You are on page 1of 21

1

AZO DYES
Contain at least one azo group (-N=N-) group. About 50% of all commercial dyes. Having been studied more than any other class of dyes. May contain contain two (disazo), three (trisazo), or, more rarely, four (tetrakisazo) or more (polyazo) azo groups. azo group is attached to two groups, of which at least one, but more usually both are aromatic. Exist in the trans form with angle of 120o In monoazo dyes A= e accepting, E= e donating Carbocyclic azo dyes, Heterocyclic azo dyes

General Synthesis
followed by coupling of the resultant diazonium salt with an electron-rich nucleophile. Primary aromatic amine is treated with nitrous acid, (generated in situ with hydrochloric acid and sodium nitrite). The nitrous acid nitrosates the amine to generate the N-nitroso compound, which tautomerises to the diazo hydroxide
NaNO2 C6H5NH2 Aniline
+ +

Azo dyes are made by diazotization of a primary aromatic amine

HCl HCl 0-5oC

HNO2 C6H5N2Cl
+
_

NaCl
+

NaNO2

NaCl

2H2O

Benzenediazonium chloride

Nitrous acid (NaNO2/HCl) produces nitrosonium ion (N=O+)


H H O N O Nitrous acid H O
+

N O

H2O

[N=O]

Nitrosonium ion
+

Nitrosonium ion combines with aniline to form nitrosoaniline.


C6H5 NH2 [N=O] H C6H5
+

N N O H C6H5 N N OH
+

Nitrosoaniline undergoes rearrangement


C6H5

H H
+

N N O H

Dehydration of the rearranged ion takes place to form diazonium ion


H C6H5 N N OH
+ +

C6H5

N N

H2O

Diazonium ion takes up Cl- to yield the diazonium salt


+

C6H5

N N

Cl

C6H5 N N Cl Benzenediazonium chloride

with highly electron rich species such as amino and hydroxy compounds. Even hydroxy compounds must be ionized for reaction to occur.

A diazonium salt is a weak electrophile and hence reacts only

naphthols are coupled in an alkaline medium (pHpKa of phenol or naphthol; typically pH 7 11),

Consequently, hydroxy compounds such as phenols and

Whereas aromatic amines such as N,N dialkylamines are


coupled in a slightly acid medium, typically pH 1 5.

Diazo Component

Aniline and Substituted Anilines. Naphthylamines and Naphthylaminesulfonic Acids

10

Diamines

11

Diamines of diphenyles

12

Diamines of diphenyles

13

14

15

16

In -naphthylaminesulfonic acids, the coupling location is influenced by the position of the sulfonic acid group 1,6-, 1,7-, and 1,8-naphthylaminesulfonic acids couple at the 4-position. 1,5-naphthylaminesulfonic acid (Laurent acid) only couples with very strong couplers (e.g., 2,4-dinitroaniline), mainly at the 4-position With diazotized aniline, chloroaniline or anilinesulfonic acids the 2- aminoazo dyes are obtained

17

18

In an acid medium the azo group enters the position ortho to the amino group, and in an alkaline medium, in the position ortho to the hydroxyl group.

19

20

Thanks & Wish You Best of Luck


21