Patent GB-822096-A (GB)
Title: Improvements relating to metallisable polyazo dyestuffs derived from hydroxy sulphobenzoquinolines and their use
IPC: C09B31/00
Filed: 1957-05-30
Abstract: The invention comprises dyestuffs of formula A-N = N-B-N = N-D, where A is an aromatic residue of the iso- and hetero-cyclic series which may contain an arylazo substituent, B is a residue of a mono- or di-nuclear aromatic-isocyclic hydrocarbon, which may be substituted, the azo groups being in the 1,4- or 1,41-positions, whilst of the neighbouring positions to these groups at least that of the second azo group is occupied by a metallizable group, or a group convertible thereto during metallization, and D is the residue of a 2-hydroxy-4methyl - (hydroxysulphobenzo) - quinoline bound in o-position to the OH group in the isocyclic ring.  The invention also includes copper complexes of the above dyestuffs.  They may be made, in conventional fashion, by coupling diazonium compounds of appropriate amines of formula A-N = N-B-NH2 with the required quinoline and, if desired, coppering in substance or on the fibre. Coupling is effected in aqueous alkaline solution, optionally in the presence of compounds such as pyridine, tertiary alkanolamines or trialkylamines.  Specified benzoquinolines are 2 - hydroxy - 4 methyl - 5,6 - (61 - hydroxybenzo) - quinoline41-, - (41 - hydroxybenzo) - quinoline - 61 - an - (31 - hydroxybenzo) - quinoline - 51 - sulphonic acids and 2 - hydroxy - 4 - methyl - 7,8 - (61 - hydroxybenzo) - quinoline - 41 - and - (31 - hydroxybenzo) - quinoline - 51 - sulphonic acids. Indicated substituents in the diazo components, which may be derived e.g. from benzene, naphthalene, stilbene, diphenyl, thiazole, triazole or tetrazole, are halogen, hydroxyl, alkyl, alkoxy, acylamino, nitro, carboxy, sulpho, carbamide and sulphonamide groups.  Indicated for residue A-NH2, which may contain arylazo groups especially in the p-position to the amino group, are aniline-3- or -4-mono- and -2,4- and - 2,5 - di - sulphonic acids, 4,6 - dimethylaniline - 2 - and 5 - amino - 2 - chlorobenzene1 - sulphonic acids, aniline - 3 - and - 4 - carboxylic acids, 5 - amino - 2 - phenol - 1 -, 5amino - 3 - sulpho - 2 - phenol - 1 - and 5 - (31and 41 - aminobenzoyl) - amino - 2 - phenol - 1carboxylic acids, 4 - aminodiphenyl - 3 - sulphonic acid, 4 - nitro -, -acetyl - amino - and - benzoylamino - 41 - aminostilbene - 2,21 - disulphonic acids, 1 - naphthylamine - 4 -, - 5 -, - 6 - and - 7 - sulphonic acids, 1 - naphthylamine - 3,6 - and 2 - naphthylamine - 3,6 -, - 5,7 - and - 4,8 - disulphonic acids 2 - (41aminophenyl) - 5 - methyl - benzthiazole - monoand - di - sulphonic acids, 2 - (41 - aminophenyl) - naphthotriazole - 5,7 - disulphonic acid, 4 - [(41,51 : 111,211 - naphtho) - 11,21,31 - triazolyl - (2)] - 4 - aminostilbene - 2,21,611 - and - 2,21,511 - trisulphonic acids and 2 - (41 - aminophenyl) - naphthothiazole - 5,7 - disulphonic acid. Indicated as middle components B-NH2 are benzenic and naphthalenic compounds and especially those compounds which contain methoxy, ethoxy or carboxymethoxy groups.  Middle components NH2-B-NH2 may also be used where B represents two benzene rings bound by a direct link or a bridging member, e.g. carbamide, carbaminyl or ethylene, and such diamines specified are 4,41-diamino-3,31-dicarboxy -, - dimethoxy -, - dihydroxy - and - dicarboxymethoxy - diphenyls, N1 - (41-amino - 31 - hydroxybenzoyl) - 1,4 - phenylenediamine - 3 - carboxylic acid, 4,41 - di - (411amino - 311 - hydroxybenzoyl) - amino - 3,31 - dimethoxydiphenyl, 4,41 - diamino - 2,21 - dimethyl - 5,51 - dimethoxydiphenyl urea and 4,41 - diamino - diphenyl urea - 3,31 - dicarboxylic acid.  The ammonium and alkali metal salts of the dyestuffs dissolve in water those of lithium, potassium and sodium being specified.  The dyestuffs dye cellulose material, especially cotton, and may be fixed by coppering.  Soluble copper complexes may also be used for dyeing.  Green and blue shades are obtained. In examples which illustrate the preparation of the dyestuffs and their use in dyeing cotton the following dyestuffs are made: (1) 5-amino-2phenol - 1 - carboxylic acid --> 1 - naphthyl amine - 2 - methoxy - 6 - sulphonic acid --> 2hydroxy - 4 - methyl - 5,6 - (31 - hydroxybenzo)quinoline - 51 - sulphonic acid; (2) 41 - amino4 - (61 - sulphonaphtho - 11,21 : 4,5 - triazolyl(2)) - stilbene - 2,21 - disulphonic acid --> 1naphthylamine - 2 - methoxy - 6 - sulphonic acid --> 2 - hydroxy - 4 - methyl - 5,6 - (41 - hydroxybenzo) - quinoline - 61 - sulphonic acid; (3) 1naphthol - 3,8 - disulphonic acid \sM o - didianisidine --> quinoline of (2); (4) salicylic acid \sM benzidine --> 1 - naphthylamine - 2methoxy - 6 - sulphonic acid --> quinoline of (1); (5) 5 - amino - 2 - phenol - 1 - carboxylic acid --> 1 - naphthylamine - 6 - sulphonic acid --> 2,5 - dimethoxyaniline --> quinoline of (1); (6) 5 - amino - 3 - sulpho - 2 - phenol - 1carboxylic acid --> 1 - naphthylamine - 7 - sulphonic acid --> 1 - naphthylamine - 2 - methoxy - 6 - sulphonic acid --> quinoline of (1) and (7) anthranilic acid --> 2 - amino - 5naphthol - 7 - sulphonic acid \sM o - dianisidine --> quinoline of (1) and the products are coppered.  Various alternative reactants, chosen from those broadly indicated above, are also indicated in the examples. Specification 782,062, [Group IV (b)], is referred to.