Patent GB-761792-A (GB)
Title: Improvements in and relating to nitro-thiazole monoazo dyestuffs
IPC: C09B29/033
Filed: 1954-02-15
Abstract: N,N - di - b  - hydroxyethyl - m - acetyl - and propionyl - aminoanilines are made by treating m-acetyl- or propionyl-aminoanilines with ethylene oxide under pressure at 180 DEG C.  N,N-di-b -hydroxyethyl and N-ethyl-N-b ,g -dihydroxypropyl - 2 - methoxy - 5 - acetylaminoanilines, N - n - butyl - N - b  - hydroxyethyl -, N - b  - hydroxypropyl - and N - b ,g  - dihydroxypropyl-and N-sec. and iso-butyl-N-b ,g -dihydroxypropyl-m-acetylaminoanilines and N,N-di-b -hydroxyethyl - 3,5 - diacetylaminoanilines are made in a similar way from appropriate anilines or mono-N-substituted-anilines and alkylene oxides or chlorhydrines. N-n-butyl-m-acetylaminoaniline is made by treating n-butyl bromide in n-butanol with m-aminoacetanilide and N - ethyl - 2 - methoxy - 5 - acetylaminoaniline is made by treating 2 - methoxy - 5 - acetylaminoaniline with ethyl bromide. 3,5-Diaminonitrobenzene is made by reducing 1,3,5-trinitrobenzene with alcoholic ammonium sulphide and is then diacetylated and reduced with hydrogen and Raney nickel to give 3,5-diacetylaminoaniline.  The acylamino-N-substituted anilines are dyestuff coupling components, (c.f. Group IV (c)). Specification 735,654 is referred to.ALSO:The invention comprises dyestuffs of formula:-<FORM:0761792/IV(b)/1> where R is a hydroxyalkyl group of 2 to 5 C atoms, R1 is an alkyl group of 1 to 6 C atoms or a hydroxyalkyl group of 2 to 5 C atoms, X is H, MeO, EtO3, CH3CO2, C2H5CO or C3H7CO, Q is H, CH3CO, C2H5CO or C3H7CO, Y is an alkyl group of 1 to 3 C atoms, 2 is H, an alkyl group of 1 to 6 C atoms, CN, CF3 or a phenyl or m- or pnitrophenyl group and one of Q and X must be H.  Preferred dyestuffs are those where Q is an acylamino group when X is H and X is acylamino when Q is H. They may be made by diazotizing an appropriate 2 - amino - 5 - nitrothiazole and coupling, advantageously in the presence of sodium acetate, with the necessary acylaminobenzene.  Specified thiazoles are 2 - amino - 5 - nitro - and 2 - amino - 4 - methyl-, -ethyl-, n-butyl-, -n-hexyl-, -cyano-, -trifluoromethyl-, -phenyl- and -m- and -p-nitro-phenyl-5-nitro-thiazoles. 2-amino-5-nitro-thiazole is preferred.  Specified groups for R and R1 are b -hydroxyethyl, b - and g -hydroxypropyl, b :g -dihydroxypropyl, b  - methyl - b  : g  - dihydroxypropyl, d  - hydroxybutyl, e  - hydroxyamyl and d  : e  - dehydroxyamyl groups.  Specified groups for Z and R1 are methyl, ethyl, n - and iso - propyl, n - butyl, n - amyl and n - hexyl groups. Methyl, ethyl and n - propyl groups are specified for Y.  The dyestuffs dye textiles made of or containing a cellulose alkyl carboxylate of 2 to 4 C atoms in the acid groups thereof, e.g. hydrolysed and unhydrolysed cellulose acetate, propionate, butyrate, acetate propionate and acetate butyrates, wool, silk, nylon, polyethylene terephthalate and modified polyacrylo-nitriles in reddish blue, blue, greenish-blue and bluish-green shades.  The dyestuffs are generally applied to the textiles as an aqueous dispersion at about 45-55 DEG C. with final treatment at 80-90 DEG C. Examples and tables are provided illustrating the preparation of the dyestuffs and their use in dyeing textiles, diazo components used additional to those specified above being 2 - amino - 4 - n - propyl - and n - amyl - 5 - nitrothiazoles the coupling components (see Group IV(b)) for their preparation) being N - n - butyl - N - b 1g  - dihydroxypropyl - and b  - hydroxypropyl - and - ethyl -, N - sec - and iso - butyl-, -ethyl - and -n- and - iso - propyl - N - b ,g  - dihydroxypropyl-, N-ethyl - N - b  - methyl - b ,g  - dihydroxypropyl-, N,N - di - b  - hydroxyethyl and -b - and -g -hydroxypropyl-, N-methyl - N - b  - hydroxyethyl - and - g  - hydroxypropyl-, N-ethyl-N-d -hydroxybutyl-, -e -hydroxyamyl-, -b -hydroxypropyl- and -d , e -dihydroxyamyl- and N-n-amyl-and -n-hexyl-N- b -hydroxyethyl-m-acetylaminoanilines, N,N - di - b  - hydroxyethyl - and N - ethyl - N - b ,g  - dihydroxypropyl - 2 - methoxy - 5 - , N,N - di - b  - hydroxyethyl - 2,5 - and - 3,5 - and N,N - di - b  - hydroxypropyl - 2,5 - di - acetylamino - anilines, N1N - di - b  - hydroxyethyl - 215 - and - 3,5 - di - n - and - di - b  - hydroxypropyl - m - butyrylaminoanilines and N1 - n - butyl - N - b  - hydroxyethyl - and N,N - dihydroxyethyl - m - propionylaminoanilines.  In the examples coupling is effected in the presence of a mixture of acetic and propionic acids and diazotization is effected with nitrosyl sulphuric acid (see Group III). Specification 735.654 is referred to.ALSO:Nitrosyl sulphuric acid is made by adding sodium nitrite in portions to concentrated sulphuric acid, allowing the temperature to rise to 65 DEG C., cooling to 5 DEG C. and adding a mixture of propionic and acetic acids, allowing the temperature to rise to 15 DEG C. and maintaining the mixture at this temperature whilst the residue of nitrite is added.  Alternatively after the temperature rise to 65 DEG C. the mixture may be cooled to -5 DEG  to -10 DEG C., crushed ice added so that the temperature does not exceed 10 DEG C., the mixture again cooled to -5 DEG  to -10 DEG C. and 50 per cent sulphuric acid added dropwise at -5 DEG C.  The acid is used for diazotizing amines, (see Group IV(c)). Specification 735,654 [Group IV(b)] is referred to.