Patent GB-482198-A (GB)
Title: Manufacture of monoazo-dyestuffs insoluble in water
IPC: C09B29/20
Filed: 1936-09-21
Abstract: Water-insoluble monoazo-dyestuffs are manufactured by coupling, in substance or on a substratum for the production of lakes, the diazo-compound from an amine of the general formula <FORM:0482198/IV/1> where X1 is hydrogen, alkyl, alkoxy or halogen, X2 and X3 are hydrogen, alkyl, alkoxy, halogen or -NHCOR, R being alkyl, aryl, aralkyl or a hydroaromatic radicle, always one of the three substituents X1, X2 and X3 being alkoxy and one of the two substituents X2 and X3 being -NHCOR, with an arylide of 2 : 3-hydroxynaphthoic acid of the general formula <FORM:0482198/IV/2> wherein the nucleus a is substituted in at least one of the positions Y1 and Y2, e.g. by alkoxy, aryloxy, alkyl or halogen, R1 and R2 are hydrogen, alkyl, aryl, aralkyl or hydroaromatic radicles, and Z is hydrogen, halogen or alkoxy and is always alkoxy when X2 is -NHCOR and simultaneously X1 or X3 is hydrogen or halogen, the components being free from solubilizing groups.  The products may be used for the manufacture of colour lakes or for colouring cellulose esters and ethers, natural and artificial resins, high molecular organic plastic masses, e.g. products made from nitrocellulose, resins from formaldehyde and urea, phenols or amines, vinyl resins, natural and synthetic rubber.  In examples: (1) 1-amino-2 : 5-diethoxy-4-benzoylaminobenzene is diazotized and coupled with 2 : 3 - hydroxynaphthoyl - 11 - amino - 41-methylbenzene - 51 - sulphoethylamide; (2) the product of (1) is added to a mixture of rubber, loading materials, sulphur and a vulcanization accelerator, which is then vulcanized; the rubber is coloured blue; (3) 1-amino-2 : 5-dimethoxy-4-benzoylaminobenzene is diazotized and coupled with 2 : 3-hydroxynaphthoyl-11 - amino - 21 - methoxybenzene - 51 - sulphodiethylamide; a mixture of the product with rubber and the usual admixtures is immersed in a solution of sulphur chloride in benzine and vulcanized in the cold; the rubber is coloured reddish-blue; (4) 1-amino-2 : 5-diethoxy-4-benzoylaminobenzene is diazotized and coupled with 2 : 3-hydroxynaphthoyl-11-amino-21-methylbenzene - 51 - sulpho - N - methylbenzylamide; a mixture of the product with rennet casein and zinc white is treated with formaldehyde, yielding a blue horn-like product.  A table gives the shades of further dyestuffs, the following additional components being specified: diazo-components: 1-amino-2 : 4 - dimethoxy - 5 - benzoylaminobenzene, 1 - amino - 2 - methoxy - 4 - acetylamino benzene, 1 - amino - 2 : 5 - diethoxy - 4 - phenacetylamino-, -21-naphthoylamino-, -hexahydrobenzoylamino- and -41-chlorobenzoylaminobenzene, 1 - amino - 2 : 5 - dimethoxy - 4-(41-chlor- and 41-methoxybenzoyl)-aminobenzene, 1 - amino - 2 - methoxy - 5 - methyl- and 5 - chloro - 4 - benzoylaminobenzene, 1 - amino - 5 - methoxy - 4 - benzoylaminobenzene and its 2-methyl- and 2-chloro-derivatives, 1 - amino - 2 - ethoxy - 5 - benzoylaminobenzene, 1 - amino - 2 - methoxy - 4 - methyl-5 - benzoylaminobenzene, 1 - amino - 4 - methoxy - 5 - acetylaminobenzene, 1 - amino - 2-methyl - 4 - methoxy - 5 - benzoylaminobenzene, 1 - amino - 2 - methoxy - 5 - methyl - 4 - benzoylaminobenzene, and 1-amino-2-chloro-5-methoxy 4-benzoylaminobenzene; coupling components: 2 : 3 - hydroxynaphthoyl - 11 - amino - 21- and 41 - methylbenzene - 51 - sulphodiethylamide, -21-ethoxybenzene-51-sulphodimethylamide, -21-phenoxy- and -21-chlorobenzene-51-sulphodiethylamide, -21-methylbenzene-51-sulphodimethylamide, -sulphonamide, -sulpho-n- and isobutylamide, -sulphobenzylamide, -sulphocyclohexylamide, -sulphoanilide, -sulpho-N-methylcyclohexylamide, -sulpho-N-methylanilide, -sulphodibenzylamide, -sulpho-N-benzyl cyclohexylamide, -sulpho-N-benzylanilide and -sulphodiphenylamide, -21-methoxybenzene-51-sulpho-N-methylanilide and -sulphodiethylamide, \41-phenoxybenzene-51-sulphodiethylamide, -21 : 41-dimethylbenzene-51-sulphodimethylamide and -21-methoxy-41-chlorobenzene-51 -sulphodimethylamide, 6-bromo- and 6-methoxy - 2 : 3 - hydroxynaphthoyl - 11-amino - 21 - methyl- and -21-methoxy-51-sulphodiethylamide.  Specifications 6379/12, 281,795, 303,838, 312,297, [all in Class 2 (iii)], 381,944; 396,519, [Group VI], 435,711, and 452,720 are referred to.ALSO:High molecular organic plastic masses, especially natural and synthetic rubber, are coloured by the addition of azo dyestuffs obtained by coupling the diazo compound from an amine of the general formula <FORM:0482198/V/1> where X1 is hydrogen, alkyl, alkoxy or halogen, X2 and X3 are hydrogen, alkyl, alkoxy, halogen or -NHCOR, R being alkyl, aryl, aralkyl or a hydroaromatic radicle, always one of the three substituents X1, X2 and X3 being alkoxy and one of the two substituents X2 and X3 being -NHCOR, with an arylide of 2 : 3-hydroxynaphthoic acid of the general formula <FORM:0482198/V/2> wherein the nucleus a is substituted in at least one of the positions Y1 and Y2, e.g. by alkoxy, aryloxy, alkyl or halogen, R1 and R2 are hydrogen, alkyl, aryl, aralkyl or hydroaromatic radicles, and Z is hydrogen, halogen or alkoxy and is always alkoxy when X2 is -NHCOR and simultaneously X1 or X3 is halogen or hydrogen, the components being free from solubilizing groups.  In examples: (1) the azo dyestuff 1 - amino - 2 : 5 - diethoxy - 4 - benzoylaminobenzene --> 2 : 3-hydroxynaphthoyl-11-amino-41 - methylbenzene - 51 - sulphoethylamide is added to a mixture of rubber, loading materials, sulphur and a vulcanization accelerator, which is then vulcanized; the rubber is coloured blue; (2) a mixture of the dyestuff 1-amino-2 : 5 - dimethoxy - 4 - benzoylaminobenzene --> 2 : 3 - hydroxynaphthoyl - 11 - amino - 21-methoxybenzene - 51 - sulphodiethylamide with rubber and the usual admixtures is immersed in a solution of sulphur chloride in benzine and vulcanized in the cold; the rubber is coloured reddish-blue; (3) a mixture of the dyestuff 1 - amino - 2 : 5 - diethoxy - 4 - benzoylaminobenzene --> 2 : 3 - hydroxynaphthoyl - 11-amino-21-methylbenzene-51-sulpho-N-methyl benzylamide with rennet casein and zinc white is treated with formaldehyde, yielding a blue horn - like product.  Specifications 6379/12, 281,795, 303,838, 312,297, [all in Class 2 (iii)], 381,944, [Group IV], 396,519, [Group VI], 435,711, and 452,720, [both in Group IV], are referred to.