Patent GB-485757-A (GB)
Title: Manufacture of azo-dyestuffs
IPC: C09B29/20
Filed: 1936-11-24
Abstract: Monoazo dyestuffs insoluble in water are manufactured by coupling, in substance or on a substratum, the diazo-compound from an amine of the general formula <FORM:0485757/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 X1, X2 and X3 being alkoxy and always one of X2 and X3 being -NHCOR, with an arylide of 2 : 3-hydroxynaphthoic acid of the general formula <FORM:0485757/IV/2> wherein the nucleus a may be further substituted, e.g. by an alkyl, alkoxy or aryloxy group or a halogen, R1 and R2 are hydrogen or alkyl, aryl, aralkyl or hydroaromatic radicles and Z is hydrogen, halogen or alkoxy, Z being alkoxy when X2 is -NHCOR and simultaneously X1 or X3 is halogen or hydrogen, only such components being used as do not contain solubilizing groups.  The products may be used for the manufacture of colour lakes and for colouring cellulose esters and ethers, natural and artificial resins, organic plastic masses of high molecular weight, e.g. products made from nitrocellulose, resins from formaldehyde and urea, phenols or amines, vinyl resins and natural or synthetic rubber.  In examples: (1) 1-amino-2 : 5-diethoxy-4-benzoylaminobenzene is diazotized and coupled with 2 : 3-hydroxynaphthoyl-11-aminobenzene-41 -sulphocyclohexylamide; the product may be converted into lakes, or the coupling may be effected in the presence of a substratum for thus purpose; (2) the product of (1) is incorporated with a mixture of rubber, loading materials, sulphur and a vulcanization accelerator, and the mixture is then vulcanized, yielding a blue vulcanizate; (3) 1-amino-2 : 5-dimethoxy - 4 - benzoylaminobenzene is diazotized and coupled with 2 : 3-hydroxynaphthoyl-11-aminobenzene - 41 - sulphobenzylamide; 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 blue; (4) 1-amino-2-methoxy-5-methyl-4-benzoylaminobenzene is diazotized and coupled with 2 : 3-hydroxynaphthoyl-11-amino-31-chlorobenzene - 41 - sulphanilide; a mixture of the product with rennet casein and zinc white is hardened with formaldehyde to produce a violet horn-like mass.  A table gives the shades of further dyestuffs, the following additional components being specified; diazo components: 1 - amino - 2 : 5 - diethoxy - 4 - (21 : 51 - dichloro) - benzoylaminobenzene, 1-amino-2 : 5 - dimethoxy - 4 - a  - naphthoylamino benzene, 1 - amino - 2 : 4 - dimethoxy - 5-benzoylaminobenzene, 1 - amino - 2 - methoxy-5 - chloro - 4 - benzoylaminobenzene, 1-amino - 2 : 5 - diethoxy - 4 - phenacetylaminoand - 4 - hexahydrobenzoylaminobenzene, 1 - amino - 2 : 5 - dimethoxy - 4 - acetylaminobenzene, 1 - amino - 2 - methoxy - 5 - benzoylaminobenzene, 1 - amino - 2 - methoxy - 4-acetylaminobenzene, 1 - amino - 3 - methoxy-4 - benzoylaminobenzene, 1 - amino - 2 - chloro5 - methoxy - 4 - benzoylaminobenzene, 1-amino - 2 - methyl - 5 - methoxy - 4 - benzoylaminobenzene, 1 - amino - 2 : 4 - diethoxy - 5-benzoylaminobenzene and 1 - amino - 4 - methoxy - 5 - benzoylaminobenzene; coupling components: 2 : 3 - hydroxynaphthoyl - 11-aminobenzene - 41 - sulpho - n - butylamide, -sulpho - N - methylbenzylamide, - sulpho - N-methylanilide, -sulphodiethylamide, -sulpho-N - ethylcyclohexylamide, -sulphamide, -sulphodiphenylamide, -sulpho - N - benzylanilide, -sulphodibenzylamide, -sulpho-N-benzylcyclohexylamide, -sulpho - b -naphthylamide and -sulphodicyclohexylamide, 2 : 3-hydroxynaphthoyl - 11 - amino - 21 - methylbenzene-41 - sulpho - N - methylanilide, -21 : 51-dimethoxybenzene - 4 1 - sulphodimethylamide, -21 - chlorobenzene - 41 - sulphodiethylamide, -21 - methylbenzene - 41 - (sulpho - 211 - amino 111 : 211 : 311 : 4 411 - tetrahydronaphthalene) and -21 : 51 - diethoxybenzene - 41 - sulphodimethyl amide, 6 - bromo- and 6-methoxy - 2 : 3-hydroxynaphthoyl - 11 - aminobenzene - 41-sulphanilide. Specifications 6379/12, 281,795, 303,838, 312,297, 313,865, [all in Class 2 (iii)], 381,944, 435,711, and 452,720 are referred to.ALSO:Plastic masses of high molecular weight, particularly natural or synthetic rubber, are coloured by the addition of monoazo dye-stuffs prepared by coupling the diazo compound from an amine of the general formula <FORM:0485757/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 X1, X2 and X3 being alkoxy and always one of X2 and X3 being -NHCOR, with an arylide of 2 : 3-hydroxynaphthoic acid of the general formula <FORM:0485757/V/2> wherein the nucleus a  may be further substituted, e.g. by an alkyl, alkoxy or aryloxy group or a halogen, R1 and R2 are hydrogen or alkyl, aryl, aralkyl or hydroaromatic radicles and Z is hydrogen, halogen or alkoxy, Z being alkoxy when X2 is-NHCOR and simultaneously X1 or X3 is hydrogen or halogen, only such components being used as contain no solubilizing groups.  In examples: (1) the dyestuff 1 - amino - 2 : 5 - diethoxy - 4 - benzoylaminobenzene --> 2 : 3 - hydroxynaphthoyl - 1 - aminobenzene - 41 - sulphocyclohexylamide is incorporated with a mixture of rubber, loading materials, sulphur and a vulcanization accelerator, and the mixture is then vulcanized, yielding a blue vulcanizate ; (2) a mixture of the dyestuff 1-amino-2 : 5-dimethoxy - 4 - benzoylaminobenzene --> 2 : 3 - hydroxynaphthoyl - 11 - aminobenzene-41 - sulphobenzylamide 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 blue; (3) a mixture of the dyestuff 1-amino-2-methoxy-5 - methyl - 4 - benzoylaminobenzene --> 2 : 3 - hydroxynaphthoyl - 11 - amino - 31-chlorobenzene - 41 - sulphanilide with rennet casein and zinc white is hardened with formaldehyde to produce a violet horn-like mass.  Specifications 6379/12, 281,795, 303,838, 312,297, 313,865, [all in Class 2(iii)], 381,944, 435,711, and 452,720, [all in Group IV], are referred to.