Patent GB-515980-A (GB)
Abstract: 515,980. Stabilized diazo compounds. CALCO CHEMICAL CO., Inc. July 7, 1938, No. 20132. Convention date. July 12, 1937. [Class 2(iii)] Stabilized diazo compounds are manufactured by reacting diazotized amines suitable for the production of coupling components (which term includes compounds containing more than one diazo group, e.g., tetrazo compounds) with a guanylurea-N-sulphonic. acid or N-nitroguanylurea or a salt thereof, the guanylurea derivative being free from substituent groups capable of azoic coupling and having at least one reactive hydrogen atom attached' to nitrogen. The reaction is carried out in an alkaline medium at pH=8.5 or higher, e.g., by working in the presence of excess of hydrated lime, in which case the calcium salt of the stable diazo compound is first formed and may be' converted into the alkali metal salt by double decomposition with an alkali metal carbonate or oxalate. Suitable amines are : aniline and its homologues, e.g., toluidines, 2:4-dimethylaniline ; halogen derivatives of aniline and of its homologues, e.g., monofluoroanilines, monochloroanilines, 2:5-difluoroaniline, 2-fluoro-5-chloroaniline; 2:5 - dichloraniline; m - and baminobenzotrifluoride, 3 - amino - 4 - chlorobenzotrifluoride, 2 - methyl - 3 -, 4 - and 5 - chloroaniline, 3 - methyl - 4 - chloroaniline, 5 - methyl - 2 - chloroaniline, 2 - methyl - 4 - chloro - 5 - bromoaniline, 2 - methyl - 4:5 - dichloroaniline, 4 - methyl - 2:5 - dichloroaniline ; nitro derivatives of aniline, its homologues and their halogen derivatives, e.g., the nitroanilines, 2 - methyl - 4 - and 5 - nitroaniline, 4 - methyl - 2 - nitroaniline, 2 - nitro - 4 - fluoroaniline, 2 - and 3 - nitro - 4 - chloroaniline, 4 - nitro - 2 - chloroaniline ; ether derivatives of primary aromatic amines and their halogen derivatives, e.g., o-anisidine, 2 - methoxy - 5 - methylaniline, 2:5-dimethoxy - aniline, - 2 - methoxy - 1 - naphthylamine, 2 - aminodiphenyl ether, 2 - amino - 4 - acetyldiphenyl ether, benzyl 2-aminophenyl ether, 3-fluoro-4-methoxyaniline, 2-methoxy-5- chloroaniline, 2:5 - dimethoxy - 4 - chloroaniline, 2 - methoxy - 4 - chloro - 5 - methylaniline; 2 - methoxy - 5 - bromoaniline, 3 - bromo - 6 - ethoxyaniline, 4 - chloro - 2 - aminodiphenyl ether, 4-amino-2- and 4<1>-chlorodiphenyl ether, 4:4<1>-dichloro-2-aminodiphenyl ether, 2:2<1>:5<1> - trichloro - 4 - aminodiphenyl ether ; ether derivatives of nitro compounds of aniline and its homologues, e.g., 2-methoxy- 4 - and 5 - nitroaniline, 2 - nitro - 4 - methoxyaniline, 2 - methoxy - 4 nitro - 5 - methyl - aniline ; monoacyl derivatives of aromatic diamines, e.g., N - hexahydrobenzo.yl - p - phenylenediamine, N - hexahydrobenzoyl - p - toluylenediamine, N - benzoyl - p - phenylene - diamine ; monoacyl derivatives of diaminophenol ethers, e.g., 2-benzoylamino-4-aminoanisole, 2 - hexahydrobenzoylaminb - 5 - aminoanisole, 2 - amino - 5 - benzoylaminohydroquinone dimethyl and diethyl ethers, 2- aniino - 5 - hexahydrobenzoylaminohydro - quinone dimethyl and diethyl ethers, 2-amino- 5 - butyrylaminohydroquinone dimethyl and diethyl ethers, 2-amino-5-phenoxyacetylaminohydroquinone diethyl