Patent GB-516851-A (GB)
Title: Improvements in the production of insoluble azo-dyestuffs
IPC: C09B39/00
Filed: 1938-07-27
Abstract: 516,851. Dyes; intermediates. COMPAGNIE NATIONALE DE MATIERES COLORANTES ET MANUFACTURES DE PRODUITS CHIMIQUES DU NORD REUNIES ETABLISSEMENTS KUHLMANN. July 27, 1938, Nbs. 22289 and 22290. Convention dates, July 27, 1937, and June 30, 1938. [Classes 2 (iii) and 15 (ii)] Insoluble azo dyestuffs are made in substance or on the fibre by coupling diazo compounds free from solubilizing groups other than the diazo group with condensation products of acylacetic esters with heterocyclic aminols of the general formula where X = either O, or S, and if X = O, a Z, or a Y, or a Y and a Z, or a Z and W, represent one or more NH 2 groups, and if X = S, a Z, or a Z and a Y, or a Z and W represent one or more NH 2 groups, and in which the benzene nuclei may be substituted by groups not capable of conferring solubility in water, such as alkyl, alkoxy, or aryloxy groups or halogen atoms. The acylacetic esters may be those derived from monobasic or polybasic acids, e.g., acetylacetic esters, benzoylacetic esters, or terephthaloylacetic esters. In examples: (1) cotton is padded with 5-acetoacetylamino-2- (p-acetoacetylaminophenyl)-benzoxazole and developed with the diazonium chlorozincate of o-nitraniline or 2:5-dichloraniline ; yellow shades are obtained; (2) cotton is padded with 6-acetoacetylamino - 5 - methyl - 2 - phenylbenzothiazole and developed with diazotized 2:5-dichloraniline; (3) cotton is padded with 6-acetoacetylamino-5- chloro-2-phenylbenzothiazole and developed with the diazo compound of 2:5-dichloraniline, o-nitraniline or p-chloro-o-nitraniline ; (4) cotton is padded with 6-acetoacetylamino-5- methoxy-2-phenylbenzothiazole and developed with diazotized 2:5-dichloroaniline ; (5) cotton is padded with 6-acetoacetylamino-2-(p<1>-acetoacetylaminophenyl)-benzothiazole and developed with diazotized 2:5-dichloraniline or o-chloraniline ; (6) cotton is padded with 5- acetoacetylamino-2-p<1>-phenylbenzothiazole and developed with diazotized 2:5-dichloraniline; (7) cotton is padded with the diacetoacetyl derivative of 5-methoxy-6-amino-2-(p<1>-aminophenyl)-benzothiazole and developed with diazotized 2:5-dichloraniline; (8) cotton is padded with 6-acetoacetylamino-2-phenylbenzothiazole and developed with diazotized 2:5-dichloroaniline ; (9) cotton is padded with 5-methoxy-6-acetoacetylamino-2-phenylbenzoxazole and developed with diazotized 2:5- dichloraniline ; and (10) m-nitro-p-toluidine is diazotized and coupled in -substance with 5- methyl - 6 - acetoacetylamino - 2 - phenylbenzoxazole. The shades on cotton from a large number of combinations are tabulated, the following additional diazo and coupling components being specified: diazo components:- 4-chlor-2-aminotoluene, 4-chlor-2-aminoanisole, 2-methoxy-4-benzoylamino-5-methylaminobenzene, 3-nitro-4-aminoanisole, 4<1>-methoxy-4- amino-diphenylamine, diaminodiphenyl-azo-3- amino-4-methoxytoluene, m-chlor- and nitroaniline, 2-chlor- and nitro-4-aminotoluene, p-nitraniline, 4-chlor-2-nitraniline, 2-nitro-4- amino-1:3-xylene, 5-chlor-2-aminotoluene, alphaaminoanthraquinone &c. ; coupling components :-6-chloro-5-acetoacetylamino-2-(p-acetoacetylaminophenyl)-benzoxazole, 5-acetoacetylamino- 2-(p-acetoacetylaminophenyl)-benzothiazole, 6- acetoacetylainino - 5 - methyl-2-phenyl-benzoxazole, 5-acetoacetylamino-2-(p-acetoacetylaminophenyl)-benzoxazole, 5-acetoacetylamino-2- phenyl-benzoxazole, 5-acetoacetylamino-2- phenyl-benzthiazole, 5-acetylamino-2-(p-acetoacetylaminophenyl)-benzoxazole, and 6-acetoacetylamino-2-phenylbenzothiazole. Specification 210,347, [Class 2 (iii)], is referred to. Heterocyclic bases.-A number of general methods for the preparation of heterocyclic bases of the above general-formulae are given. 2-p-Aminophenyl-benzoxazole is made by condensing o-nitrophenol with p-nitrobenzoyl chloride, and reduction and. cyclization with stannous chloride. 6-Amino-5-methyl-2-phenylbenzothiazole is'made by transforming 2-nitro- 4-methyl-1-chlorobenzene into the disulphide, partially reducing with glucose to give 2-nitro- 4-methyl-1-thiophenol, condensing with benzoyl chloride, and reducing to give 5-methyl-2- phenylbenzothiazole, nitrating and again reducing. 5-Chloro-6-amino-2-phenyl-benzothiazole is made by converting 2:5-dichloro'-1-acetylamino-4-nitrobenzene into the disulphide, re- 'ducing with glucose to form 1-chloro-2-acetylamino - 5 - nitro - 4 - thiophenol, condensing with benzoyl chloride, and reducing and hydrolyzing. 5 - Methoxy-6-amino-2-phenylbenzothiazole is similarly made from 1-acetylamino- 2-methoxy-4-nitro-5-chlorbenzene. 6-Amino-2- (p-aminophenyl)-benzothiazole is made by nitrating 2-(p-nitrophenyl)-benzothiazole and reducing. 5-Chlor and-methoxy-6-amino-2-(paminophenyl)benzothiazole are made by similar reactions from 1:4-dichloro-2-acetylamino-5- nitrobenzene and 2-nitro-4-methoxy-5-acetylamino-6-thiophenol.