Patent GB-462601-A (GB)
Title: Manufacture of azo-dyestuffs insoluble in water
Filed: 1935-09-11
Abstract: Azo dyes; lakes; azo dyes, forming upon the material; regenerated celluloses, dyeing; printing.--Azo dyes are manufactured by coupling in substance, on the fibre or on a substratum for the production of lakes, an acetoacetic arylide of the formula <FORM:0462601/IV/1> where R is alkyl and of X and Y one is halogen 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.  The production of the dyestuffs on the fibre may be effected by the ice-colour process or by one of the usual printing methods, e.g. by direct printing or by the nitrosamine printing process.  In examples: (1) the dyestuff 1-amino-3-methyl-2 : 4-dichlorobenzene --> 1 - acetoacetylamino - 2 : 5 - dimethoxy - 4 - bromobenzene is produced in substance, or on a substratum to yield a greenish-yellow lake; (2) cotton yarn is impregnated with 1-acetoacetylamino-2 : 5 - dimethoxy - 4 - chlorobenzene and developed with diazotized 1-amino-2-methyl-5-chlorobenzene, producing a greenish-yellow dyeing; 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 also on wool or other animal fibres, e.g. spun silk, on which a more reddish dyeing is obtained; (3) cotton piece goods are impregnated with 1-acetoacetylamino-2 : 4-dimethoxy-5-chlorobenzene and a yellow dyeing is developed by means of diazotized 1-amino-2-methoxy-5-chlorobenzene; (4) cotton piece goods are printed with a paste containing sodium 2 - methyl - 4 : 5 - dichlorobenzene - 1 - nitrosamine, 1 - acetoacetylamino-2 : 5-dimethoxy-4-chlorobenzene, caustic soda, turkey red oil, and neutral starch tragacanth thickening, and then steamed, yielding a yellow print; (5) the nitrosamine in (4) is replaced by the disodium salt of the diazoamino-compound from 2-methyl-4-chloro-1-diazobenzene and 1 - amino - 2 - carboxybenzene - 4 - sulphonic acid, a greenish yellow print being developed by steaming in the presence of acetic and formic acid vapours.  A table gives the properties of further dyestuffs, the following additional components being specified: diazo-components: 1 - amino - 2 - and 4 - methyl - 3 - chlorobenzene, 1 - amino - 3 - methyl - 4 : 6 - dichlorobenzene, 1 - amino - 4 - methyl - 2 : 5 - dichlorobenzene, 1 - amino - 2 : 5 - diethoxy - 4 - chlorobenzene, 1 - amino - 2 - chlorobenzene, 1 - amino - 2 : 5 - dichlorobenzene, 1 - amino - 2 : 3 : 4 - trichlorobenzene, 1-amino-2-phenoxy-5- and 3-chlorobenzene, 1-amino-2-methyl-4-bromobenzene, 1-amino-2-methyl-5-bromobenzene, 1-amino-2-methyl-4-iodobenzene, 1-amino-4-methyl-2 : 3-dichlorobenzene, 1-amino-2-methyl-5-chloro-4-bromobenzene, 1-amino-2- and 4-methoxy-3-chlorobenzene, 1 - amino - 2 - ethoxy - 5 - chlorobenzene, 1 - amino - 2 - methoxy - 4 : 5 - dichlorobenzene, 1-amino-2-ethoxy-4-bromo-5-chlorobenzene, and 1-amino-2-methyl-3 : 4- and 4 : 6-dichlorobenzene; coupling component: the acetoacetyl compound of 1 - amino - 2 : 5-diethoxy - 4 - bromobenzene. Specifications 16928/12 and 332,932, [both in Class 2 (iii)], are referred to.  The Specification as open to inspection under Sect. 91 refers also to the use, as diazo-components, of 1-amino-2-(4<1>-chloro-, 2<1>-methyl-, and 4<1>-methoxy-phenoxy)-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 the action of acetoacetic ester on the appropriate amines at a raised temperature, if desired in the presence of a diluent.  1-Amino-2-methoxy- and 2-phenoxy-3-chlorobenzene are obtainable from 1-nitro-2 : 3-dichlorobenzene by replacing the chlorine atom in position 2 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.