Patent GB-546017-A (GB)
Title: Manufacture and use of new azo dyes
IPC: C09B39/00
Filed: 1940-07-01
Abstract: 546,017. Dyes and dyeing. KODAK, Ltd. (Eastman Kodak Co.) July 1, 1940, No. 11084. [Classes 2 (iii) and 15 (ii)] Azo dyes are obtained by coupling a diazo compound with a Py-tetrahydroquinoline derivative having an acylamino group in the 5- and/ or 7-position. Specified acyl groups are formyl, acetyl, dimethylaminoacetyl, sulphoacetyl, propionyl, butyryl, oleyl, benzoyl, furoyl, tetrahydrofuroyl, lactyl, -COOR (wherin R represents alkyl, cycloalkyl, aralkyl or aryl), -CO.NH 2  and - CO.NH.CH 3 . The tetrahydroquinoline may be substituted in the 1-position by alkyl or substituted alkyl, by a short chain unsaturated hydrocarbon group such as allyl, propenyl, -CH 2 .CH 2 .- CH=CH 2  or -CH 2 .CH 2 .CH 2 .CH=CH 2 , by cycloalkyl, or by phenyl or substituted phenyl and may be substituted once or twice in each of the positions 2, 3 and 4 by alkyl or substituted alkyl, alkoxy or hydroxy and in the 5- and 8- position by halogen, hydroxy, alkyl or substituted alkyl, alkoxy or substituted alkoxy, amino or substituted amino, including acylamino. Specified substituted alkyl groups are #-hydroxyethyl, #- or γ-hydroxypropyl, # : γ- dihydroxypropyl, #-methoxyethyl, #-ethoxyethyl, #-chloroethyl, #-sulphoethyl, #- or γ- sulphopropyl, #-sulphatoethyl, #-cyanoethyl, γ-cyanopropyl, #- or γ- sulphatopropyl, #- phosphatoethyl, γ-phosphatopropyl, #-phosphitoethyl, furfuryl and substituted furfuryl. Specified alkoxy groups are methoxy, ethoxy, propoxy, butoxy, #-methoxyethoxy and #- ethoxyethoxy. Specified cycloalkyl groups are cyclobutyl, cyclohexyl and cycloheptyl. Specified substituted amino groups are methylamino, ethylamino, isopropylamino, butylamino, glycerylamino, diethylamino, methylethylamino, furfurylamino, tetrahydrofurfurylamino, benzylamino, phenylethylamino, anilino, 4- ethoxyanilino, 2-toluidino, cyclohexylamino, cycloheptylamino, #-methoxyethylamino, #- sulphoethylamino, #-sulphatoethylamino, #- hydroxyethylamino, γ-hydroxypropylamino and ethyl-#-hydroxyethyl-amino. The products are more particularly suitable,for dyeing wool, viscose and cotton or for dyeing organic derivatives of cellulose according as they do or do not carry nuclear sulphonic acid groups. The dyeings are fast to light and to washing and those obtainable on cellulose acetate artificial silk are readily dischargeable. Examples relate to the production of the dyestuffs, (1) 4-aminoacetophenone # 7-acetylamino tetrahydroquinoline or its 1-allyl - or 3-methoxy derivative or 5-acetylamino - 1-tetrahydrofurfuryltetrahydroquinoline ; (2) nitroaniline # the 7-formylamino - 1-# hydroxyethyl-, 7-acetylamino - 1-phenyl-, 7-acetylamino - 3-methyl- or 7-acetylamino-5-chloro - derivatives of tetrahydroquinoline ; (3) 4-nitro-2-fluoroaniline # the 5-propionylamino - 1-# : γ- dihydroxylpropyl-, 5-propionylamino-3 - hydroxy-, 5 - formylamino - 3 - methoxy- or 5- acetylamino - 8 - chloro - derivatives of tetrahydroquinoline ; (4) 4-nitro-2-chloroaniline # the 7-lactylamino - 1-methyl-, 7-acetylamino -1 - methyl - 8 - ethoxy - or 7 - acetylamino - 4 - ethyl derivatives of tetrahydroquinoline ; (5) 4-nitro-2-bromoaniline # the 7-methyl - 5-butyrylamino-1-#-sulphoethyl-, 5 : 7 di- (acetylamino) - or 