Patent GB-761800-A (GB)
Title: Manufacture of tris- and poly-azo dyestuffs
IPC: C09B35/38
Filed: 1954-04-01
Abstract: The invention comprises dyestuffs of formula <FORM:0761800/IV(b)/1> where X is hydrogen, methyl, methoxy, chlorine or SO3H or COOH; A is a diazo component residue; B is a coupling component residue and to the residue of a compound of benzene or naphthalene series.  They may be made by combining the tetrazo compound of a 4,41 -diamino - diphenylamine sulphonic acid in an acidic medium with 1 mol of the compound of the benzene or naphthalene series to give a diaminoazo compound which is treated in a neutral to weakly alkaline medium with a diazo compound and the diazoazo compound thus obtained is combined with any coupling component.  Alternatively they may be made by coupling 1 mol of the benzene or naphthalene compound with a diazo compound in an acidic or neutral to weakly alkaline medium and reacting the azo dyestuff thus obtained with the above tetrazo compound to give a tetratriazo dyestuff or if a free diazo group is still present coupling the diazoazo compound thus obtained with a coupling component.  4, 41 - diamino - 31 - methyl -, - methoxy -, - carboxy -, - chloro - and - sulpho - diphenylamine - 2 - sulphonic acids and 4, 41 -diamino-diphenyl - amine - 2 - sulphonic acid are specified diphenylamine - 2 - sulphonic acids.  Specified compounds from which G is derived are 1 - amino - 5 - naphthol - 3 -, 7 - and 8 - sulphonic acids, 1 - amino - 6 - and 7 -naphthol-3 - and 4 - sulphonic acids, 1 - amino - 8 - naphthol - 3 -, 4 -, 5 - and 6 - sulphonic acids, 1 - and 2 - amino - 3 naphthol - 6 - sulphonic acids, 2 - amino - 5 - napthol - 7 and - 8 - sulphonic acids, 2 - amino- 5 - and 6 - naphthol - 8 - sulphonic acid, 1 - amino - 8 - naphthol - 3, 5 - , 3, 6 - and 4, 6 - disulphonic acids, 1 - amino - 5 - naphthol - 3, 7 - disulphonic acids, 1 - amino - 3 - hydroxyben - zene - 4 - and 6 - sulphonic acids, 1, 3 - diamino - benzene - 4 - sulphonic acid, 1, 3 - diamino - 2 - and - 4 - methyl -, chloro - and - methoxy - benzene - 5 - sulphonic acid, 1, 5 - diaminonaphthalene - 3 - mono - and 3, 7 - disulphonic acids, 1, 8 - diaminonaphthalene - 4 - mono - and 3, 6 - di-sulphonic acids, 1, 3 - diaminonaphthalene - 6 sulphonic acid, 1, 3 - dihydroxybenzene-4 - sulphonic acid, 1, 5 - dihydroxynaphthalene - 7 - mono - and 3, 7 - disulphonic acids, 1, 7 - dihydroxynaphthalene 3 - sulphonic acid, 1, 8 dihydroxynaphthalene - 4 - mono - and 3, 6 - di - sulphonic acids, 2, 5 - dihydroxynaphthalene - 7 - sulphonic acid, 1, 3 - diamino - benzene, 1, 3 - diamino - 4 - chloro - methyl -, -methoxy - and - nitro - benzenes, 1 - methyl- and - hydroxyethyl - amino - 3 - aminobenzenes, 1, 3 - diaminobenzene - 5 - carboxylic acids, 1, 3 - diamino - 2 - and - 4 - chlorobenzene - 5 - carboxylic acids, 1 - amino - 3 - hydroxybenzene, 1 - amino - 3 - hydroxy - 4 - and - 6-chloro - and - methyl - benzenes, 1, 8 - and 1, 5 - diaminonaphthalenes, 1 - amino - 3 -, 5 - and 7 - naphthols, 2 - amino - 5 - naphthol, phenol, #s and p - cresol, 1, 3 - dihydroxybenzene, 1, 3 6 - and 1, 2, 3 - trihydroxybenzenes and 2, 4 and 3, 5 - dihydroxybenzoic acid. Residue A may be derived from any diazo compound which may also be a diazoazo compound and may contain solubilizing groups, e.g. sulphonic acid groups.  Residue B may be derived from any amino, hydroxy or amino-hydroxy aromatic or heterocyclic compound capable of coupling or a compound with a reactive methylene group and may contain solubilizing groups or be an azo dyestuff.  The dyestuffs are especially suitable for leather although cotton, rayon and other synthetic fibres may also be dyed.  Red, violet, brown, grey, blue, green and black shades are obtained. Dyestuffs containing a metallizable group in #s position to an azo group e.g. ( -OH, - COOH, - OCH3, - OCH2COOH) or a salicyl grouping may be metallized on the fibre or in substance with e.g. copper or chromium salts.  Examples are provided of the use of certain of the above specified reagents in the preparation of dyestuffs, components used from which B is derived being: 1, 2 - and 1, 3 - dihydroxy - and - diamino -, benzenes, phenol, 2 - naphthol, 1 - amino - 3 - hydroxy - and - hydroxyethylamino - benzenes, 1 - phenyl - and - diethylamino - 3 - hydroxybenzene, 1, 21 and 41 - methylphenyl - benzenes, 1, 3 - diamino - 4-methyl -, chloro -, - methoxy- and - nitro - benzenes, 1 - hydroxy - 4 - methylbenzene, acetoacetanilide, 2, 4 - dihydroxyquinoline, a - methyl - indole, phenyl methyl pyrazolene and N - diethyl - m - amino - acetanilide, components from which A is derived being aniline, 2 - and 4 - chloraniline, 2 -, 3- and 4 - nitranilines, 2 - chloraniline - 4 - and 5 - sulphonic acids, 4 - nitroanilines, 2 - sulphonic acid, 2-nitraniline - 4 - sulphonic acid, aniline - 2-, 3 - and 4 - mono- and 2, 4- and 2, 5 - disulphonic acids, 4 - acetyl - amino - 1 - aminobenzene, 1 - nitro - 2, 4 - diaminobenzene, 4, 6 - dinitro - 2 - amino - 1 - phenol, 4 - chloraniline - 2 - and 3 - sulphonic acids, aniline - 2 - methoxy - and - hydroxy - 5 - sulphonic acids, 1 - naphthylamine and its 4 - sulphonic acid and 4 - nitro - 41 - amino - diphenylamino - 2 - sulphonic acid, additional values for G being derived from 3 - aminophenol - 4 - and 6 - sulphonic acids and 1, 5 - and 2, 6 - dihydroxy - naphthalene.  In Example 9 a tetrakis - azo dyestuff is made from 4, 41 - di - aminodiphenylamine - 2 - sulphonic acid and the monoazo dyestuff from diazotized aniline - 4 - sulphonic acid and 1, 3 - dihydroxybenzene; in all other examples trisazo dyestuffs are obtained.