Patent GB-616523-A (GB)
Title: Manufacture of direct dyestuffs and intermediates
IPC: C09B43/16
Filed: 1944-08-31
Abstract: Dye intermediates of the stilbene or dibenzyl series are manufactured by treating a condensation product of the general formula <FORM:0616523/IV(b)/1> (wherein X represents -CH=CH- or -CH2-CH2-, Y represents a halogen atom and each Z represents H, -COOH or -SO3H) with at least one aromatic amine so as to exchange at least one halogen atom for the residue of an amine which, after the exchange, is capable of forming azo-dyestuffs, and exchanging any other halogen atoms for amino groups and/or the residues of amines, which may be identical or different, by treatment with ammonia and/or amines.  The amines capable after the condensation of forming azo dyestuffs are those which contain a further diazotizable amino group or a group convertible thereto by saponification or reduction, or which contain substituents which enable coupling with diazo components to be brought about. Advantageously the amines employed also contain one or more groupings which enable metallization to be effected.  In examples and tables, the following components are employed: the dicyanuric derivatives of 4 : 41-diaminostilben-and it's 2 : 21-disulphonic acid and 3 : 31-dicarboxylic acid, and 4 : 41-diaminodibenzyle 2 : 21-disulphonic acid; 2 : 5 : 7- or 2 : 8 : 6-aminonaphtholsulphonic acids or their N-aminobenzoylated derivatives; ammonia, mono- and di-methylamine, aniline, N-methylaniline, 3-aminoacetanilide (which may be subsequently saponified), 1 - chloro - 2 : 4-diaminobenzene, p-phenylenediamine, metanilic acid, 1 - amino - 4 - hydroxybenzene - 3 - carboxylic acid, 1-(31- or 41-aminobenzoyl)amino-4-hydroxy-3-carboxybenzene-5-sulphonic acid, 1 - (41 - aminobenzoyl)amino - 2 - hydroxy - 3-carboxybenzene - 5 - sulphonic acid, 1 - amino-4 - hydroxy - 3 - carboxybenzene - 5 - sulphonic acid, 5-amino-2-(21- or 41-hydroxy-31-carboxy-51 - sulphophenyl) - 1 : 3 - benztriazole and 41 - amino - 5 : 61 - dimethyl - 4 - hydroxy-diphenylmethane-3-carboxylic acid. Specifications 265,203, [Class 2 (iii)], 578,014 and 595,181 are referred to.  1 - (31 - and 41 - Aminobenzoyl) - amino - 4-hydroxy - 3 - carboxybenzene - 5 - sulphonic acids are obtainable by acylating 1-amino-4-hydroxy-3-carboxybenzene-5-sulphonic acid with 3- or 4-nitrobenzoyl chloride in aqueous solution, and reducing the nitro group, e.g. with sodium sulphide.  41 - amino - 5 : 61 - dimethyl - 4 - hydroxydiphenylmethane - 3 - carboxylic acid is obtainable by condensing chloromethyl-o-cresotinic acid with m-toluidine.ALSO:Dyes of the stilbene or dibenzyl series are manufactured by treating a condensation product of the general formula <FORM:0616523/IV (c)/1> (wherein X represents -CH=CH- or -CH2 -CH2-, Y represents a halogen atom and each Z represents H, -COOH or -SO3H) with at least one aromatic amine so as to exchange at least one halogen atom for the residue of an aminoazo compound or for the residue of an amine which, after the exchange, is converted into the residue of an azo-dyestuff, and exchanging any other halogen atoms for amino groups and/or the residues of amines, which may be identical or different and may contain azo groups, by treatment with ammonia and/or amines.  The amines to be converted after the condensation into the residues of azo dyestuffs are those which contain a further diazotizable amino group or a group convertible thereto by saponification or reduction, or which contain substituents which enable coupling with diazo components to be brought about, and such coupling may subsequently be performed in substance or on the fibre. Advantageously, the amines or aminoazo compounds employed also contain one or more groupings which enable metallization to be effected in substance or on the fibre (e.g. by treatment with trivalent or hexavalent chromium salts or with copper salts), or metallizable groups may be subsequently introduced by diazotizing an amine containing a metallizable group in o-position, e.g. an o-aminocarboxylic acid or an o-aminophenol, and coupling with a condensation product containing a component capable of coupling in o-position to a hydroxy group, e.g. the residue of an aminonaphtholsulphonic acid.  