Patent GB-466886-A (GB)
Title: Manufacture of dyestuffs
IPC: C09B43/16
Filed: 1935-11-04
Abstract: Azo dyes; anthraquinone dyes; lakes; azo dyes, forming upon the material; regenerated celluloses, dyeing; substantive dyes, dyeing with.--Azo dyestuffs containing simultaneously an azo chromophore and an a -aminoanthraquinone residue are manufactured by combining both an a -aminoanthraquinone compound containing at least one reactive amino group and an aminoazo dyestuff containing a reactive amino group with a cyanuric halide, e.g. the chloride or bromide, phosgene, or a compound containing a divalent carbon residue equivalent to --CO-- in a halogen-substituted heterocyclic ring and containing at least two exchangeable halogen atoms in the molecule, e.g. dichloroquinazoline or tribromopyrimidine. Alternatively, instead of an aminoazo dyestuff there is used a compound which can be converted into an aminoazo dyestuff by diazotization and combination with a coupling component or by coupling with a diazo compound, and the completion of the aminoazo dyestuff is effected after the condensation, if necessary after the application of a reduction or saponification in order to form a diazotizable amino group.  As a -aminoanthraquinone compounds may be employed simple a -aminoanthraquinones and also a -aminoanthraquinone compounds containing an amino group in an external group, e.g. a -aminobenzoylaminoanthraquinones or aminophenylated a -aminoanthraquinones.  The products yield yellow, orange, red, violet, blue, green, brown or black dyeings, e.g. on regenerated cellulose artificial silk, or on natural fibres, e.g. cotton or silk, and may also be used for the manufacture of pigments and for colouring lacquers or varnishes, advantageously after precipitation with suitable compounds.  When they contain a suitable grouping, e.g. that of salicylic acid, they may be converted in substance or on the fibre into complex metal compounds, e.g. of copper or chromium.  In examples: (1) cyanuric chloride is condensed successively with 4 - amino - 4<1> - oxy - 1 : 1<1> - azobenzene-3<1> - carboxylic acid, 1-amino-4-(4<1>-amino-3<1>-sulpho) - anilidoanthraquinone - 2 - sulphonic acid, and aniline; the aniline may be replaced by a further quantity of the aminoazo dyestuff or the anthraquinone compound by a sulphonated 1 - methylamino - 4 - benzidinoanthraquinone (produced by the reaction of equimolecular proportions of 1-methylamino-4-bromoanthraquinone and benzidine); methyl-groups may be introduced into the aminoazo dyestuff, e.g. by using a cresotinic acid in its preparation; (2) the initial condensation product of (1) is condensed with 1 : 5-dioxy-4 : 8 - diaminoanthraquinone - 2 : 6-disulphonic acid and then with aniline; the product dyes cotton and viscose yellow-green shades becoming yellower on after-treatment with an agent yielding copper; (3) cyanuric chloride is condensed successively with the p  dyestuff metanilic acid --> o-anisidine, 1-amino-4-(4<1>- or 3<1> - amino) - anilidoanthraquinone - 2-sulphonic acid (produced by reaction between equimolecular proportions of 1-amino-4-bromoanthraquinone - 2 - sulphonic acid and p- or m-phenylenediamine), and aniline; the aminoazo dyestuff may be replaced by 4-amino-1 : 1<1>-azobenzene-4<1>-sulphonic acid; (4) cyanuric chloride is condensed successively with the condensation product from 1-amino-4-bromoanthraquinone - 2 - sulphonic acid and 1 : 4-diaminobenzene - 3 - sulphonic acid, the dyestuff 1 - aminobenzene - 3 - carboxylic acid --> m-toluidine, and aniline; (5) the aminoazo dyestuff of (4) is replaced by that obtained by reducing the dyestuff 4-nitro-1-aminobenzene - 2 - sulphonic acid --> acetoacetic anilide; for the final condensation there may be employed p-, o- or m-phenylenediamine, benzidine or methylamine, some of the products being capable of diazotization on the fibre; (6) m-phenylenediamine