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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
+ +
HNO2 C6H5N2Cl
+
_
NaCl
+
NaNO2
NaCl
2H2O
Benzenediazonium chloride
N O
H2O
[N=O]
Nitrosonium ion
+
N N O H C6H5 N N OH
+
H H
+
N N O H
C6H5
N N
H2O
C6H5
N N
Cl
with highly electron rich species such as amino and hydroxy compounds. Even hydroxy compounds must be ionized for reaction to occur.
naphthols are coupled in an alkaline medium (pHpKa of phenol or naphthol; typically pH 7 11),
Diazo Component
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