Patent GB-481747-A (GB)
Title: Manufacture of azo-dyestuffs insoluble in water
IPC: C09B29/20
Filed: 1936-09-18
Abstract: Water-insoluble azo-dyestuffs are manufactured by coupling the diazo-compound of a 1-amino-4-nitrilobenzene, substituted in 2- and 5-positions, in substance, on the fibre or on a substratum for the production of lakes, with an o-hydroxyarylcarboxylic acid arylamide or a b -ketocarboxylic acid arylamide, the components being free from solubilizing groups.  The production of the dyestuffs on the fibre, e.g. on native or regenerated cellulose fibres or animal fibres, may be effected by the ice-colour method or by one of the usual printing methods, e.g. by direct printing or by the use of nitrosamines or diazoamino compounds.  In examples: (1) cotton yarn is impregnated with 2 : 3-hydroxynaphthoic acid a -naphthylamide, and a blue-red dyeing is developed with diazotized 1 - amino - 3 - methoxy - 6 - chloro - 4 - nitrilobenzene; by using 2 : 3-hydroxynaphthoic anilide as coupling component a yellow-red dyeing is obtained; (2) cotton piece goods are padded with 2 : 3-hydroxynaphthoic anilide and a yellow-red dyeing is developed with diazotized 1 - amino - 2 : 5 - dichloro - 4 - nitrilobenzene; (3) a mixed fabric of cotton and viscose artificial silk is impregnated with di(acetoacetyl)-o-tolidide, developed with diazotized 1 - amino - 3 - methyl - 6 - chloro - 4 - nitrilobenzene, and then printed with a discharge containing sodium formaldehyde-sulphoxylate, potassium carbonate, an anthraquinone paste and neutral starch-tragacanth thickening, yielding a white discharge on a reddish-yellow ground; (4) cotton piece goods are impregnated with 2 : 3-hydroxynaphthoic anilide, printed with a resist containing a stabilized diazo-compound from 1-amino-3-methyl-6-chloro-4-nitrilobenzene, aluminium sulphate and neutral starch-tragacanth thickening, and developed with diazotized 4-amino-41-methoxydiphenylamine, producing a yellowish-red effect on a blue ground; (5) silk is impregnated with 2 : 3-hydroxynaphthoic acid 2-methyl-4-chloranilide and a yellow-red dyeing is developed with diazotized 1 - amino - 3 - methoxy - 6 - trifluoromethyl-4-nitrilobenzene; (6) cotton piece goods are printed with a paste containing the potassium compound of 3-methyl-6-chloro-4-nitrilobenzene-1-nitrosamine or a diazoamino compound from 1 - amino - 3 - methyl - 6 - chloro - 4 - nitrilobenzene, 2 : 3-hydroxynaphthoic anilide, caustic soda, turkey red oil, alcohol, chromate solution and neutral starch-tragacanth thickening, and then steamed to produce a yellowish red print; alternatively, di-(acetoacetyl)-o-tolidine is used as coupling component, yielding a reddish - yellow print; (7) the dyestuff 1 - amino - 3 - methyl - 6 - chloro - 4 - nitrilobenzene --> 2 : 3-hydroxynaphthoic acid 2-methoxy-5-bromanilide is produced in substance, and may be worked up with a substratum to form a red lake; (8) linen piece goods are impregnated with 2-hydroxycarbazole-3-carboxylic acid p-chloranilide and a reddish-brown dyeing is developed with diazotized 1 - amino - 2 : 5-dimethoxy-4-nitrilobenzene.  A table gives the shades of further dyestuffs, the following additional components being specified: diazo components: the 5 - methyl - 2 - bromo-, 2-methoxy - 5 - chloro-, 5 - ethoxy - 2 - chloro-, 2 - phenoxy - 5 - chloro-, 2 : 5 - dimethyl-, 5-methoxy - 2 - methyl-, 2 : 5 - dimethoxy- and 5 - methyl- or methoxy - 2 - diethylaminosulphonyl-derivatives of 1-amino-4-nitrilobenzene; coupling components: the b -naphthylamide, o- and p-anisidide, o- and p-phenetidide, o-toluidide, 4-methoxy-2- and 3-methylanilide, 2 : 4-dimethoxy-3- and 5-chloranilide, 2 : 4- and 2 : 5 - dimethoxyanilide, m - chloranilide, 4-methoxy - 1 - naphthylamide, 2 : 5 - dimethoxy-4-chloranilide and m-nitranilide of 2 : 3-hydroxynaphthoic acid, the 2 : 4-dimethoxyanilide of 6-bromo-2-hydroxy-3-naphthoic acid, the o-anisidide of 6-methoxy-2-hydroxy-3-naphthoic acid, the o-toluidide of 2-hydroxyanthracene-3-carboxylic acid, the p-anisidide of Bz2-hydroxy-1 : 2-benzocarbazole-Bz3-carboxylic acid, 4 : 41-di - (211 - hydroxynaphthalene - 311 - carboylamino)-3 : 31-dimethoxydiphenyl, terephthalobis - (acetyl - 1 - amino - 2 : 4 - dimethoxy - 5-chlorobenzene) and terephthalo-bis-(acetyl-1-amino-2-methoxy-5-methyl-4-chlorobenzene) . Specifications 301,410, [Class 2 (iii)], and 481,735 are referred to. 1-Amino-4-nitrilobenzenes substituted in the 2- and 5-positions are obtainable by diazotizing the corresponding p-aminonitrobenzenes, replacing the diazo-group by the nitrilo-group by the Sandmeyer reaction, and reducing the nitro-group.