Patent GB-722949-A (GB)
Title: Trisazo dyestuffs, their copper complex compounds and process for their manufacture
IPC: C09B35/366
Filed: 1952-08-26
Abstract: The invention comprises trisazo dyestuffs of formula <FORM:0722949/IV (c)/1> where R is an aryl group which may be substituted, R1 is an aryl group which may be sulphonated or substituted otherwise, one X is SO3H and the other H, Y is a group ortho to the azo1 group and capable of forming a metal complex, 2 is an amino group which may be alkylated, arylated or acylated or H and n is 1-3, and OH is in the ortho position and azo in the para position to the azo group, and their copper complexes.  They may be made by coupling the tetrazo compound from 1 mol. of 4,41-diamino-1,11-diphenyl-3-sulphonic acid with 1 mol. of an aceto-acetic acid arylamide advantageously in sodium carbonate or bicarbonate solution and preferably in formic or acetic acid solution and 1 mol. of an aromatic amine which couples in the para position to the amino group and which may be sulphonated and which has a group capable of forming metal complexes in the ortho position to the amino group, diazotizing the aminodisazo dyestuff obtained, coupling with 1 mol. of the requisite hydroxynaphthalene derivative advantageously in weak alkaline solution, e.g. sodium bicarbonate or ammonia solution with pyridine or quinoline and preferably treating with copper-yielding agents.  Alternatively 1 mol. of 4,41-diamino-1,11-diphenyl-3-sulphonic acid which may be monoacylated is diazotized and coupled with 1 mol. of an acetoacetic acid monoarylamide, the acylamino group if present is saponified, and the amino azo compound obtained coupled with 1 mol. of the required aromatic amine to yield an aminodisazo compound which is diazotized and coupled with the appropriate hydroxynaphthalene derivative and treated with copper-yielding substances if desired.  The dyestuffs may also be made by diazotizing a monoacylated 4,41-diamino - 1,11 - diphenyl - 3 - sulphonic acid and coupling with the aromatic amine, the amine so formed being diazotized and coupled with the hydroxynaphthalene derivative and the acyl group of the product removed by saponification before diazotization and coupling with an acetoacetic acid arylamide with subsequent coppering if desired. Saponifications are preferably effected in an alkaline medium. Specified aromatic amides of aceto-acetic acid are acetoacetylaminobenzene-1-acetoacetyl - amino - 2 -, - 3 - or 4 - methyl or methoxy - benzene, 1 - acetoacetyl - amino - 3 - or - 4 - sulphonic acid or - 2 - methoxybenzene - 3 - or - 4 - sulphonic acid, 1 - acetoacetylaminobenzene - 4 - carb - oxylic acid, 1 - acetoacetylamino - 3 - hydroxy - benzene - 4 - carboxylic acid, 1 - acetoacetyl - amino - 4 - hydroxybenzene - 3 - carboxylic acid, and 2 - acetoacetylaminonaphthalene - 3,6 -, - 4,8 -, - 5,7 - or - 6,8 - disulphonic acid.  Aromatic amines specified are 1-amino-2-methoxy - or - 2,5 - dimethoxy - benzene, 1 - amino - 2 - methoxy - 5 - methylbenzene, 1 - amino - 2 - methoxy - or - ethoxy - naphthalene - 6 - sulphonic acid or 1 - amino - 2 - methoxy - 5 - acetylaminobenzene. Hydroxynaphthalene compounds specified are 1- and 2-hydroxynaphthalene, 1 - hydroxynaphthalene - 3 -, - 4 - or - 5 - mono - and - 3,6 - and - 3,8-disulphonic acids, 2 - hydroxynaphthalene - 4 -, - 6 - and - 7 - mono - and - 3,6 - disulphonic acids, 2 - amino -, - methylamino -, - ethylamino -, propylamino -, - cyclohexylamino -, - phenylamino -, - (41 - sulpho -, 31 - or 41 - carboxy -, - methyl - or - methoxy - or 41 - hydroxy - 31 - carboxy - or 31 - hydroxy - 41 - carboxy - phenylamino) -, - acetylamino -, - propionylamino -, - decanoylamino -, - benzoylamino - or - 21 -, - 31 - or - 41 - nitro -, bromo -, chloro -, amino -, methyl - or ethoxy - benzoylamino -, 5 - hydroxynaphthalene - 1,7 - disulphonic acid.  4 - Amino - 41 - acetyl -, formyl -, oxalyl - or carbethoxy - amino - 1, 11 - diphenyl - 3 - sulphuric acid are specified monoacylated derivatives. Coppering may be effected with cuprammonium hydroxide solutions or by fusing alkali metal salts of low molecular aliphatic monocarboxylic acids with copper melts. Cellulose fibres are dyed bright green to olive tints by the dyestuffs before or after coppering.  Examples are given of the use of various of the components specified above.