Patent GB-744877-A (GB)
Title: Improvements in benzothiazole-azoaniline compounds and their application to the dyeing or colouring of textile materials
Filed: 1953-10-29
Abstract: 2 - Amino - 6 - methylsulphonylbenzothiazole is prepared by adding a solution of bromine in acetic acid to a mixture of p-aminophenyl-methylsulphone and sodium thiocyanate in acetic acid, filtering the reaction product, dispersing it in water, boiling the mixture then adding alkali to pH6, cooling and filtering.  2 - Acetylamino - 6 - thiocyanobenzothiazole is prepared by passing chlorine into a mixture of aniline, ammonium thiocyanate and sodium acetate, filtering the product, boiling this with water, adding sodium acetate and treating the precipitate so obtained with acetic acid-acetic anhydride mixture.  2- Amino - 6 - ethylsulphonybenzothiazole is prepared by refluxing 2-acetylamino-6-thiocyanobenzothiazole with sodium sulphide in alcohol, adding ethyl iodide, refluxing further, pouring the mixture into water, filtering off 2-acetylamino-6-ethylthiobenzothiazole (which may be hydrolysed to 2-amino-6-ethylthiobenzothiazole) oxidizing with hydrogen peroxide in acetic acid and hydrolysing with aqueous hydrochloric acid.  2-Acetylamino-6-, n- or iso-propyl-, n- or iso-butyl- or allyl-thiobenzothiazoles and 2-amino-6-, n- or iso-propyl-, n- or iso-butyl-, or allyl-sulphonylbenzothiazoles are similarly prepared.ALSO:The invention comprises monoazo dyes of formula:-<FORM:0744877/IV(c)/1> wherein R is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, a hydroxyalkyl group of 2 to 4 carbon atoms, an alkoxyalkyl group of 3 to 4 carbon atoms, a cyanoalkyl group of 3 to 5 carbon atoms, a b -acetoxyethyl, carbomethoxymethyl, carboethoxymethyl, b -carbomethoxyethyl or b -carboethoxyethyl group, R1 is the same as R or a b , b  - difluoroethyl, b , b -difluoron-propyl, g , g -difluoropropyl, g , g -difluoro-n-butyl, d , d -difluoro-n-amyl, b , b , b -trifluoroethyl, g , g , g -trifluoropropyl or d , d , d -trifluorobutyl group, Y is a hydrogen atom, a methyl ethyl, methoxy or ethoxy group, X is the same as Y or a bromine or chlorine atom, or an acetylamino, propionylamino, or n-butyrylamino group, and Z is an allyl group, or an alkyl group of 1 to 4 carbon atoms.  The dyes are primarily used for colouring textile materials made of or containing a cellulose carboxylate derived from an aliphatic carboxylic acid of 2-4 carbon atoms. Specified cellulose carboxylates are hydrolyzed and unhydrolyzed cellulose acetate, cellulose propionate, butyrate, acetate propionate or acetate butyrate.  When applied to the aforesaid materials the dyes give scarlet, red, pink, reddish-violet, violet and blue dyeings.  The dyes also colour wool, silk, nylon, polyethylene terephthalate and modified polyacrylonitrile fibres. The dyes are prepared by diazotizing a 2-amino-6-alkyl or allyl-suphonylbenzothiazole (see Group IV(b)) and coupling with a suitable N-substituted aniline.  