7-acetylamino-5-methoxyderivatives of tetrahydroquinoline ; (6) 5-nitro- .2 - aminophenyl # the 7 - tetrahydrofuroylamino - 1-# - hydroxypropyl- or 7 - acetylamino - 5 - hydroxy - derivatives of tetrahydroquinoline ; (7) 2 : 4 - dinitroaniline - the 7 - ureido- 1-# : y - dihydroxypropyl - 3 - hydroxy - 4 - methyl- or 5 - ureido - 1-- methyl - 8 - hydroxyderivatives of tetrahydroquinoline ; (8) 2 : 4- dinitroaniline substituted in 6 - position by a chlorine, fluorine, bromine, or iodine atom or a methoxy, hydroxy, acetyl, methylsulphone or carboxylic ester or amide group # the ammonium salt of the sulphuric acid ester of 7-ureido -1- γ-hydroxypropyl - tetrahydroquinoline ; (9) 2 : 4 - dinitroaniline - 6 - sulphonethylamide # the 5-acetylamino-1-#-hydroxyethyl- or 7- acetylamino - 1 - # - hydroxypropyl - 3 - hydroxy derivatives of tetrahydroquinoline ; (10) 2 : 4- dinitro-6-chloroaniline, 4-nitro-2-methylaniline, 4 - nitroaniline - 2 - sulphonamide, 4-nitroaniline- 2-ethylsulphone or 4 - nitro - 2 - carboxyethylaniline # 5 - acetylamino - 1-# : γ-dihydroxypropyltetrahydroquinoline ; (11) 4 - aminoazobenzene # 7 - dimethylaminoacetylamino- 2 : 2 : 4-trimethyl-tetrahydroquinoline; (12) 4 - nitroaniline - 2 - sulphonic acid # 7 - carbethoxyamino - 1 - ethyl - 5 : 8 - dimethyl-tetrahydroquinoline ; (13) dianisidine disulphonic acid <SP>#</SP># 5 - acetylamino - 1 - (4<SP>1</SP>-sulpho) phenyl - tetrahydroquinoline (2 mols.); (14) 2 : 4-dinitroaniline - 6 - sulphonic acid # 7-sulphoacetylamino - 1 - cyclohexyl - tetrahydroquinoline ; (15) 1 : 5 : 7 - aminonaphtholsulphonic acid # 5 - acetylamino - 1 - sulphatoethyl - tetrahydroquinoline. Other specified diazo components are 4 - nitro - 2 - cyanoaniline, 2 - amino - 6 - methoxybenzoxazole, 2-amino - 6 - methoxybenzothiazole, 2 : 4-dinitro - 6 - cyanoaniline, 1 - naphthylamine and its 2 : 4 - dinitro-, 3-, 4-, 5- and 6-sulphonic acid and 3 : 8- and 4 : 8- disulphonic acid derivatives, aniline - 3- or 4- sulphonic acid, aniline-2 : 4-disulphonic acid, 2- chloroaniline - 4 - sulphonic acid and 2 : 8- naphthylaminesulphonic acid. 5- and/or 7 - Acylamino - tetrahydroquinoline derivatives are obtainable by acylation of the amino groups in the products of reduction of the nitro groups in the corresponding 5- and/or 7-nitro-tetrahydroquinolines. 5-nitro - tetrahydroquinoline is obtainable by hydrogenation of 5-nitro quinoline. 7-Acetylamino - 1 - allyl - tetrahydroquinoline is obtained by the action of allyl chloride or bromide in alcohol, and in the presence of sodium bicarbonate, on the product obtained by reducing 7-nitroquinoline, acetylating the resulting amino group and hydrogenating the 7-acetylamino compound. 7 - Acetylamino 3 - methoxy - tetrahydroquinoline is obtained from 7 - nitro - 3 - hydroxyquinoline by successive methylation with methyl iodide, reduction, acetylation and hydrogenation. 5- Acetylamino - 1 - tetrahydrofurfuryl - tetrahydroquinoline is obtained by hydrogenation of a mixture of 5-acetylamino-tetrahydroquinoline and furfural in alcohol in presence of finely divided nickel. 7 - Formylamino - 1 - # - hydroxyethyl - tetrahydroquinoline is obtained by the action of ethylene oxide in dioxane at 170-190‹C. on the product obtained from 7-nitroquinoline by successive reduction, formylation and hydrogenation. 