Patent GB-507260-A (GB)
Abstract: 507,260. Azo compounds; dyeing and printing. CALCO CHEMICAL CO., Inc. April 2, 1938, No. 10141. Convention date, April 2, 1937. [Classes 2 (iii) and 15 (ii)] A diazotized aromatic or heterocyclic amine, not containing a sulphonic or carboxylic group, is coupled with biguanide or a derivative thereof which contains at least one hydrogen atom linked to a biguanide nitrogen atom, but which 'does not contain an aromatic or heterocyclic radicle carrying a hydroxyl or amino group. Coupling is generally effected at a low temperature in a slightly alkaline medium, but a slightly acid medium may be used with diazo compounds which readily form isodiazotates. The following examples are given, the nitrogen atoms of the biguanide molecule being numbered 1-5 in the order shown in the formula NH2C( : NH)NH C( : NH)NH2. (1) Diazotized 2-methyl-5-chloraniline is added to a solution of biguanide acid sulphate in caustic soda solution; the azo compound formed is filtered, and excess of biguanide is recovered from the filtrate by addition of ammoniacal copper sulphate solution, whereby a precipitate of copper-biguanide sulphate is obtained; this may be decomposed with hydrogen sulphide or sodium sulphide; in place of diazotized 2-methyl-5-chloraniline the diazo compounds from 2-methyl-4-chloraniline, 2- methoxy-5-chloraniline, o-, m- or p-chloraniline, o-anisidine, aniline, p-toluidine, xenylamine and 2-methyl-5-nitraniline may be used ; (2) diazotized 2 : 5-dichloraniline is coupled with' biguanide acid sulphate in a weakly acid medium ; (3) diazotized 2-methyl-4-nitraniline or 2-methoxy-4-nitraniline is coupled with biguanide as in example 1 ; (4) tetrazotized o-dianisidine is coupled with biguanide as in example 1; (5)-(7) diazotized 2-methyl-5- chloraniline is coupled with 1-methylbiguanide, 1 : 1 - diethylbiguanide, 1 : 1 - cyclopentamethylenebiguanide, 1-phenylbiguanide or 1- benzylbiguanide; (8) diazotized 2 : 5-dichloraniline is coupled as in example 2 with 1-methylbiguanide, 1 : 1-diethylbiguanide, or 1:1- cyclopentamethylenebiguanide or (example 9) with 1-phenylbiguanide; (10) diazotized 2- methoxy-4-nitraniline or 2-methyl-4-nitraniline is coupled with 1-phenylbiguanide. Other specified biguanide derivatives are 1-ethylbiguanide, 1 : 2-dimethylbiguanide, 1 : 1 : 2- trimethylbiguanide, 1 : 5-dimethylbiguanide, 1 : 1 : 5 : 5-tetramethylbiguanide, homologues of 1-phenylbiguanide, such as 1-(4<1>-methylphenyl)biguanide, 1-alpha- and -#-naphthylbiguanides and their homologues, 1-cyclohexylbiguanide and its homologues, homologues of 1 - benzylbiguanide, 1 - (4' - chlorophenyl)- biguanide, 1 - (4<1> -nitrophenyl)biguanide, 1- (4<1> - methoxyphenyl)biguanide, 1 - (4<1> - carboxyphenyl)biguanide and 1 - (1<1> - sulpho - 21 - naphthyl)biguanide. Other specified diazo compounds are those derived from (a) aniline homologues such as the toluidines and 2 : 4- dimethylaniline; (b) halogen derivatives of aniline and its homologues, such as fluoranilines, 2: 5-difluoraniline, 2-fluoro-5-chloraniline, m- or p-aminobenzotrifluoride, 3 - amino - 4 - chlorobenzotrifluoride, 2 - methyl - 3 - chloraniline, 3 - methyl - 4 - chloraniline, 5 - methyl - 2 - chloraniline, 2 - methyl - 4 - chloro - 5 - bromaniline, 2-methyl-4 : 5-dichloraniline and 4-methyl 2 : 5- dichloraniline; (c) nitro derivatives of aniline and its homologues and of their halogen derivatives, such as the nitranilines, 4-methyl-2- nitraniline, 2 - nitro - 4 - fluoraniline, 2 - nitro - 4-chloraniline, 3-nitro-4-chloraniline and 4- nitro-2-chloraniline; (d) ether derivatives of primary aromatic amines and their halogen derivatives, such as 2-methoxy-5-methylaniline, 2 : 5-dimethoxyaniline, 2-methoxy-1-naphthylamine, 2-aminodiphenylether, 2-amino-4-acetyldiphenyl ether, benzyl-2-aminophenyl ether, 3- fluoro-4-methoxyaniline, 2 : 5-dimethoxy-4- chloraniline, 2 - methoxy - 4 - chloro - 5 - methylaniline, 2 - methoxy - 5 - bromaniline, 3 - bromo - -- 6 - ethoxyaniline, 4 - chloro - 2 - aminodiphenyl ether, 4 - amino - 4<1> - chlorodiphenyl ether, 4 : 4<1>-dichloro-2-aminodiphenyl ether and 2 : 2<1> : 5<1>-trichloro-4-aminodiphenyl ether; (e) ether derivatives of aniline and its homologues containing nitro groups, such as 2-methoxy-5-nitraniline, 2-nitro-4- methoxyaniline and 2 - methoxy - 4 - nitro - 5 - methylaniline; (f) monoacyl derivatives of aromatic diamines, such as hexahydrobenzoyl-pphenylene diamine, hexahydrobenzoyl - p - toluylenediamine and benzoyl - p - phenylenediamine ; (g) monoacyl derivatives of diaminophenol ethers, such as 2-benzoylamino-4-aminoanisole, 