The diazotization and coupling are carried out in mineral or organic acids of mixtures thereof, sulphuric acid being preferred.  In examples the following diazo components are specified, 2-amino-6-methyl-, ethyl-, n- or iso-propyl-, n- or iso-butyl, or allyl-sulphonylbenzothiazoles. Azo components specified are:-N-methyl-, N, N-di-b -hydroxyethyl-, N-b -hydroxyethyl-, N-b - hydroxyethyl-N-n-butyl, N-b -hydroxyethylN-n-propyl-, N-b -methoxyethyl-N-ethyl-, N-b -ethoxyethyl-N-b -hydroxyethyl-, N-b - cyanoethyl-N-b -hydroxyethyl-, N-b -cyanoethyl-, N, N-di-b -cyanoethyl-, N-b -cyanoethyl-N-b -methoxyethyl- N-b -cyanoethylNg  -hydroxypropyl-, N-d -cyanobutyl-N-b -hydroxyethyl - N - b  - cyanoethyl -, N - b  - ethoxyethyl -, N - b  - cyanoethyl - N - b  - hydroxypropyl - , N - b - acetoxy - ethyl-N-b -cyano-, or hydroxy-ethyl, N-b -carbomethoxyethyl-N-b -cyanoethyl-, N-carbomethoxymethyl-N-b -cyanoethyl-, N-b -carboethoxyethyl-N-b -cyanoethyl-, N-carboethoxy methyl-N-b -hydroxyethyl-, N, N-dib -carbomethoxyethyl-, N-b -carbomethoxyethyl - N - b  - hydroxyethyl - N, N - di - b  - carbomethoxyethyl - N - b  - carbomethoxyethyl-N-ethyl-, N-b -carboethoxyethyl-N-g -cyanopropyl, N-b -carboethoxyethyl-N-b -hydroxyethyl-, N-b , b -difluorethyl-N-b  -hydroxyethyl-, N-b , b -difluoropropyl-N-b -hydroxyethyl, N-g , g -difluoropropyl-N-b -hydroxyethyl-, N-g , g -difluorobutyl-N-b -hydroxyethyl, N-b , b , b ,-trifluoroethyl-N-b -hydroxyethyl, N-g , g -difluoro-n-amyl-N-b -hydroxyethyl, N-g , g , g -trifluoropropyl-N-b -hydroxyethyl-, N-d , d , d -trifluorobutyl-N-b -hydroxyethyl, N-b , b -difluoroethyl-N-n-butyl-, N-b , b -difluoroethyl-N-b , g -dihydroxypropyl-, N-g , g -difluoropropyl-N-b -cyanoethyl-, N-b , b -difluoroethyl-, and N-b -b , b -trifluoroethyl-anilines; N-b -cyanoethyl -N-b -hydroxyethyl-, N-b , g -dihydroxypropyl-N-ethyl-, N, N-di-b -hydroxyethyl-, N-b -hydroxyethyl-N-ethyl-, N-b -hydroxyethyl-, N, N-di-b -methoxyethyl-, N-b , b -difluoroethyl-N-b -hydroxyethyl-, and N-b -b  -b -trifluoro ethyl-N-b -hydroxyethyl-m-toluidines; N-b -cyanoethyl-N-b , g -dihydroxypropyl-o-toluidine; N-b -hydroxyethylN-b -cyanoethyl-3-bromo-, N-b -hydroxyethyl -N-b -cyanoethyl-2-methoxy-5-bromo-, N, N-di-b -hydroxyethyl-2-methoxy-5-bromo-N-b  - hydroxyethyl-N-b -cyanoethyl-3-chloro-, N, N - di - b  - hydroxyethyl - 3 - chloro - N, N-di - b  - hydroxyethyl - 2 - methoxy - 5 - chloro-, N, N-di-b -hydroxyethyl-2-ethoxy-5-chloro, N-b -hydroxyethyl-N-b -cyanoethyl-2-or-3-ethyl-, methoxy- or ethoxy-, N, N-di-b -hydroxyethyl-3-acetylamino-, N, N-di-b , b -difluoroethyl-2-ethoxy-5-acetylamino-, N, N-di-b -hydroxyethyl-2-methoxy-5- acetylamino, N-b -hydroxyethyl-N-b -cyanoethyl-3-propionylamino-, N-b -hydroxyethyl-3-butyrylamino-, N, N-di-b -hydroxyethyl-2:5 -dimethoxy-or 2-methyl-5-methoxy- and N, N-di - b  - cyanoethyl - 2 - methoxy - 5 - methyl-anilines