GB898353A - Process for the manufacture of new metallisable 4-hydroxy-5-carboxyphenyl-2:2-dihydroxy-azo-dyestuffs - Google Patents

Abstract

Sulphonyloxyarylhydroxy carboxylic acids are made and converted into amines for use as dyestuff intermediates, (see Group IV (c)) 2-(41-Methylbenzenesulphonyloxy) - 4 - hydroxy - benzene-5-carboxylic acid is made by treating the disodium salt of 2,4-dihydroxybenzoic acid with tosyl chloride and the free acid liberated from the sulphonate salt thus formed is coupled with diazotised aniline to give an azo compound which is split with acid, in the presence of iron, to yield the required amine. Aniline-4-sulphonic acid may replace aniline to provide a more water-soluble product. Other specified amines obtained by a number method are 1-amino-2-benzenesulphonyloxy - and - (41 - chloro - and -methoxy-, 31,41-dichloro- and naphthalene-(11)-sulphonyloxy) - 4 - hydroxybenzene - 5 - carboxylic acid.ALSO:The invention comprises dyes which contain at least one grouping of formula <FORM:0898353/IV (c)/1> and their heavy metal complexes. The dyes are made in substance, or on the fibre, by the alkaline hydrolysis of the corresponding o-arylsulphonyloxy, o1-hydroxy dyes which are prepared from appropriate o-aryl-sulphonyloxy diazo and hydroxy coupling components. Metallisation may be effected in substance, or on the fibre, at the o,o1-dihydroxy group either during or after hydrolysis. Metallisation on the fibre at the o-hydroxycarboxy group may be effected before hydrolysis, or after metallisation at the o,o1-dihydroxy group. Values specified for the aryl residue in the arylsulphonyloxy groups are benzene, which may contain halogen, alkyl or alkoxy substituents and naphthalene. Illustrative of coupling components which form monoazo dyes are acetoacetylarylamides, pyrazolones, 1,3-dihydroxy benzene and naphthols, preferably those containing sulphonic acid groups. Carboxyl, hydroxyl, sulpho, sulphophenyl, amino and acylamino substituents may be present in the coupling components. Illustrative of coupling components which yield disazo dyes are resorcinol, 1, 8 - dihydroxynaphthalene - 3, 6 - di - sulphonic acid, 2, 5 - dihydroxynaphthalene - 7 - sulphonic acid, 5, 51 - dihydroxy [dinaphthyl - (2) aminel - 7,71\h - disulphonic acid, [5 - hydroxy - 7 sulphonaphthyl(2 and 3)]urea, 2 or 3-acetoacetylamino - 5 - naphthol - 7 - sulphonic acid, 4, 41 - diacetoacetylaminostilbene - 2, 21 - di - sulphonic acid, 1, 11 - diphenylene (4, 41) - bis - (3 - methyl - 5 - pyrazolone) - 3, 31 - disulphonic acid condensation products of one mol of cyanuric chloride and two mols of coupling components containing amino groups and coupling components which contain azo groups such as 4-nitraniline acid-->1-amino-8-naphthol3,6-disulphonic acid and 2-aminophenol-4-sulphonic acid --> 2 - amino - 5 - naphthol - 7 - sulphonic acid or resorcinol (1 mol). Dyes may also be obtained from dyes of the invention which contain a free amino group by appropriate diazotisation and coupling. The dyes colour animal, vegetable, and synthetic fibres and may be used on anodically oxidised aluminium. Chroming may improve light and wet fastness. Copper, nickel cobalt and chromium are specified metals. Examples and tables are provided of the preparation of mono-, dis-, and tris-azo dyes and their metal complexes and the use of the dyes and their complexes in colouring processes a variety of colour shades being obtained. The diazo components are obtained by acid splitting the corresponding -1,11-azobenzene-5-carboxylic acid.