7 - Acetylamino - 1- phenyl - tetrahydroquinoline is obtained by heating 7-acetylamino-tetrahydroquinoline with bromobenzene at 210‹C. in presence of copper powder. 7 - Acetylamino - 3 - methyl - tetrahydroquinoline is obtained by treating #-methylglycerol or #- methylacrolein with 3-nitroaniline in sulphuric acid in presence of an oxidising agent, e.g. arsenic acid, and subjecting the resulting 7 -nitro - 3 - methylquinoline to successive reduction, acetylation and hydrogenation. 7 - Acetylamino - 5 - chloro - tetrahydroquinoline is obtained by similarly treating glycerol with 5 - chloro - 3 - nitroaniline and subjecting the resulting 7-nitro-5-chloroquinoline to successive reduction, acetylation and hydrogenation. 5-Propionylamino-1-# : γ-dihydroxypropyltetrahydroquinoline is obtained from 5-nitroquinoline by successive reduction, propionylation, hydrogenation and treatment with glycerol chlorhydrin at 140-145‹C. in presence of sodium carbonate. 5 - Propionylamino - 3 - hydroxy-tetrahydroquinoline is obtained from 3-hydroxy quinoline by successive nitration, reduction, propionylation and hydrogenation. 5 - Formylamino - 3 - methoxy - tetrahydroquinoline is obtained from 5-nitro-3-hydroxyquinoline by successive methylation with methyl iodide, reduction, formylation and hydrogenation. 5 - Acetylamino - 8 - chloro - tetrahydroquinoline is obtained from 5-nitro-8-chloroquinoline by successive reduction, acetylation and hydrogenation. 7 - Lactylamino - 1 -methyl - tetrahydroquinoline is obtained from 7-nitro-quinoline by successive reduction, heating with methyl lactate, hydrogenation and methylation with methyl iodide. 7 - Acetylamino - 1 - methyl - 8 - ethoxy - tetrahydroquinoline is obtained from 3-nitro-2- ethoxyaniline by formation therefrom by Skraup's synthesis of 7-nitro-8-ethoxyquinoline and subjecting this to successive reduction, heating with methyl acetate and hydrogenation. 7 - Acetylamino - 4 - ethyltetrcahydroquinoline is obtained by subjecting to successive reduction, acetylation and hydrogenation 7-nitro-4- ethylquinoline prepared by Skraup's synthesis from 3-nitroaniline and ethyl vinyl ketone. 7 - Methyl - 5 - butyrylamino - 1- # - sulphoethyltetrahydroquinoline is obtained as sodium salt from 7 -methylquinoline by successive nitration, reduction, butyrylation, hydrogenation and heating with sodium #-bromo - α- sulphoethane in presence of sodium bicarbonate. 5 : 7-Di-(acetylamino)-tetrahydroquinoline is obtained from 5 : 7 -dinitroquinoline by successive reduction, acetylation and hydrogenation. 7 - Acetylamino - 5 - methoxy - tetrahydroquinoline is obtained by subjecting to successive reduction, acetylation and hydrogenation 7- nitro-5-methoxyquinoline obtained by Skraup's synthesis from 3-nitro-5-methoxyaniline. 7 - Tetrahydrofuroylamino - 1 - # - hydroxypropyl tetrahydroquinoline is obtained from 7- nitroquinoline by successive reduction, treatment with tetrahydrofuroyl chloride in presence of sodium carbonate, hydrogenation and reaction with 1 : 2-propylene oxide. 7 - Acetylamino - 5 - hydroxy - tetrahydroquinoline is obtained by subjecting to successive reduction, acetylation and hydrogenation 7- nitro -5 -hydroxyquinoline obtained by Skraup's synthesis from 3-nitro-5-hydroxyaniline. 7 - Ureido - 1 -