Patent GB-548902-A (GB)
Title: Manufacture of arylazo dye compounds and material coloured therewith
IPC: D06P3/34
Filed: 1940-07-01
Abstract: 548,902. Dyes and dyeing. KODAK, Ltd. July 1, 1940, No. 11085. Convention date, July 1, 1939. Drawings to Specification. [Classes 2 (iii) and 15 (ii)] Azo dyes are obtained by coupling a diazotized non-sulphonated aniline derivative, substituted in 4-position by NO  2  or phenylazo and further substituted or not, with Py-tetrahydroquinoline or a derivative thereof which may be substituted in the 1-position by alkyl or substituted alkyl (other than carboxy-substituted alkyl), once in the 3- and 1- or 4-positions by alkyl, substituted alkyl, amino or substituted amino and in place of hydrogen atoms remaining in the 2-, 3- and/or 4-positions by alkyl or hydroxyalkyl, in the 5-position by methyl or methoxy and in the 7- and/or 8-positions by chlorine, methyl or methoxy, with the exclusion of those dyestuffs containing at least twice the group SO  2 - R<SP>4</SP>, wherein R<SP>4</SP> represents alkyl, aralkyl or aryl, and of those derived from a diazo component substituted by a carboxylic acid ester group. The products, as well as the corresponding dyestuffs derived from a non- sulphonated diazotized nitronaphthylamine or any non-sulphonated diazotized nitroaniline or phenylazoaniline, are suitable for dyeing wool, silk and materials of an organic derivative of cellulose, some of the latter dyeings being valuable dischargeable blue shades, fast to light and to acid fading. Examples relate to the preparation or use of the dyestuffs, (1) 4-nitro- 2 - chloroaniline # 1 - # -hydroxyethyl - tetrahydroquinoline, which dyes cellulose acetate artificial silk rubine ; (2) 2:4 - dinitroaniline # 1 - #:γ - dihydroxy-propyl - tetrahydroquinoline, which dyes cellulose acetate artificial silk violet ; (3) 2:4 - dinitro - 6 - chloroaniline # 1 - #:γ - dihydroxypropyl - 7 - methyl - tetrahydroquinoline, which dyes cellulose acetate artificial silk blue ; (4) 2:4 - dinitro - 6 - bromoaniline # 1 - #- hydroxy - γ - chloropropyl - 7 - methyl - tetrahydroquinoline, which dyes cellulose acetate artificial silk blue ; (5) picramide # 1 - # - sulphoethyl - 7 - methoxy - tetrahydroquinoline, which dyes cellulose acetate artificial silk blue ; (6) 4 - nitro - 2 - aminophenol # 1 - # - methoxy - ethyl - 2:2:4 - trimethyl - 8 - chloro - tetrahydroquinoline, which dyes cellulose acetate artificial silk magenta; (7) 2:4 - dinitro - 6 - chloroaniline# 1:8 - dimethyl - 4 - di - # - hydroxyethylamino - tetrahydroquinoline, which dyes cellulose acetate artificial silk blue ; (8) 2:4-dinitro-6-cyanoaniline # 1 - #<SP>1</SP> - hydroxy - # - ethoxyethyl - 3 - acetylamino - 8 - methyl - tetrahydroquinoline, which dyes cellulose acetate artificial silk reddish blue. A table is also given showing the shades obtainable on cellulose acetate artificial silk with the dyestuffs from various combinations of components, additional diazo components being 4 - nitroaniline, 4 - nitro - 3 - chloroaniline, 4 - nitro - 2 - or 3 - bromoaniline, 4 - nitro - 2:5 - dichloro - or dibromo - aniline, 5 - nitro - 2 - aminophenol and its 3 - chloro - and 3 - bromo - derivatives, 4 - aminoazobenzene and 2:4 - dinitro - 1 - aminonaphthalene, and additional coupling components being the 7- chloro, 8 - methoxy, 1 - methyl - 7 - chloro, 2:2:4 - trimethyl, 1 - # - hydroxyethyl - 2:2:4 - trimethyl, 1 - y - hydroxypropyl, 1 - y - methoxy - # - hydroxypropyl, 1 - y - chloro - # - hydroxypropyl, 1 - # - sulphatoethyl, 1 - # - sulphoethyl, 1 - # - methoxyethyl - 8 - niethyl. 1 - # - or y - hydroxypropyl - 7 - methyl, 1 - #:γ - dihydroxypropyl - 5 - methyl, 1 - #:γ - dihydroxypropyl - 2:2:4 - trimethyl - 7 - methoxy, 1 - #:γ - dihydroxypropyl - 2:2:4 - trimethyl - 5:8 - dimethoxy, 1 - ethyl - 4 - amino, 2 - ethyl and 4 - methylamino derivatives of tetrahydroquinoline. Specifications 485,336 and 548,903 are referred to. Tetrahydroquinoline derivatives as above are obtained by catalytic hydrogenation of the corresponding quinoline derivatives, which are obtainable from corresponding aniline derivatives by the Skraup synthesis or by reaction with the appropriate ketone. Hydroxyalkyl substituents in the 1-position may be introduced by alkylation, e.g. with alkylene oxides or chlorhydrins. The Specification as open to inspection under Sect. 91 comprises also the manufacture and' use of the dyestuffs, (a) 4-aminoacetophenone # tetrahydroquinoline or various derivatives thereof, (b) 2:4 - dinitro - 6 - fluoraniline # 7 - methyl-tetrahydroquinoline substituted in the 1-position by. the group -CH 2 -(CH-OH) 4 -CH 2 - OH, (c) 2:4 - dinitro - 3:6 - dichloro - aniline # 1 - γ - hydroxypropyl - 5 - methyl - tetrahydroquinoline, (d) the corresponding nuclearsulphonated dyestuffs, which are suitable for dyeing wool and silk. 4 - Nitro - 2 - and 3 - fluoro - anilines, 4 - nitro - 2:5 - difluoro - aniline and 2 - amino - 3:5 - dinitro - phenylmethylsulphone are also specified as diazo components. This subject-matter does not appear in the Specification as accepted.