
Chemical Reactions:
6. Reaction with Nitrous Acid:
c. Tert aromatic amines undergo C-nitrosation.
 Aromatic Amines
Chemical Reactions:
7. Oxidation: Aromatic Amines are readily
oxidised to give products depending on
conditions. For example. Aniline on oxidation
with potassium dichromate and sulphuric acid
gives p-benzoquinone.
 Aromatic Amines
Chemical Reactions:
Pertrifluoroacetic acid (CF3COOOH) oxidizes the
–NH2 group to –NO2 group.
 Aromatic Amines
Chemical Reactions:
8. Hofmann Martius Rearrangement: With N, N-
dialkylanilines in strong acid media at 400 0C,
intermolecular migration occurs to give 2,4-
dialkylaniline.
 Aromatic Amines
Chemical Reactions:
Electrophilic Aromatic substitution Reaction: Aromatic
amines are highly activated towards substitution in the
ring by electrophilic reagents. The –NH2 group directs
upcoming electrophile towards ortho and para positions.
For example, halogenation is so facile that all
unsubstituted ortho and para positions become
substituted.
 Aromatic Amines
Chemical Reactions:
 Aromatic Amines
Chemical Reactions:
 Aniline
Structure of Aniline:
 Aniline
Structure of Aniline:
 Aniline
Structure of Aniline:
Aromatic nature of Aniline: Aniline is aromatic
because it fulfils the following requirements for
aromaticity;
1. Cyclic.
2. Planar: all carbons of phenol ring are sp2
hybridized.
3. Conjugation.
4. Huckels rule: Follows number of pi electrons
as per the Huckels Rule 4n+2 (where n=1).
 Aniline
According to resonance theory, aniline is
considered to be hybrid of following resonance
structures.
 Aniline
Preparation Methods for Aniline:
Aniline is prepared in the laboratory by reducing
nitrobenzene with tin and concentrated
hydrochloric acid.
 Aniline
Preparation Methods for Aniline:
The acid salt is then treated with sodium
hydroxide solution to liberate aniline.
 Aniline Chemical Reactions:
Reactions of NH2 Group:
1. Reaction with strong acid to form salts: Aniline
is a weak base and forms salts with mineral
acids.
These salts are decomposed by alkalis to
regenerate aniline.
 Aniline Chemical Reactions:
Reactions of NH2 Group:
2. Reaction with alkyl halides; Alkylation: Aniline
reacts with alkyl halides to form sec amine. The
amine so formed reacts with HX to form salts.
The salt can be treated with aq. NaOH to
regenerate free sec amine.
Aniline Chemical Reactions:
 Aniline Chemical Reactions:
Reactions of NH2 Group:
3. Reaction with acid chlorides; Acetylation:
Aniline reacts with acid chlorides to form the
corresponding amides called as anilides.
H O H O
N H + Cl C CH3 N C CH3 + HCl

Acetanilide
Aniline Chemical Reactions:
 Aniline Chemical Reactions:
Reactions of NH2 Group:
4. Reaction with Benzenesulfonyl Chloride:
Aniline reacts with benzenesulfonyl chloride to
form N-phenylbenzenesulfonamide.
 Aniline Chemical Reactions:
Reactions of NH2 Group:
5. Reaction with Benzaldehyde: Aniline
condenses with benzaldehyde to give
benzylideneaniline (Schiff’s base).
 Aniline Chemical Reactions:
Reactions of NH2 Group:
6. Carbylamine Reaction: Aniline reacts with
chloroform and alcoholic KOH to give phenyl
isocyanide (phenylcarbylamine) which has an
offensive smell.
 Aniline Chemical Reactions:
Reactions of NH2 Group:
7. Reaction with nitrous acid: Aniline reacts with
nitrous acid in the presence of HCl at 0 to 5 0C to
give benzenediazonium chloride.
 Aniline Chemical Reactions:
Reactions of NH2 Group:
8. Coupling with diazonium salts: Aniline reacts
with benzenediazonium chloride to give p-
aminoazobenzene.
 Aniline Chemical Reactions:
Reactions of NH2 Group:
9. Oxidation: Aniline undergoes oxidation with
potassium dichromate to give p-benzoquinone.
 Aniline Chemical Reactions:
Reactions of Benzene Ring:
1. Halogenation: 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-trichloroaniline is
immediately formed.
 Aniline Chemical Reactions:
Reactions of Benzene Ring:
 Aniline Chemical Reactions:
Reactions of Benzene Ring:
2. Sulfonation: On heating with fuming sulphuric
acid, aniline is sulfonated to form mainly
sulfanilic acid (p-amino benzene sulfonic acid).
 Aniline Chemical Reactions:
Reactions of Benzene Ring:
3. Nitration: Aniline reacts with a mixture of
Conc. Nitric acid and sulphuric acid to give m-
nitroaniline.
 Aniline Chemical Reactions:
Reactions of Benzene Ring:
Why meta product?
Nitric acid is a proton acid. It reacts with the
amino group to form anilinium ion. C6H5NH3+.
Because of the positive charge, the NH3+ group is
meta directing.
 Aniline Chemical Reactions:
Reactions of Benzene Ring:
-p-Nitroaniline can be obtained by first
protecting the –NH2 group by acylation.
 Diazonium Salts
• This important class of compounds is characterized
by the presence of the functional group (diazonium
ion) directly bonded to an aryl group. The
arenediazonium ion forms salt with anions such as
Cl, Br, NO2, etc. These salts are called
arenediazonium salts.
 Diazonium Salts

