Patent GB-462674-A (GB)
Title: Manufacture of water-insoluble azo-dyestuffs
Filed: 1935-09-11
Abstract: Azo dyes; lakes; azo dyes, forming upon the material; regenerated celluloses, dyeing; printing.--Azo dyestuffs insoluble in water are manufactured by coupling in substance, on the fibre or on a substratum, an arylide of acetoacetic acid of the general formula <FORM:0462674/IV/1> where of X and Y one is alkyl and the other alkoxy, with the diazo-compound from a monoamine of the benzene series containing as substituents at least one halogen atom and, if desired, alkyl, alkoxy or aryloxy groups.  When produced in substance, the dyestuffs may be used for the preparation of pigments. The formation of the dyestuffs on the fibre may be effected by the ice-colour method or by one of the usual printing methods, e.g. in direct printing or by the nitrosamine printing process.  In examples: (1) 1 - amino - 2 - methyl - 4 : 5-dichlorobenzene is diazotized and coupled with 1 - (acetoacetylamino) - 5 - methoxy - 2 - methyl - 4 - chlorobenzene; the product yields a greenish-yellow lake when worked up with a substratum, advantageously in the form of a paste; (2) bleached cotton yarn is impregnated with 1 - (acetoacetylamino) - 2 - methoxy - 5 - methyl - 4 - chlorobenzene and a greenish-yellow dyeing is developed by means of diazotized 1-amino-3-methyl-2 : 4-dichlorobenzene; the dyestuff may also be produced on other vegetable fibres, on native cellulose, e.g. linen, on regenerated cellulose, e.g. viscose artificial silk, or on wool or other animal fibres, e.g. spun silk; (3) de-sized and bleached cotton piece goods are impregnated with 1 - (acetoacetylamino) - 2 - methoxy - 5 - methyl - 4 - bromobenzene and a lemon-yellow dyeing is developed by means of diazotized 1-amino-2-methyl-4-chlorobenzene; (4) de-sized and bleached cotton piece goods are printed with a paste containing sodium 3 - methyl - 4 : 6 - dichlorobenzene - 1 - nitrosamine, 1 - (acetoacetylamino) - 2 - methoxy - 5 - methyl - 4 - chlorobenzene, caustic soda, turkey red oil and starch tragacanth thickening, and then steamed, or exposed to air overnight, passed through a hot acetic acid solution, rinsed and soaped, yielding a lemon-yellow print.  A table gives the tints of further dyestuffs, the following additional diazo-components being specified: 1 - amino - 2 - methyl - 3 - and 5 - chlorobenzene, 1-amino-2 : 5-dichlorobenzene, 1-amino-2 : 3 : 4-trichlorobenzene, 1-amino-2-phenoxy-3- and 5-chlorobenzene, 1-amino-4-methyl-3-chlorobenzene, 1-amino-2-methyl-4- and 5-bromobenzene, 1 - amino - 2 - methyl - 3 : 4 - dichlorobenzene, 1-amino-4-methyl-2 : 3- and 2 : 5-dichlorobenzene, 1-amino-2-methoxy-3- and 5 - chlorobenzene, 1 - amino - 2 - ethoxy - 5 - chlorobenzene, 1 - amino - 2 - ethoxy - 4 - bromo - 5 - chlorobenzene, 1 - amino - 2 - methoxy - 4 : 5 - dichlorobenzene, 1 - amino - 2 - methyl - 4 - iodobenzene, 1 - amino - 2 - methyl - 4 - bromo - 5 - chlorobenzene, and 1-amino-2 : 5-dimethoxy-4-bromobenzene.  Samples have been furnished under Sect. 2 (5) of dyestuffs obtained by coupling 1-(acetoacetylamino) - 2 - ethoxy - 5 - methyl - 4 - chlorobenzene in substance and on the fibre with diazotized 1-amino-2-methyl-5-chlorobenzene, 1-amino-3-methyl-2:4-dichlorobenzene, 1-amino-2-methyl-4 : 5 - dichlorobenzene, 1 - amino - 2 - ethoxy - 4 - bromo - 5 - chlorobenzene, 1 - amino - 3 - methyl 4 : 6 - dichlorobenzene, 1 - amino - 2 - methyl - 3 - chlorobenzene, 1 - amino - 2 - phenoxy - 5 - chlorobenzene, 1 - amino - 2 - methyl - 4 - bromobenzene and 1 - amino - 2 - methyl - 4 - bromo - 5 - chlorobenzene.  The Specification as open to inspection under Sect. 91 refers also in the table to the dyestuffs from 1 - (acetoacetylamino) - 2 - methoxy - 5 - methyl-4-chlorobenzene and diazotized 1-amino-2 - methyl - 4 - chlorobenzene, 1 - amino - 2 - (2<1>-methylphenoxy)-5-chlorobenzene and 1-amino-2-(4<1>-methoxyphenoxy)-5-chlorobenzene, and from 1 - (acetoacetylamino) - 2 - methoxy - 5 - methyl-4-bromobenzene and diazotized 1-amino-2 - (4<1> - chlorophenoxy) - 5 - chlorobenzene and 1 - amino - 2 - (naphthyl - 2<1> - hydroxy) - 5 - chlorobenzene. This subject-matter does not appear in the Specification as accepted. Acetoacetic arylides of the formula given above are obtainable by reacting acetoacetic ester with the appropriate amine according to Specification 16928/12, [Class 2 (iii)].  1-Amino-2-methoxy- and 2-phenoxy-3-chlorobenzene are obtainable from 1-nitro-2 : 3-dichlorobenzene by replacing the chlorine atom in the 2-position by a methoxy- or phenoxy-group respectively, and reducing the nitro-group.  1-Amino-2-ethoxy-4-bromo-5-chlorobenzene is obtainable by chlorinating 1-acetylamino-2-ethoxy - 4 - bromobenzene and removing the acetyl group by saponification.