Patent GB-766381-A (GB)
Title: Improvements in or relating to stilbene polyazo dyestuffs and metal complexes thereof
IPC: C09B45/24
Filed: 1954-08-26
Abstract: The invention comprises copper and/or nickel-containing triazo dyestuffs which in their metal-free state are of formula <FORM:0766381/IV(b)/1> where X is a nitro or an -NH-acyl group or a naphthalene-triazole residue in which the naphthalene radicle is connected in 1, 2- position with the triazole ring, y is COOH, Me O or Et O, w is H, lower alkyl, lower alkoxy or acylamino, one Z is OH and the other -N=N-R where R is a benzene or naphthalene residue containing #s to -N=N- one OH or COOH group and the -N=N- marked (a) is in a 4 or 5 position of A.  The term "lower" refers to alkyl and alkoxy groups containing at most 6 carbon atoms The dyestuffs may be made by diazotizing, preferably by an indirect method, an appropriate stilbene aminoazo dyestuff and coupling, advantageously in alkaline medium and optionally in the presence of compounds such as pyridine or quinoline, with the necessary naphthol monoazo dyestuff containing Z or a metal complex thereof (obtainable as in Specifications 388,322, [Group IV] and 697,488 and German Specifications 571,859 and 807,289) complete metallization being effected in substance or on the fibre.  The stilbene components may be made by coupling the appropriate diazotized stilbene compound and aminobenzene which couples p to the NH2 group and which may be used as an o -methane-sulphonic acid derivative or by condensing appropriate nitro- or naphthalene-triazole stilbene compound with m- or p-diaminobenzenes in aqueous caustic alkali medium.  Stilbene components may also be made by diazotizing and coupling appropriate stilbene compounds with #s-acetylamino-phenol, alkylating the hydroxy group and hydrolizing the acylamino group. Dyestuffs in which X is a naphthalene-triazole residue may also be made by preparing the corresponding dyestuff where X is NO2 or NH-acyl and which does not contain any amino, nitro or acylamino groups other than those specified, converting X to an amino group, diazotizing the amino-triazo dyestuff thus obtained, coupling with a 1- or 2- amino-naphthalene which couples #s to NH2 and oxidizing the #s aminoazo group to a triazole ring before or simultaneously with metallization in substance. The naphthalene triazole residue may contain substituents, preferably water-solubilizing groups e.g. SO3 groups. NHCO- groups mentioned are derived from formic, acetic, propionic, butyric and isobutyric acids, -NH CO, COOH, -NH CO CH2 COOH, -NH CO CH =CH COOH, those derived from benzoic and m and p-nitrobenzoic acids monoacyl-amino groups from benzene 1, 2-, 1, 3- and 1, 4-dicarboxylic acids where the second COOH group is free or esterified, carbacylamino groups from 1-carboxybenzene - 4 - mono- and -2, 4 - di-sulphonic acids, -NH COOCH3, -NH COOC2H5 and -NH COO C2H4OC2H5 R may also contain substituents such as C1, CH3, OCH3 OC2H5, COOH COOCH3, COOC2H5, So3H, SO2CH3 SO2NH2, SO2NHCH3, SO2NH C2H4 OCH3, NO2, NH2, NHCH3 and NHC6H5 groups. The metal-free or partly or completely metallized dyestuffs dye cotton and fibres of regenerated cellulose in reddish-blue, grey, brown to olive-green shades Metallisation is effected in conventional fashion.  In examples which illustrate the preparation of the dyestuffs and their use in dyeing cotton and regenerated cellulose fibres stilbene aminoazo components used are 4-nitro - 41 (211 - methyl - 411 - amino - 511 - dimethoxy)-, -(311 - carboxy or -methoxy-411-amino)-, -)211, 5 -dimethoxy or -diethoxy - 411 - amino) -, - (311 - amino 411-methoxy)- or -(211-acetyl- or propionylamino-411-amino-, 511-methoxy)-, 4-acetylamino-41- (211-methyl or -acetylamino-4 - amino - 511 - methoxy) and - (211, 511-dimethoxy-411-amino)- and 4-benzoyllamino - 41 - (211 - methyl - 41 - amino-511-methoxy-or-ethoxy)- phenylazo-stilbene 2, 21-disulphonic acids and 2- (1111, 2111 - naphthalene) triazole - 41 (211 - methyl - 411 - amino - 511 - methoxy)- and 4 - (1111, 2111 - naphthalene) triazole - 41 - (311 carboxy - or - methoxy - 411 -amino)-, -211 - methyl - 411 - amino - 511 - methoxy)-and -(411-methoxy-311-amino) -phenylazo stilbene -2, 21, 411-trisulphonic acids and naphthol mono-azo dyestuffs used are copper complexes of 1-(21carboxy)-phenylazo-2, 5-dihydroxy-napthalene-7-mono- and 51, 7-di-sulphonic acids, 1-(21-hydroxy)-phenylazo-2, 5-dihydroxy-naphthalene-41, 7-disulphonic acid, 1, 5-dihydroxy-2-(21-hydroxy) -naphthyl- (11)-azonaphthalene-41, 7-disulphonic acid, 1, 5-dihydroxy-2- (11-hydroxy) -naphthyl(21)- azonaphthalene-31, 61, 7-trisulphonic acid, 1- (21-hydroxy)- naphthyl-(11)-azo-2, 5-dihydroxynaphthalene-41, 7-disulphonic acid and nickel and copper complexes of 1 - (21 - carboxy - 41 - nitro)-phenylazo-2, 5-dihydroxy-naphthalene-7-sulphonic acid the products being completely metallized by treatment with a copper or nickel-yielding agent.