Verfahren zur Herstellung von Azofarbstoffen und deren Metallkomplexverbindungen

摘要

The invention comprises dyestuffs and metal complexes of dyestuffs of the general formulae wherein D is a radical of a diazo component which may contain additional substituents, R is hydrogen or an alkyl group, n is 1 or 2 and X is halogen or a group -O-CO-alkyl, -O-CO-aryl, -O-SO2-alkyl, -O-SO2-aryl, -O-SO3H, -S-SO3H, -O-aryl or -N(alkyl)2. D may be a benzene, naphthalene, azobenzene, azonaphthalene, phenylazonaphthalene, diphenyl, diphenylamine, dehydrothiotoluidine or stilbene radical which may be substituted by sulphonic acid, carboxylic, alkyl-sulphonyl (C1-C6), sulphonic acid amide, carboxylic acid amide, halogen, alkyl, alkoxy, acyl, acylamino, arylamino, hydroxy, nitro, cyano, trifluoromethyl or heterocyclic groups. Cobalt and chromium form 2:1 dye:metal and copper and nickel 1:1 dye:metal complexes. The dyestuffs may be prepared by (1) diazotizing an amine D-NH2 and coupling to a coupling component of general formulae or (2) reacting dyestuffs of general formula or their metal complexes with isocyanates of general formulae or their carbamic acid derivatives, wherein D, R and X are as defined above at neutral pH values, at temperatures of -5 DEG to +30 DEG C. in presence of an emulsifier or a solvent, e.g. benzene, toluene, chlorobenzene or acetone. In a preferred feature the groups -SO2CH = CH2 or -SO2CH2CH2X which may be converted, e.g. -SO2CH = CH2 to -SO2CH2CH2S-SO3H, and -SO2CH2CH2X where X is chlorine to -SO2CH2CH2N(C2H5)2 of Example 18 and 25. When the diazo components contain hydroxy, alkoxy or carboxylic acid groups oto the azo link the corresponding metal complexes may be formed and when hydrogen is oto the azo link the dye may be treated with a copper salt and an oxidizing agent, e.g. H2O2 (35%) to form a copper complex which may be decoppered and exchanged for another metal which complexes with the thus formed O, O1 dihydroxy compound. Conventional metallizing agents are used, metallization taking place at 20-130 DEG C. in weakly acid or neutral conditions, optionally in the presence of organic solvents, e.g. alcohol or dioxane. The preferred coupling components are derived from 1-amino-8-hydroxynaphthalene 3,6- or 4,6-disulphonic acids and many examples are specified.ALSO:Dyestuff intermediates of the general formulae wherein R is H or alkyl, and X is halogen, O-CO-alkyl, O-SO3H, -S-SO3H, -O- phenyl or N (alkyl)2 and n is 1 or 2 are prepared by condensing compounds of the general formula with compounds of the general formulae wherein R, X and n are as defined above. The reaction takes place at low temperatures, e.g. 0-10 DEG C. at neutral pH values and when a carbamic acid derivative is used reaction takes place at 50-60 DEG C. (see Example 5).