• Preparation of Diazonium Salts:

Diazonium Salts
 Diazonium Salts
• Chemical Reactions of Diazonium Salts:

1. Reduction of Arenes: A diazonium salt is reduced by

hypo phosphorus acid (H3PO2) to give the respective
arene.
N2+Cl-

+ H3PO2 + H2O + N2 + H3PO3 + HCl

Benzenediazonium Benzene
chloride
 Diazonium Salts
• Chemical Reactions of Diazonium Salts:

2. Synthesis of Phenol: Aqueous solution of the

diazonium salt is acidified and heated to form
phenol.
 Diazonium Salts
• Chemical Reactions of Diazonium Salts:

3. Synthesis of Aryl chloride, Aryl bromide and aryl

nitriles: When a cold diazonium salt solution is
treated with cuprous chloride, cuprous bromide or
cuprous cyanide, the product is aryl chloride, aryl
bromide or aryl nitrile. These reactions are known as
Sandmeyer reactions.
 Diazonium Salts
• Chemical Reactions of Diazonium Salts:
 Diazonium Salts
• Chemical Reactions of Diazonium Salts:

4. Synthesis of Aryl fluoride: The diazonium salt is

treated with fluoroboric acid (HBF4) when diazonium
fluoroborate (C6H5N2+BF4-) precipitates. This is
isolated, dried and heated to give aryl fluorides. This
procedure of preparing fluorobenzene is called
Schiemann reaction.
 Diazonium Salts
• Chemical Reactions of Diazonium Salts:
 Diazonium Salts
• Chemical Reactions of Diazonium Salts:

5. Synthesis of Aryl iodides: When aqueous solution of

a diazonium salt is heated with excess of potassium
iodide, aryl iodide is obtained.
 Diazonium Salts
• Chemical Reactions of Diazonium Salts:

6. Synthesis of thiophenols: Reaction of diazonium salts

with potassium hydrosulfide yields thiophenols.
 Diazonium Salts
• Chemical Reactions of Diazonium Salts:

7. Synthesis of Nitro compounds: When a diazonium

salt is heated with NaNO2 in the presence of Cu
powder, aromatic nitro compounds are formed.
 Diazonium Salts
• Chemical Reactions of Diazonium Salts:

8. Arylation reaction: Arylation provides a convenient

preparation of unsymmetrical biaryls in which the
diazonium group is replaced by an aromatic ring.
Diazotization is carried out in the usual way. The
solution is made basic and the resulting solution is
treated with an arene at 0 to 5 0C. This reaction is
called as Gomberg-Bachmann reaction.
Diazonium Salts
 Diazonium Salts
• Chemical Reactions of Diazonium Salts:

9. Reduction to arylhydrazines: When reduced with

sodium bisulfite or stannous chloride, aryldiazonium
salts yield arylhydrazines.
 Diazonium Salts
• Chemical Reactions of Diazonium Salts:

10. Azo Coupling reaction: The second general reaction

of diazonium salts is coupling. When a diazonium salt
is treated with an aromatic compound that contains
a strong electron donor group, the two rings join
together to form an azo compound.
 Diazonium Salts
• Chemical Reactions of Diazonium Salts:
 Diazonium Salts
• Applications:
 Applications of Diazonium Salts:
1. Synthesis of p-Nitrobenzoic acid from benzoic
acid:
COOH
COOH

HNO3
H2SO4
NHCOCH3
Benzoic Acid
HNO3
H2SO4
COOH

COOH COOH

H3PO2
H2O
NaOH
NH2 NHCOCH3
NO2

NO2 NO2
p-Nitrobenzoic Acid
 Applications of Diazonium Salts:
2. Synthesis of 3, 5-dichlorophenol from benzene:

OH
N2+Cl-

H2O
Heat
Cl Cl
Cl Cl
3, 5-dichlorophenol
 Applications of Diazonium Salts:
3. Synthesis of 1, 3, 5-tribromobenzene from
benzene: NH2

Br Br

Br
NaNO2
HCl

N2+Cl-

Br Br

H3PO2

Br
 Applications of Diazonium Salts:
4. Synthesis of m-cyanobenzoic acid from toluene:
 Applications of Diazonium Salts:
5. Synthesis of m-hydroxy benzoic acid from
toluene: COOH

CH3

Na2Cr2O7
[O] NO2

Sn/HCl
Toluene
NaOH

COOH

NaNO2
HCl
NH2