Patent GB-548903-A (GB)
Title: Improvements in azo compounds and material coloured therewith
IPC: C09B29/08
Filed: 1940-07-01
Abstract: 548,903. Dyes. KODAK, Ltd. July 1, 1940, Nos. 11086 and 11087. Convention dates July 1, 1939 and Dec. 16, 1939. [Classes 2 (iii) and 15 (ii)] Monoazo dyes are obtained by coupling on the benzene nucleus (a) a mono-or di-N- substituted phenylamine or (b) an N-substituted Py-tetrahydroquinoline or (c) an N-substituted phenmorpholine, with a diazotized amine of the general formula shown in Fig. 1 wherein Y represents H, halogen, alkyl, substituted alkyl, alkoxy or nitro and R 1  and R 2  represent H, alkyl, substituted alkyl, cycloalkyl, aryl or a heterocyclic group and may be the same or different. The products free from sulphonic or carboxylic acid groups are suitable for dyeing organic derivatives of cellulose, wool or silk, while those containing such groups are suitable for dyeing wool or silk. The use for dyeing organic derivatives of cellulose of the corresponding dyestuffs in which Y represents SO  2 NR 1 R  2  is also claimed. Specified alkyl groups are methyl, ethyl, propyl, butyl and amyl and alkenyl, e.g. allyl, groups are included. Specified substituted alkyl groups are #- hydroxyethyl, #-or γ-hydroxypropyl, #:γ-dihydroxypropyl, #-methoxyethyl, #-ethoxyethyl, #-chloroethyl, #-sulphoethyl, #- or γ-sulphopropyl, #-sulphatoethyl, #- or γ-sulphatopropyl, #-phosphatoethyl, γ-phosphatopropyl, #-phosphitoethyl and furfuryl. Specified alkoxy groups are methoxy, ethoxy, propoxy, butoxy, #-methoxyethoxy and #-ethoxyethoxy. Specified cycloalkyl groups are cyclobutyl, cyclohexyl and cycloheptyl. The preferred tetrahydroquinoline and phenmorpholine derivatives are those in which the N-substituent is an alkyl or substituted alkyl group, hydrogen atoms in the 3-and 4-positions of the tetrahydroquinoline nucleus or the 3-position of the phenmorpholine nucleus may be replaced by alkyl or amino (including alkylamino or acylamino) groups, any remaining hydrogen atoms in the 2-, 3- or 4- positions of the tetrahydroquinoline nucleus or the 2- or 3- positions of the phenmorpholine nucleus may be replaced by alkyl, and the 7- or 8 - position may be replaced by alkyl, substituted alkyl or alkoxy. Specified acyl groups are furoyl, formyl, acetyl, propionyl, butyryl, benzoyl, naphthoyl, and palmityl. Examples (1) to (4) relate to the production of the dyestuffs, (1) 5-nitro-2-aminobenzenesulphonamide # N:N- di-(#-hydroxyethyl)- aniline, (2) 5 - nitro-2-aminobenzenesulphon - methylamide # N - ethyl - N - # - hydroxyethylaniline, (3) 5-nitro-2-aminobenzenesulphonanilide # 3 - chloro - N:N - di (# - hydroxyethyl) - aniline, (4) (5) - nitro - 3 - bromo - 2 - aminobenzenesulphonamide # N:N - di - (# - hydroxyethyl) - aniline. Example (5) relates to the use for dyeing organic derivatives of cellulose of the dyestuff, 4-nitroaniline-2:6- di - sulphondimethylamide # N - glycerylcresidine. Examples (6) to (18) relate to the production of the dyestuffs, (6) 5-nitro-3-methoxy-2- aminobenzenesulphonamide # 3 - chloro - N - ethyl - N - 8 - sulphatobutyl - aniline, (7) 2:4 - dinitroaniline - 6 - sulphonethylamide or the corresponding methylamide, #- hydroxyethylamide, dibutylamide or sulphoethylamide# N - glyceryl - cresidine, 3:6 - dimethoxy - N - glyceryl - aniline, N - ethyl - N - glyceryl - aniline or 3 - carbamide - 6 - methoxy - N:N - di - (#- hydroxyethyl) - aniline, (8) 2:4 - dinitroaniline - 6 - sulphonmethylamide # N:N - di - (# hydroxyethyl) - m - toluidine, N - allyl - m - toluidine, N - cyclohexyl - - m - toluidine, N - tetrahydr ofurfuryl - m - toluidine, N:N - di - (# - methoxyethyl) - m - toluidine or N:N - di - (# - hydroxypropyl) - m - toluidine, (9) 2:4 - dinitroaniline - 6 - sulphon - # - methoxyethylamide # 2 - ethoxy - 5 - acetylamino - N - ethyl - N - glyceryl - aniline, 3 - formylamino - N - ethyl - aniline, 3 - lactylamino - N:N - di - (# - hydroxyethyl) - aniline, 2 - ethoxy - 5 - butyrylamino - N - ethyl - N - glyceryl - aniline, 2 - chloro - 5 - benzoylamino - N - # - hydroxyethyl - aniline, 2 - methyl - 5 - furoylamino - N - ethyl - N - glyceryl - aniline, 2 - ethoxy - 5 - palmitylamino - N - ethyl - N - glyceryl - aniline, 3 - carbamido - N - ethyl - N - glyceryl - aniline, 2 - ethoxy 5 - cyanoacetvlamino - N - ethyl - N - glyceryl - aniline or 3 - methylsulphonamino - N - # - hydroxyethylaniline, (10) 2:4 - dinitroaniline- 6 - sulphonethylamide # 7 - methyl - N - glyceryl - phenmorpholine, (11) 2:4 - dinitroaniline - 6 - sulphon - # - hydroxyethylamide # 2:7 - dimethyl - N - y - hydroxypropyl - phenmorpholine, (12) 2:4 - dinitroaniline - 6 - sulphonpropylamide # 3 - hydroxy - 7 - methyl - N - glyceryl - tetrahydroquinoline, (13) 2:4 - dinitroaniline - 6 - sulphonbutyl - amide # 7 - methoxy - N - # sulphoethyl - tetrahydroquinoline, (14) 2:4 - dinitroaniline - 6 - sulphoncyclohexylamide # 4 - methyl - N - ethyl - tetrahydroquinoline, (15) 4 - nitroaniline - 6 - sulphonallylamide # 3 - methyl - N - # - methoxyethyl - tetrahydroquinoline, (16) 4 - nitro - 2 - chloroaniline - 6 - sulphonanilide # 3 - methyl - N - # - hydroxyethyl - tetrahydroquinoline, (17) 4 - nitro - 2 - methoxy - aniline - 6 - sulphonglycerylamide # 3 - amino - N - y - hydroxypropyltetrahydroquinoline, (18) 2:4 - dinitroaniline - 6 - sulphonethylamide # 7 - methyl - N - glyceryl - tetrahydroquinoline. A table is also given showing the shades obtainable on cellulose acetate materials with the dyestuffs from various combinations of components ; additional diazo components are 5 - nitro - 2 - aminobenzenesulphondimethyl - amide and the corresponding di-(#-hydroxyethyl) amide, tetrahydrofurfurylamide cetylamide and n-amylamide, 5-nitro- 3-chloro-or bromo - 2 - aminobenzene - sulphonmethyl - amide, 2:4 - dinitroaniline - 6 - sulphonallyl - amide and the corresponding methylethylamide, 5 - nitro - 3 - methyl - 2 - aminobenzenesulphonpropylamide, 4 - nitroaniline - 2:6 - di - sulphon - ethyl - or butyl - amide, 4 - nitro - 2 - chloroaniline - 6 - sulphonglycerylamide and 4 - nitro - 2 - methylaniline - 6 - sulphonethyl - amide ; additional phenylamine coupling components are diphenylamine, N:N-dimethylaniline, N - methyl - N - propylaniline, N - methyl - N - butylaniline, N - ethyl - m - toluidine, N - # - hydroxyethyl - aniline, N - # - hydroxyethyl - m - toluidine, N - # - sulphoethyl - N - propyl - m - toluidine, N - ethyl - N - glyceryl - m - toluidine, N - # - hydroxyethyl - m - anisidine, N - ethyl - N - glyceryl - m - anisidine, N:N - dibutyl - cresidine, N - ethyl - N - glyceryl - cresidine, N - sulphato - ethyl - N - butyl - cresidine, N - # - hydroxy - ethyl - N - glyceryl - cresidine, N - # - hydroxy - ethyl - m - chloroaniline, N - # - sulphatoethyl - N - butyl - m - chloraniline, 5 - chloro - 2 - methoxy - N - # - hydroxyethyl - aniline, the 2 - ethoxy - 5 - acetylamino, 2 - ethoxy - 5 - butyrylamino, 2 - methyl - 5 - furoylamino, 2 - ethoxy - 5 - palmitylamino- 3 - carbamido and 2 - methoxy - 5 - chloro derivatives of N - ethyl - N - glyceryl - aniline, 2 - ethoxy - 5 - cyanacetylamino - N - glyceryl - aniline, 5 - bromo - 2 - methoxy - N - ethyl - N - sulphatoethyl - aniline, 2:5 - dimethoxy - N - butyl- N - sulpho - or sulphato - ethyl - aniline and 2:5 - dimethyl - N - ethylaniline ; additional tetrahydroquinoline coupling components are the 7 - methoxy - N - glyceryl, 7 - methyl - N - γ - methoxy - # - hydroxypropyl, 7 - ethoxy - N - butyl, N - ammonium sulphatoethyl, N - # - hydroxyethyl, 5 - methyl - N - glyceryl, 5 - methyl - N - # - hydroxyethoxyethyl, 7 - ethyl - N - glyceryl, 5 - propyl - N - glyceryl, 7 - hydroxymethyl - N - glyceryl, 7 - bromo - N - sodium phosphatoethyl, N - glyceryl and 7 - propyl - N - # - hydroxyethyl derivatives of tetrahydroquinoline; additional phenmorpholine coupling components are the 2:5:7- trimethyl - N - glyceryl, 2 - ethyl - N - glyceryl, 3 - ethyl - 7 - methoxy - N - # - hvdroxypropyl, 7 - ethoxy - N - # - chloroethyl, 7 - chloro - N - glyceryl, 5 - methyl - N - glyceryl, 2:5 - di - methyl - N - glyceryl, 7 - propoxy - N - glyceryl and 7 - methoxy - N - glyceryl derivatives of phenmorpholine. Specifications 243,737, [Class 2 (iii], 419,945, 454,445, 526,007 and 548,902 are referred to. Amines of the general formula shown in Fig. 1 are obtainable by treating 4-nitroaniline or the corresponding derivative thereof with chlorosulphonic acid and treating the product with ammonia or an amine of the formula NHR 1 R 2 ; the monosulphonamides are also obtainable by treating the corresponding 5- nitro - 2 - chlorobenzenesulphonamides with alcoholic ammonia. 2:4 - Dinitroaniline - 6 - sulphonethylamide is obtainable by the action of ethyl sulphate on 2:4-dinitroaniline-6-sulphonamide in methyl alcohol. Tetrahydroquinoline derivatives, referred to above, are obtainable by hydrogenating the corresponding quinoline derivatives in presence of nickel or a like hydrogenation catalyst and N- substituting the products, the quinoline derivatives being obtainable by various modifications of the Skraup synthesis. NGlyceryl-aniline derivatives are obtained by reaction of the corresponding substituted aniline with glycerol- α-monochlorhydrin at 140-150‹C. in presence of sodium bicarbonate. 3- Carbamido - 6 - methoxy- N: N-di-(#-hydroxyethyl)-aniline is obtained by reaction of 3- carbamido - 6 - methoxyaniline with ethylene chorhydrin or ethylene oxide. 3 - Chloro N - ethyl - N - # - sulphatobutyl - aniline is obtained by treating with chlorosulphonic acid in carbon tetrachloride the product of reaction of α:#-butylene chlorhydrin with 3-chloro-N-ethyl-aniline, obtained by treatment of 3-chloroaniline with ethyl sulphate ; other specified N-sulphatoalkyl aniline derivatives are obtainable by analogous methods. NAllyl-m-toluidine. is obtained by reaction of allyl chloride with m-toluidine; the N- cyclohexyl, N-tetrahydrofurfuryl, and N-di- (#-methoxyethyl) derivatives of m-toluidine are obtain