2 - hexahydrobenzoylamino - 5 - aminoanisole, 2 - amino - 5 - benzoylaminohydroquinone dimethyl or diethyl ether, 2-amino-5- hexahydrobenzoylaminohydroquinone dimethyl or diethyl ether, 2-amino-5-butyrylaminohydroquinone dimethyl or diethyl ether, 2-amino-5- phenoxyacetylaminohydroquinone diethyl ether, the monomethyl-, monobenzyl- or monophenylurethane of 2.5-diaminohydroquinone dimethyl or diethyl ether, 1-amino-3-benzoylamino-4.6- dimethoxybenzene, and analogous monoacyl derivatives of 2 : 5-diamino-4-alkoxytoluenes or of 2 : 5-diamino-4-alkoxychlorobenzenes or of 2 : 5-diamino-4-alkoxybenzenesulphodialkylamides or of 1 : 3-diamino-4 : 6-dimethylbenzene; (h) the diethylamide of 3-amino-4- (4<1>-chlorophenoxy)benzoic acid; (i) monoacyl derivatives of diamino-p-chlorophenyl ethers, ethers, such as 2-amino-4-chloro-5-acetylaminodiphenyl ether and 2-benzoylamino-4-chloro-5- aminoanisole; (j) aminoaryl sulphones, such as 3-amino-4-methyldiphenyl sulphone, 2-amino- 4<1>-methyldiphenyl sulphone, 2-amino-4-acetyldiphenyl sulphone, the ethyl ester of 3-amino-4- (p-toluenesulphonyl)benzoic acid, 4-methoxy-3- aminophenylethyl sulphone, 4 - methoxy - 3 - aminophenylbenzyl sulphone, 4 - ethoxy - 3 - aminodiphenyl sulphone, and 2 - amino - 4 - trifluoromethylphenylethyl sulphone; (k) amino derivatives of aromatic dialkylsulphonamides, such as 3-amino-4-methylbenzene-dimethylsulphonamide and -diethylsulphonamide and 3 - amino - 4 - methoxybenzene - diethylsulphonamide-; (l) alpha- and #-naphthylamine, 1 - aminoanthraquinone, 2 - amino - 3 - nitrofluorene and 2-amino-3-nitroflurorenone; (m) aminodiaryl amines and their ether and nitro derivatives, such as 2 - methoxy - 5 - aminodiphenylamine, 4 - methoxy - 4' - aminodiphenylamine, 4 - ethoxy - 4<1> - aminodiphenylamine and 3 : 4'-dinitro-4-aminodiphenylamine ; (n) aminoazo compounds such as 3 : 2<1>- dimethyl- 4 - aminoazobenzene, 2 - methyl - 4 - amino - 5 - methoxy - 4<1> - chlorazobenzene, 4 - amino - 41 - nitro - 3 - methoxy - 6 - methylazobenzene, 4 - amino - 4<1> - nitro 2 : 5 - dimethoxyazobenzene, 4 - amino - 4<1> - chloro - 3 - methoxy-6-methylazobenzene, and the dye from diazotized o-anisidine and alpha-naphthylamine; (o) aromatic diamines with only one diazotizable amino group, such as 2: 6-dichloro-1 : 4-phenylenediamine ; (p) diamines in which both amino groups are diazotizable, such as benzidine, o-tolidine, 4 : 4<1>-diaminostilbene, 4 : 41-diaminodiphenylamine, 2 : 2<1>-dimethyl-4 : 4<1>- diaminodiphenylamine, and 1 : 5-diaminonaphthalene ; (q) heterocyclic amines and diamines such as 2-aminocarbazole, 3 : 6-diaminocarbazole, 2-nitro-3-aminocarbazole, 2-nitro-3- aminodibenzofurane, 2 - amino - 3 - nitrodibenzothiophcne and 2-amino-6-fluorobenzthiazole. The azo-biguanide compounds are generally stable to alkalies but easily decomposed by acids. They may be used in producing azo dyes on the fibre, and for this purpose an alkaline composition containing an azobiguanide compound and an enolic or phenolic coupling component may be printed on the fibre and the dyestuff then developed by treatment with an acid bath or with steam containing an acid vapour, such as formic or acetic acid vapour. For use in such compositions the azo-biguanide compounds may be treated with a deflocculating agent and a protective colloid with or without a wetting agent and a hydrotropic substance. The following examples of the use of the products are given : (11) an aqueous mixture of 2-methyl-5-chlorobenzeneazo-biguanide, 2 : 3-hydroxynaphthoic acid ophenetidide, the sodium salt of disulphodinaphthylmethane, trisodium phosphate and dextrin is prepared and dried ; a printing paste is then prepared by dispersing the product in aqueous caustic soda solution and adding glycol monoethyl ether and starch-tragacanth thickener; printing is effected in the usual manner, and the dyestuff is developed with steam containing acetic acid vapour, a scarlet print being obtained ; (12) as in example 11, except that the dyestuff components used are 3-chlorobenzene-azo-biguanide and 2:3-hydroxynaphthoic acid o-toluidide ; (13) as in example 12, except, that the azo-biguanide compound used is 2<1>-methyl-5<1>-chlorobenzeneazo-1-methylbiguanide. Other specified coupling components are arylides of acetoacetic acid or of hydroxycarbazole or hydroxynaphthocarbazole carboxylic acids, and 1-phenyl-3- methyl-5-pyrazolone. The Specification as open to inspection under Sect. 91 includes an example in which diazotized aniline is coupled with m-phenylene-bis-1- biguanide. This subject-matter does not appear in the Specification as accepted.