is condensed successively with the initial condensation products of (4) and (1) and the product is condensed with aniline; the product dyes cotton green shades which may be coppered on the fibre; the m-phenylenediamine may be replaced by p-phenylenediamine or a sulphonic acid thereof, benzidine or its disulphonic acid, or diaminostilbenedisulphonic acid; (7) cyanuric chloride is condensed successively with the condensation product from 1-amino-4-bromoanthraquinone 2-sulphonic acid and 1 : 4-diaminobenzene-2-sulphonic acid, 1 : 8-aminonaphthol-3 : 6-disulphonic acid, and aniline, and the product is coupled with the diazo compound of the aminodisazo dyestuff 1-amino-8-(4<1>-toluenesulpho)-oxynaphthalene - 3 : 6 - disulphonic acid --> 3-amino-4-cresol methyl ether --> 2 - amino - 5 - naphthol - 7 - sulphonic acid; the anthraquinone component may be replaced by the corresponding condensation product with p-phenylenediamine or benzidine, the 1 : 8 : 3 : 6 - acid by its isomers or by mono-sulphonic acids, and the diazo component by other diazotizable aminoazo dyestuffs; (8) cyanuric chloride is condensed successively with the dyestuff obtained by condensation of N-methyl-4-bromo-1-anthrapyridone (produced by acetylating 1 - methylamino - 4 - bromo-anthraquinone and treating the product with condensing agents) with p-phenylenediamine and subsequent sulphonation, the dyestuff obtained by reducing the dyestuff 1-amino-4-nitrobenzene - 2 - sulphonic acid --> 2-phenylamino - 5 - naphthol - 7 - sulphonic acid, and aniline; the aminoazo dyestuff may be replaced by the disazo dyestuff 1-amino-8-naphthol - 3 : 6 - disulphonic acid --> 1-amino - 2 - methoxy - 5 - methylbenzene --> 2 amino - 5 - naphthol - 7 - sulphonic acid; (9) 4 - methyl - 2 : 6 - dichloropyrimidine is condensed, successively in either order or simultaneously, with 4-amino-4<1>-oxy-1 : 1<1>-azobenzene - 3<1> - carboxylic acid and 1 - amino - 4-(4<1> - amino - 3<1> - sulpho) - anilidoanthraquinone-2-sulphonic acid; (10) phosgene is passed into a solution of 1-amino-4-(4<1>-amino-3<1>-sulpho) - anilidoanthraquinone - 2 - sulphonic acid sodium salt and 4-amino-4<1>-oxy-1 : 1<1>-azobenzene - 3<1> - carboxylic acid in aqueous sodium carbonate; (11) cyanuric chloride is condensed successively with the product obtained by condensation of 1 - amino - 4-bromo-anthraquinone - 2 - sulphonic acid with 1-acetylamino - 3 - benzenesulphamide and subsequent saponification, the dyestuff 1-methoxy - 2 - aminobenzene - 4 - sulphonic acid --> 2-amino-5-naphthol-7-sulphonic acid, and aniline; (12) the anthraquinone component in (11) is replaced by 1 : 4-oxyaminoanthraquinone-5-sulphonic acid; the aminoazo dyestuff may be replaced by 4-amino-4<1>-oxy-1 : 1<1>-azobenzene - 3<1> - carboxylic acid; (13) cotton is dyed green shades with the product of (1) (first alternative) from a bath containing also sodium carbonate and sodium sulphate.  Specifications 209,723, 288,159, 300,987, 309,102, 315,664, and 315,665, [all in Class 2 (iii)], are referred to.  The Specification as open to inspection under Sect. 91 comprises in general the use in the condensation of compounds of the anthraquinone series, including the dibenzanthrone, pyranthrone, pyrazolanthrone, anthanthrone and dibenzpyrenequinone series, containing a reactive amino group, and of halides of organic acids and their analogues, e.g. isocyanates, dichlorides of terephthalic and isophthalic acids, dichlorides of dioxyphenylacetic acids, dichlorophthalazine, carbon bisulphide, in some cases in the form of mustard oils, also products to be regarded as derivatives of mono-basic acids, e.g. nitrobenzoyl chloride, nitro or acidylamino derivatives of anhydrides or halides of other aromatic or fatty aromatic carboxylic acids such as oxyphenylacetic or phenylacetic acid.  This subject-matter does not appear in the Specification as accepted.