1.

Preparation of Diazonium salt

2. Coupling Reaction with
Phenols

Student handout

Dotsha J. Raheem
College of Science/ Department of
Chemistry
University of Salahadin
May 2010

1
Diazonium salt formation (diazotization reaction)

NaNO2 / HCl
NH2 N N Cl
o
0-5 C

aniline Diazonium salt

or any other primary
aromatic amine

Mechanism of the Reaction

1. Formation of the nitrosonium ion

NaNO2 + HCl NaCl + HNO2

H H
H O N O + H H O N O H O + N O N O
Nitrosonium ion

2. Nitrosation of the amine

H
H2O
NH2 + N O N N O N N O + H3O
H H
N-nitrosoamine

3. Tautomerism

Tautomerism
N N O N N OH
H

N-nitrosoamine diazenol

2
4. Formation of the diazonium salt

H3O H
N N OH N N OH

-H2O
N N N N N N

N N N N

The Diazonium Salt: N N Cl

Diazotization reaction of different amines

Diazonium salts obtained from aliphatic amines are less stable than
aromatic diazonium salts, and they undergo decomposition to the
corresponding carbonium ion with the liberation of N2 gas.

RCH2-NH2 NaNO2
RCH2-N N Cl RCH2 + N2
primary aliphatic HCl unstable diazonium carbonium ion
amine salt

NaNO2
NH2 N N Cl
HCl
primary aromatic diazonium salt
amine

Secondary amines both aliphatic and aromatic, form N-nitrosoamines upon reaction with HNO2

(R) NaNO2 (R)

Ar NH Ar N N O
R HCl
R
secondary amines N-nitrosoamine

3
 R NaNO2 R
N O N N
R HCl R
tertiary aromatic p-nitrosoamine
amine

NaNO2 no reaction
R 3N
HCl
tertiary aliphatic
amine

Reactions of diazonium compounds:

1. Coupling

2. Displacement

N N X

X = -OH, -NH2, -OR

Coupling

N N X CuX
X + N2
X= Cl or Br
Displacement KI
I + N2

HBF4 + N2
F

CuCN CN + N2

H2O
OH + N2
heat
H3PO4
H + N2

4
Diazonium salts
A class of organic compounds with the general formula ArN +≡NX-, where
Ar is an aryl group and X is ananion; made by the action of nitrous acid on
aromatic amines, and used in dyeing and as useful intermediates in organic
synthesis.

Q/ Aromatic diazonium salts are more stable than the aliphatic ones, why?

A/ That is because in aromatic diazonium salts the azo group is stabilized by

becoming a part of a conjugated system, an effect which is absent in the
aliphatic ones.

Importance of Diazotization Reaction

Aryldiazonium salts are very important class of compounds because they

can be transformed into a large number of other functional groups.

1. Used in the preparation of organic compounds that can’t be prepared

otherwise [e.g. 3,5-dibromotoluene from toluene].

2. Used in the preparation of dyes and indicators.

Azo Dyes

OH
HNO2 HO
NH2 N NX N N
10% NaOH

azo dye

The coupling reaction between diazonium salts and a phenol (and some
other activated arenes) will result in colored compounds called ”azo dyes”.
The color of these compounds is due to the high levels of conjugation which
extends through the –N=N- group to the aryl system.

The basic structure (Ar-N=N-Ar) may be substituted with different

functional groups (e.g. –NO2, -SO3Na, -NH2, -CH3, -OH, -OCH3) that affect
the color of the dye due to their conjugation with the azo system.

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Mechanism of the reaction (coupling with phenols)

O H
Na OH O Na O
H2O +

O
O
N N + N N
Cl H
2-naphthol
Cl

O HO
-H +H
N N N N

red azo dye

1-phenylazo-2-naphthol

Examples on azo dyes:

Some common dyes synthesized by diazo coupling reaction:

H3C
N N O2N N
H3C
N SO3Na N OH

COOH
Methyl orange Alizarin yellow R
red in acid - yellow in base

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 NH2 H2N
N N
N N
NaO3S SO3Na

Congo red

HO
NaO3S N O2N N
N OH N

Orange 1
4-[(p-benezenesulfonyl)azo]-1-naphthol Para red

Try to fill this table with different azo dye combinations

Aroma
tic
amines

Coupling
agents

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Procedure:

Preparation of the diazonium salt

1. Place 1 g of the aniline, 5 ml of water and 2.5 ml of conc. HCl in a
flask and shake. Keep the flask in ice bath.

2. Dissolve 1g NaNO2 in 5 ml of water and put it in ice too. Add this

solution dropwise to the solution of aniline. Keeping the
temperature between 0-5 oC.

Coupling reaction
1. Dissolve 1 g 2-naphthol in 10 ml 10% NaOH keep this solution
also in ice.

2. Now add the diazonium solution slowly to the cold solution of 2-

maphthol: a brilliant red dye is produced.

3. Filter on a buchner funnel.