The dyestuffs yield on cellulose fibres chiefly yellow, orange, red, violet or brown dyeings, which may be after-treated with formaldehyde.  Some of them may also be used in conjunction with wool dyestuffs (especially those capable of being chromed) for dyeing mixtures or mixed fabrics of cellulosic and animal fibres.  In examples and tables, the following components are employed: the dicyanuric derivatives of 4 : 41-diaminostilbene and its 2 : 21-disulphonic acid and 3 : 31-dicarboxylic acid, and 4 : 41-diaminodibenzyl-2 : 21-disulphonic acid; 4-amino-1 : 11-azobenzene-31-sulphonic acid, 4 - amino - 3 - methoxy - 1 : 11 - azobenzene - 31 - carboxylic acid, 4 - amino - 2 - acetylamino - 41 - chloro - 1 : 11 - azobenzene - 31 - sulphonic acid, 4 - amino - 41 - hydroxy - 1 : 11 - azobenzene - 31 - carboxylic acid, 4 - amino - 2 - methoxy - 21 - hydroxy - 1 : 11 - azobenzene - 51 - sulphonic acid, 4-amino-2-methyl-6-methoxy-41-acetylamino-1 : 11-azobenzene-51-sulphonic acid, 4-amino-2-methyl-41-hydroxy-31-carboxy-1 : 11-azobenzene-51-sulphonic acid, 4-amino-2-methyl - 5 - methoxy - 1 : 11 - azobenzene - 41 - sulphonic acid, 4-amino-41-acetylamino-5-methoxy - 2 - methyl - 1 : 11 - azobenzene - 31 - sulphoni acid, 4-amino-2 : 5-dimethoxy-21-hydroxy-1 : 11-azobenzene-51-sulphonic acid, the monoazo dyestuffs 2-aminonaphthalene-4 : 8-disulphonic acid --> 3-aminoacetanilide, 1 : 8-aminonaphthol-3 : 6-disulphonic acid p-toluenesulphonic ester --> 1 - amino - 3 - methyl - 6 - methoxy - benzene (saponified), and 1-(41- or 31-aminobenzoyl) -amino-4-hydroxy-3-carboxybenzene-5-sulphonic acid or 1-(41-aminobenzoyl)-amino-2-hydroxybenzene-3-carboxylic acid or 1-amino-3-carboxybenzene-5-sulphonic acid --> 1-amino-2-methyl-6-methoxybenzene, and the disazo-dyestuff 4 - amino - 1 : 11 - azobenzene --> (alkaline) 2 : 5 : 7-aminonaphtholsulphonic acid; 2 : 5 : 7- or 2 : 8 : 6-aminonaphtholsulphonic acids or their N-aminobenzoylated derivatives, subsequently coupled with diazotized anthranilic acid, or (in the case of 2 : 5 : 7-acid) with diazotized 4-amino-1 : 11-azobenzene or on the fibre with diazotized p-nitraniline; ammonia, mono- and di-methylamine, aniline, N-methylaniline, 3-aminoacetanilide (which may be subsequently saponified and the dyestuff diazotized on the fibre and developed, e.g. with 1-phenyl-3-methyl-5-pyrazolone or b -naphthol), 1-chloro-2 : 4 - diaminobenzene, p - phenylenediamine, metanilic acid, 1-amino-4-hydroxybenzene-3-carboxylic acid, 1-(31- or 41-aminobenzoyl)-amino - 4 - hydroxy - 3 - carboxybenzene - 5 - sulphonic acid, 1 - (41 - aminobenzoyl) - amino - 2 - hydroxy - 3 - carboxybenzene - 5 - sulphonic acid, 1 - amino - 4 - hydroxy - 3 - carboxybenzene - 5 - sulphonic acid, 5-amino-2-(21- or 41-hydroxy-31-carboxy-51-sulphophenyl)-1 : 3-benztriazole and 41 - amino - 5 : 61 - dimethyl - 4 - hydroxydiphenyl - methane - 3 - carboxylic acid.  Specifications 265,203, [Class 2 (iii)], 578,014 and 595,181 are referred to.  The Specification as open to inspection under Sect. 91 comprises also an additional example in which the condensation product from two molecular proportions of cyanuric chloride and one of 4 : 41-diaminostilbene-2 : 21-disulphonic acid is condensed with two molecular proportions of 4-amino-41-hydroxy-1 : 11-azobenzene-31-carboxylic acid and the product is then condensed with a further two molecular proportions of the same aminoazo compound.  This subject-matter does not appear in the Specification as accepted.