ether, the monoethyl, monobenzyl and monophenyl methanes of 2:5- diaminoxydroquinone dimethyl and diethyl ethers, 1 - amino - 3 - benzoylamino - 4:6 - dimethoxybenzene ; analogous monoacyl derivatives of 2:5 - diamino - 4 - alkoxytoluenes, of 2:5 - diamino - 4 -alkoxychlorobenzenes and of 2:5 - diamino - 4 - alkoxybenzenesulphodialkyl - amides ; analogousmonoacyl derivatives of 1:3 - diamino - 4:6 - dimethylbenzene ; the diethylamide of 3-amino-4-(4<1>-chlorophenoxy)- benzoic acid ; monoacyl derivatives of diaminop-chlorophenyl ethers, e.g., 2-amino-4-chloro-5- acetylaminodiphenyl ether, 2 - benzoylamino - 4 - chloro - 5 - aminoanisole ; amino derivatives of aromatic sulphones, e.g., 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-aminophenyl ethyl sulphone, 4-methoxy-3-aminophenyl benzylsulphone, 4-ethoxy-3-aminodiphenyl sulphone, 2-amino-4-trifluoromethylphenyl ethyl sulphone; amino derivatives of aromatic dialkylsulphonamides, e.g., 3-amino-4- methylbenzenesylphodimethylamide and diethylamide, 3-amino-4-methoxybenzenesulphodiethylamide ; xenylamine ; alpha - and # - naphthylamine ; alpha - aminoanthraquinone ; 2 - amino - 3 - nitrofluorene and 2 - amino - 3 - nitrofluorenone ; aminodiarylamines and their ether derivatives and nitro derivatives; e.g., 2 - methoxy - 5 - aminodiphenylamine, @4 - methoxy - 4<1> - aminodiphenylamine, 4 - ethoxy - 4<1 >- aminodiphenylamine, 3:4<1> - dinitro - 4 - aminodiphenylamine; aminoazo compounds, e.g., 3:2 <1> -dimethyl - 4 - aminoazobenzene, 2 - methyl - 4 - amino - 5 - methoxy- 4<1> - chloroazobenzene, 4 - amino - 4<1> - nitro 3 - methoxy - 6 - methylazobenzene, 4 - amino 41 - nitro - 2:5 - dimethoxyazubenzene, 4 - amino - 4<1> - chloro - 3 - methoxy - 6 - methvlazo - benzene and the azo dye o-anisidine# alphanaphthylamine; aromatic diamines in which only one of the amino groups is diazotized, e.g., 2:6 - dichloro - 1:4 - phenylenediamine, or in which both amino groups are diazotized, e.g., p-phenylenediamine, benzidine, o-tolidine, odianisidine, 4:4<1>-diaminostilbene, 4:4<1>-diaminodiphenylamine, 2:2<1>-dimethyl-4:4<1>-diaminodiphenylamine, 1:5 - diaminoaphthaleiie; and heterocyclic amines, e.g., 2-aminocarbazole, 3:6- diaminocarbazole, 2 - nitro - 3 - aminocarbazole, 2 - nitro - 3 - aminodibenzofuran, 2 - amino - 3 dibenzothiophene and 2 - amino - 6-fluorobenzothiazole. In examples : (1) 2- methyl - 5 - chloroaniline is diazotized and condensed with guanylurea - N - sulphonic acid in aqueous causitc soda solution ; (2) 2:5- dichloroaniline is diazotized and condensed with guanylurea-N-sulphonic acid in the presence of hydrated lime ; (3) 2-nitro-4-methylanilne is diazotized and condensed with guanylurea- N-sulphonic acid in the presence of hydrated lime and calcium acetate ; (4) 3-chloroaniline is reacted as in (1) ; (5) 2-methoxy-5-chloroaniline is reacted as in (2) ; (6) benzidine is tetrazotized and condensed as in (1); (7) 2- methyl- 5-chloroaniline is diazotized and condensed with N-nitroguanylurea in aqueous caustic soda 'solution. The alkyl and aryl derivatives of guanylurea-N-sulphonic acid and of N-nitroguanylurea may also-be employed. Specification 515,981 is referred to.