Patent GB-775011-A (GB)
Title: Manufacture of new cobaltiferous azo-dyestuffs
IPC: C09B45/20
Filed: 1953-12-29
Abstract: The invention comprises cobaltiferous mixed complexes of monoazo dyestuffs which contain, bound to one atom of cobalt, two different monoazo dyestuffs free from sulphonic and carboxylic acid groups, one of which dyestuffs is an o:o1 - dihydroxymonoazo dyestuff and the other is of formula R - N=N - A - NH2 (1) where R is the residue of a hydroxybenzene bound to the azo linkage in ortho - position to the hydroxyl group, A is a naphthalene residue bound to the azo linkage in ortho position to the amino group, and one of the residues R and A contains a methyl sulphone group.  They are prepared by treating a mixture of the dyestuffs advantageously containing approximately equimolar amounts of the two dyestuffs, with a cobalt-yielding agent. The dyestuffs of formula (1) are prepared by coupling an ortho-hydroxy diazo compound of the benzene series with an aminonaphthalene coupling ortho to the amino group, both components being free from sulphonic and carboxylic acid groups, and selecting the diazo and coupling components so that one of them contains a methyl sulphone group.  Specified components for the dyestuffs of formula (1) are:- diazo components; 4 - chloro - 2 - amino - 1 - hydroxybenzene - 5 - or - 6 - methylsulphone, 6 - chloro - 2 - amino - 1 - hydroxybenzene - 4 - methylsulphone, 2 - amino - 1 - hydroxybenzene - 4- or -5-methyl sulphone, 6- or 5-nitro - 2 - amino - 1 - hydroxybenzene - 4 - methylsulphone, 4 - nitro - 2 - amino - 1 - hydroxybenzene - 6 - methylsulphone, 4 - or - 5 - or 6 - nitro - 2 - aminophenol, 4 - nitro - 6 - chloro - 2 - aminophenol, 6 - nitro - 4 - chloro - 2 - aminophenol, 4 - nitro - 6 - acetylamino - 2 - aminophenol, 6 - nitro - 4 - acetylamino - 2 - aminophenol and 4:6-dinitro - 2 - aminophenol: coupling components; 6 - bromo - or - methoxy - or -methyl - 2 - aminonaphthalene, 2 - aminonaphthalene.  2 - aminonapthalene - 4 - or - 5 - or - 6 - or - 7 - methylsulphone and 1 - aminonaphthalene - 4 - or - 5 - methylsulphone.  Specified reagents which may be used in the preparation of the o:o1 - dihydroxy - monoazo dyestuffs are:- diazo components; those described above, 2-amino - 1 - hydroxybenzene - 4 - sulphonamide, 6 - nitro - or - chloro - 2 - amino - 1 - hydroxybenzene - 4 - sulphonamide, 2 - amino - 1 - hydroxybenzene - 4 - or - 5 - sulphonic acid methylamide and 4 - nitro - or - chloro - 2 - amino - 1 - hydroxybenzene - 5 - or - 6 - sulphonamide: coupling components; para - substituted phenols, 5:8 - dichloro - 1 - naphthol, 2 - naphthol, 1 - acetylamino - or - n - butynylamino - 7 - naphthol, 1 - phenyl - 3 - methyl - 5 - pyrazolone, 1 - (21 - or 31 - or 41 - chlorophenyl)- methyl - 5 - pyrazolone, 1 - phenyl - 3 - methyl - 5 - pyrazolone - 31 - sulphonic acid methylamide, 2:4 - dihydroxyquinoline, 5 - chloro - 8 - oxyquinoline, barbituric acid, acetoacetic acid anilide and 1 - acetoacetylamino - 2 - or - 3 - or - 4 - chlorobenzene.  The metallization of the mixture of dyestuffs is carried out in weakly acid, neutral or preferably alkaline medium advantageously at raised temperature and if desired in the presence of an organic acid salt, a base or an organic solvent.  In general the amount of cobalt-yielding agent used corresponds to between 1/2 and 1 atomic proportion of cobalt per molecular proportion of each dyestuff in the mixture. Cobalt yielding agents specified are complex compounds of aliphatic hydroxycarboxylic or dicarboxylic acids, cobalt acetate, cobalt sulphate and cobalt hydroxide.  The dyestuffs dye and print silk, leather, superpolyamides, superpolyurethanes and especially wool in olive, grey, brown, blue and green tints.  In examples the following pairs of monoazo dyestuffs are mixed and metallized with cobalt-yielding agents: (1) 6 - nitro - 2 - amino - 1 - hydroxybenzene - 4 - methylsulphone --> 2 - aminonaphthalene and 4 - nitro - 2 - aminophenol --> 1 - phenyl - 3 - methyl - 5 - pyrazolone or 5 - nitro - 2 - aminophenol --> 1 - acetylamino-7 - naphthol or 2 - amino - 1 - hydroxybenzene - 4 - sulphonic acid methylamide --> acetoacetylamino - 2 - chlorobenzene; (2) 4:6 - dinitro - 2 - aminophenol --> 2 - aminonaphthalene - 6 - methylsulphone and 2 - amino - 1 - hydroxybezene - 4 - sulphonamide --> 1 - (41 - chlorophenyl) - 3 - methyl - 5 - pyrazolone or 2 - amino - 1 - hydroxybenzene - 4 - sulphonic acid isopropylamide --> acetoacetic anilide; (3) 5 - nitro - 2 - aminophenol --> 2 - aminonaphthalene - 6 - methylsulphone and 2 - amino - 1 - hydroxybenzene - 4 - sulphonic sulphonic acid methylamide --> acetoacetylamino - 2 - chlorobenzene or 4 - nitro - 2 - aminophenol --> 3 - methyl - 5 - pyrazolone or 2 - amino - 1 - hydroxybenzene - 5 - sulphonamide --> 5:8 - dichloro-1 - naphthol or 2 - amino - 1 - hydroxybenzene - 4 - sulphonic acid isopropylamide --> acetoacetic acid anilide.  Specification 759,636 is referred to.