Patent GB-425168-A (GB)
Title: The manufacture of water-insoluble azo-dyestuffs and of intermediate products therefor
IPC: C09B29/32
Filed: 1933-09-08
Abstract: 2-Acylacetaminoarylenethiazoles are prepared by condensing a 2-aminoarylenethiazole free from groups inducing solubility in water with an arylacetic ester in the presence or absence of a solvent such as chlorobenzene or xylene, the arylene thiazole may be derived from aminobenzene, aminonaphthalene, aminocarbazole, aminodiphenylene oxide, aminoacenaphthene or aminocumarone and the acyl radicle may be aliphatic or aromatic such as acetyl or benzoyl.  Azodyestuffs are prepared from the products by coupling them with a diazotized component free from groups inducing solubility in water in substance or on a substratum.  In examples the following 2-acylacetaminoarylenethiazoles are produced by condensation of 2-aminoarylenethiazoles with an acylacetic ester:--(1) acetoacetyl - 2 - aminobenzothiazole, (2) benzoylaceto - 2 - amino - 6 - ethoxybenzothiazole, (3) acetoacetyl - 2 - amino - 6 - chlorobenzothiazole, (4) acetoacetyl - 2 - amino - 6 - methoxybenzothiazole, acetoacetyl - 2 - amino - 6 - ethoxybenzothiazole, acetoacetyl - 2 - amino - 6 - methylbenzothiazole, acetoacetyl - 2 - amino - 6 - benzoylaminobenzothiazole, acetoacetyl - 2 - amino - 4 - chlorobenzothiazole, acetoacetyl - 2 - amino - 4 - chloro - 6 - methoxybenzothiazole, acetoacetyl - 2 - amino - (1<1> - 2<1>) - naphthothiazole, acetoacetyl - 2 - amino - (2<1> - 1<1>) - naphthothiazole, acetoacetyl - 2 - amino - 6<1> - methoxy - (1<1> - 2<1> - naphtho) - thiazole, 2 - acetoacetylamino - (9<1> - ethyl - 2<1> - 3<1> - carbazolethiazole, 2 - acetoacetylamino - 1<1> - 2<1> - cumaronethiazole acetoacetyl - 2 - amino - 3<1> - 4<1> - acenaphthenethiazole, acetoacetyl - 2 - amino coumaronethiazole. In further examples the following dyes are formed on cotton yarn in known manner:--1 - amino - 2 - methyl - 5 - chlorobenzene, 1 - amino - 2 - nitro - 4 - methylbenzene, 1 - amino - 2 - methyl - 4 - chlorbenzene or 1 - amino - 2 - chlorobenzene --> 2 - acetoacetylamino-6-ethoxybenzothiazole, 1-amino-2-methyl - 4 - chlorobenzene --> 2 - acetoacetylamino - (9<1> - ethyl - 2<1> - 3<1> - carbazole) - thiazole, 1 - amino - 2 - methyl - 5 - chlorobenzene --> acetoacetylamino - (3<1> - 4<1> - acenaphthene) - thiazole, 1 - methoxy - 2 - aminobenzene - 4 - sulphodiethylamide --> 2 - acetoacetylamino - (2<1> - 1<1> - naphtho) - thiazole, 4 - chloro - 2 - aminodiphenylether or 1-amino-2-nitro-4- methoxybenzene --> 2 - acetoacetylamino - 6<1> - methoxy - (1<1> - 2<1> - naphtho) - thiazole.  In example (11) the dye 1-amino-2-methyl-4-chlorobenzene --> 2 - acetoacetylaminodiphenyleneoxidethiazole.  In examples (12) and (13) printing pastes for cotton are prepared from (12) 2 - acetoacetylamino - (1<1> . 2<1> - naphtho) - thiazole and the diazoamino compound derived from diazotized 4-chloro-2-methoxy-1-aminobenzene and sarcosine or (13) 2 - acetoacetylamino - (2<1> - 1<1> - naphtho) - thiazole and the diazoamino compound derived from diazotized 4 - nitro - 2 - methoxy - 1 - aminobenzene and 1 - methylaminobenzene - 2 - carboxylic acid - 4 - sulphonic acid and aqueous caustic soda, neutral chromate solution, thiodiglycol and starch-tragacanth thickener.  The Specification as open to inspection under Sect. 91 refers also to the manufacture of acylacetyl derivatives of thiazoles other than arylenethiazoles and the manufacture therefrom of azo dyestuffs.  In examples acetoacetyl-2-aminothiazole, and 4 - methyl - 2 - aceto - (or benzoyl -) aminothiazole are prepared, and the dyestuffs are prepared in known manner on cotton.  2 - methoxy - 4 - nitro - 1 - aminobenzene -->2 - acetoacetylamino - 4 - methylthiazole, 4 - chloro - 2 - methyl - 1 - aminobenzene --> 2 - benzoylacetylamino-4-methylthiazole, 4 - methoxy - 2 - nitro - 1 - aminobenzene --> 2 - acetoacetylamino - 4 - phenylthiazole, 2 - methoxy - 5 - sulphodiethylamide - 1 - aminobenzene --> 2 - acetoacetylamino - 4 : 5 - diphenylthiazole, 2 - chloro - 4 - trifluoromethyl - 1 - aminobenzene --> 2 - acetoacetylamino - 4 : 5 - diphenylthiazole.  There are also examples illustrating the preparation of 5 - methoxy - 2 - acetoacetylaminobenzothiazole and 1 - methyl - 2 - acetoacetylaminobenzothiazole; the preparation of the following dyes in known manner on cotton 2 - amino - 4 - chlorodiphenylether --> 6 - methoxy - 2 - aceto - acetylaminobenzothiazole, 1 - amino - 2 - nitro - 4 - methoxybenzene--> 6 - methoxy - 2 - aceto - (or benzo - ) - acetylbenzothiazole, 1 - amino - 2 - methyl - 4 - (or - 5 - ) chlorobenzene --> 2 - acetoacetylamino - 6 - benzoylaminobenzothiazole, 1 - aminopyrene --> 6 - methoxy - 2 - acetylaminobenzothiazole, 2 - methoxy - 3 - aminofluorenone --> 2 - acetoacetylamino - 6 - ethoxybenzothiazole, a  - naphthylamine --> 2 - acetoacetylamino - 6 - ethoxybenzothiazole; the preparation of the dye 1-amino-2-methyl-5-chlorobenzene --> 2 - benzoylacetylamino - 6 - ethoxybenzothiazole in the presence of pyridine; and the preparation of printing pastes from 2 - acetoacetylamino - 6 - ethoxybenzothiazole and the diazoamino compound derived from diazotised 5 - chloro - 2 - methyl - 1 - aminobenzene and sarcosine or diazotised 4-nitro-2-methoxy - 1 - aminobenzene and 1 - methyl-aminobenzene-2-carboxylic acid - 4 - sulphonic acid.  This subject-matter does not appear in the Specification as accepted.