Patent GB-765355-A (GB)
Title: Mixed complexes of metalliferous mono-azo-dyestuffs and process for making them
IPC: C09B45/14
Filed: 1954-06-08
Abstract: The invention comprises metal compounds which contain one atom of chromium or cobalt bound in complex union with two molecules of different #s:#s1-dioxy-, #s - carboxy - #s1 - oxy - or #s - oxy - #s1 - amino - monoazo - dyestuffs, of which both are free from carboxylic acid groups other than in #s - position to the azo linkage and from sulphonic acid ester, sulphonic acid amide and sulphone groups, and of which one contains a sulphonic acid group and the other is free from sulphonic acid groups the products being free from substantial amounts of metal compounds which contain one atom of metal per molecule of dyestuff or one atom of metal bound in complex union to two molecules of the same dyestuff.  They may be made by reacting together appropriate metallizable metal-free dyestuffs and chromium or cobalt complexes of dyestuffs containing one atom of metal per molecule of dyestuff in a molecular ratio of about 1:1 in an aqueous neutral to weakly alkaline medium at ordinary or elevated temperatures e.g. 50-120 DEG C. advantageously the metallized dyestuff reactant containing the sulphonic acid group.  Alternatively appropriate mixtures of metal free monoazo - dyestuffs may be metallized.  The reactants are made by known methods of diazotization; coupling and metallization. Advantageously the dyestuffs contain no hydroxy groups other than those taking part in the metallization.  Amines indicated for the production of diazo compounds are #s-carboxyamines of the benzene series and especially #s - oxyamines of the benzene and naphthalene series which may contain nitro, alkyl, alkoxy and acylamino groups and halogen atoms those specified being 2-amino - benzoic acid and its 5 - chloro - derivative, 4 - and 5 - chloro-, 4-, 5 - and 6 - nitro, 4, 6 - dichloro-, 3, 4, 6 - trichloro-, 4 - chloro - 5 - and - 6 - nitro-, 4 - nitro - 6 - chloro - and - acetylamino-, 6 - nitro - 4 - methyl - and acetylamino - and 4, 6 - dinitro - 2 - amino - 1 - phenol, 1 - amino-2 - naphthol, 2 - amino - 1 - carboxybenzene - 4 - and - 5 - sulphonic acids, 2 - amino - 1 - phenol - 4 - and - 5 - sulphonic acids, 4 - chloro - and - methyl - 2 - amino-1 - phenol - 5 - and 6 - sulphonic acids, 4 - nitro - 2 - amino - 1 - phenol - 6 - sulphonic acid, 6 - nitro - 2 - amino - 1 - phenol - 4 - sulphonic acid and especially 2 - amino - 1 - naphthol - 4 - and - 8 - sulphonic acids, 6 - bromo-, - methoxy - and - methyl - 1 - amino - 2 - naphthol - 4 - sulphonic acid and particularly 1 - amino - 2 - naphthol - 4 - sulphonic acid and its 6 - nitro - derivative.  Specified coupling components not containing sulphonic acid groups are p - cresol, p - tert. amyl - phenol, 4 - methyl - 1 - acetylamino - 1 - phenol, 4 - methyl - 1 - acetylamino - 1 - phenol, 4 - acetylamino - 1 - phenol, acetoacetic acid anilide, 1 - acetoacetylamino - 2 -, - 3 - and - 4 - chloro - benzenes, 1 - phenyl - and - n - octyl - 3 - methyl - and 1, 3 - diphenyl - 5 - pyrazolones 1 - (21-, 31 - and 41 - chloro - and - methyl-, 21 - ethyl - and 21, 51 - dichloro - phenyl, and naphthyl - (11) and - (21)) - 3 - methyl - 5 - pyrazolones, 1 - phenyl - 5 - pyrazolone - 3 - carboxylic acid phenylamide, oxyquinolines, barbituric acids, 6 - bromo -, - methoxy - and - methyl - 2 - naphthylamines, 2 - phenylaminonapthalene, b  - naphthylamine and its 1 - sulphonic acid which loses the sulphonic acid group on coupling, 6 - bromo - and - methoxy - 2 - naphthols and especially 1 - acetyl-, - n - butyryl-, - benzoyl - and - carbethoxy - amino - 7 - naphthols, 5 - and 8 - chloro - 1 - naphthols, 5, 8 - dichloro - 1 - and - 2 - naphthols and 1 - and 2 - naphthols.  Specified coupling components containing a sulphonic acid group are 1 - phenyl - 3 - methyl - 5 - pyrazolone - 21-, - 31 - and - 41 - sulphonic acids, 21 - chloro - 1 - phenyl - 3 - methyl - 5 - pyrazolone - 41 - and - 51 - sulphonic acids, 21, 51 - dichloro - 1 - phenyl - 3 - methyl - 5 - pyrazolone - 41 - sulphonic acid, 1 - (naphthyl - (11)) - 3 - methyl - 5 - pyrazolone - 41 -, - 51 -, - 61 - - 71 - and - 81 - sulphonic acids, 1 - (naphthyl - (21)) - 3 - methyl - 5 - pyrazolone - 21 - and - 81 - sulphonic acids, 1 - acetoacetylaminobenzene - 4 - sulphonic acid and especially 2 - amino - or - oxy - naphthalene - 4 -, - 5 -, - 6 - and - 7 - sulphonic acids, 1 - naphthol - 3 -, - 4 -, - 5 - and - 8 - sulphonic acids and 2 - phenylaminonaphthalene - 31 -, - 41 - and - 6 - sulphonic acids.  The dyestuffs dye animal materials e.g. silk, leather and wool and synthetic fibres of superpolyamides, superpolyurethanes and polyacrylonitrile from weakly alkaline to weakly acid baths. Examples are provided illustrating the preparation of the metallized dyestuffs from certain of the above specified components and their use in dyeing wool and nylon in black, navy blue, red, brown, grey and green shades, a diazo component used additional to those indicated above being 4 - n - butyrylamino - 1 - phenol.