Patent GB-477887-A (GB)
Title: Manufacture of azo-dyestuffs on the fibre
IPC: C09B31/02
Filed: 1936-06-04
Abstract: Water-insoluble azo dyes are made on vegetable fibres by impregnating with an arylide of an o-hydroxyarylcarboxylic acid or b -ketocarboxylic acid and developing with a diazo compound of a p-aminoazo compound of the benzene or naphthalene series which contains as a substituent at least one group containing the radical--CO--or --SO2--, which on the one hand is connected with a hydrocarbon radical directly or through an oxygen bridge or through a nitrogen bridge having as a substituent at the third bond a hydrocarbon radical, and on the other hand is connected with the benzene or naphthalene radical of the p-aminoazo compound directly or through an oxygen bridge and/or a hydrocarbon bridge or through a nitrogen bridge containing as a substituent at the third bond a hydrocarbon radical but only directly or through a hydrocarbon bridge when the radical --SO2-- is on the other hand connected with the hydrocarbon radical through an oxygen bridge.  Various shades of high fastness to light are obtained. In examples: (1) cotton yarn is grounded with 1-(2<1> : 3<1>-hydroxynaphthoylamino) - 2 - methyl - 4 - chlorbenzene and developed with 2 : 5 - dimethoxy - 4<1> - nitro - 2<1> - carboxylic acid - dimethylamide - azobenzene - 4-diazonium chloride or its zinc chloride double salt (dark blue); the 2 : 4-dimethoxy-5-chloranilide and a -naphthylamide may also be used; (2) cotton goods are grounded with the o-toluidide of 2 : 3 - oxynaphthoic acid and developed with diazotized 2 - methoxy - 5-methyl - 4<1> - nitro - 2<1> - carboxylic acid - dimethylamide - 4 - aminoazobenzene (deep dark blue); (3) cotton yarn is grounded with the arylide of the formula <FORM:0477887/IV/1> and developed with 2 : 5 - dimethoxy - 2<1> - N - phenylsulphonylmethylaminoazobenzene - 4 - diazonium chloride, or diazotized 2 : 5-dimethoxy - 2<1> - carboxylic acid - diethylamide - 4 - aminoazobenzine, or diazotized 2 : 5 : 2<1>-trimethoxy-5<1> - carboxylic acid - diethylamide - 4 - aminoazobenzene, or diazotized 4 - amino - 2 - methoxy - 5 methyl - 2<1>- or 4<1> - carboxylic acid - diethyl-amide-azobenzene (black shades); the corresponding p-anisidide also gives blacks with diazotized 4 - amino - 2 : 5 - dimethoxy - 4<1> - N methylphenylsulphonylaminoazobenzene, 4-amino - 3 - methoxy - 3<1> - carboxylic acid - diethyl-amide-azobenzene or 4-amino-2 : 5-dimethoxy-2<1> - phenylsulphonylmethyl - azobenzene; (4) cotton yarn is grounded with 1-(2<1>-hydroxy-3<1>-carbazole - carboylamino) - 4 - chlorbenzene and developed with 2 : 5-dimethoxy-3<1>-acetylazobenzene - 4 - diazonium - chloride zinc chloride double salt (violet brown); other diazo components specified are 2 : 5-dimethoxy-2<1>-carboxylic acid-dimethyl- or diethylamide-4-aminoazobenzene, 2 - methyl - 5 - methoxy - 4<1> - carboxylic acid-diethylamide-4-aminoazobenzene, or 4 - amino - 2 : 5 - dimethoxy - 4<1> - phenylsulphonylmethyl - azobenzene; (5) mercerized calico is grounded with diacetoacetyltolidine and printed with a paste containing diazotized 2 : 5 - dimethoxy - 2<1> : 5<1> - bis - (carboxylic acid diethylamide)-4-aminoazobenzene, dried and developed in a sodium carbonate solution (scarlet red); other diazo components specified are 4 - amino - 2 : 5 - dimethoxy - 4<1> - acetylazobenzene, 4 - amino - 2 : 5 - dimethoxy - 3<1> : 4<1> - bis (carboxylic acid ethyl ester) - azobenzene, 4 - amino - 2 : 5 - dimethoxy - 3<1> - carboxylic acid diethylamide - 4<1> - chloroazobenzene, 4 - amino-2 : 5 - dimethoxy or diethoxy - 2<1> - carboxylic acid - dimethylamide - 4<1> - nitroazobenzene, 4 - amino - 2 : 5 - diethoxy - 2<1> - carboxylic acid ethyl ester - 4<1> - nitroazobenzene, 4 - amino - 2 : 5-dimethoxy - 2<1> - methylsulphonyl - 4<1> - nitroazobenzene and 4-amino-2 : 5-dimethoxy-2<1>-sulphonic acid - diethylamide - 4<1> - nitroazobenzene; (6) bleached cotton piece goods are grounded with the anilide of 2 : 3-oxynaphthoic acid, printed with a paste containing 2 : 5-dimethoxy - 4<1> - nitroazobenzene - 2<1> - carboxylic acid ethyl ester-4-diazonium chloride, dried, passed through hot aqueous sodium carbonate and soaped (deep black).  A table showing the shades obtained from a large number of other combinations is given.  Samples have been furnished under Sect. 2 (5) of 54 dyeings produced according to a schedule given in the Specification.  Specifications 203,032 and 214,516, [both in Class 2 (iii)], are referred to.  m - Aminophenyl-o -carboxylic ethyl ester is made in a manner similar to that used for making the p-amino compound (see Ber. 31, p. 1065).  o - Aminobenzylsulphonic acid N-methylphenyl-amide is made by converting o-nitrobenzylsulphonic acid into the acid chloride, condensing with N-methylaniline and reducing.  p - Aminophenol - o  - dimethyl - sulphonamide is made by condensing potassium p-nitrophenolate with chlorsulphonic acid-dimethyl amide and reducing.  3 - N - methyl - N - sulphodimethylamide - 1 - aminobenzene is made by condensing 3-nitro-1-methylaminobenzene with chlorsulphonic acid dimethylamide and reducing.  1 - Aminobenzene - 3- or 4 - N - methylcarbamic acid ethyl ester is made by condensing chlorformic ethyl ester with 1-methylamino- 3-or 4-nitrobenzene and reducing.  1 - Aminobenzene - 4 - N - ethylcarbamic acid dimethylamide is made by causing phosgene to act on 1-ethylamino-4-nitrobenzene, treating the acid chloride with dimethylamine and reducing.  o - or p-Aminobenzylsulphonic acid diethylamide is made by condensing o- or p-nitrobenzylsulphonic acid chloride with diethylamine and reducing.  4 - N - methyl - N - sulphodimethylamide - 1 - aminobenzene is made by condensing 4-nitro-1-methylaminobenzene with chlorsulphonic acid dimethylamide and reducing.  m - Aminobenzylsulphonic acid phenylester is made by reacting m-nitrobenzylsulphochloride with sodium phenolate in benzene and reducing.