Patent GB-409014-A (GB)
Title: The manufacture of new azodyestuffs
IPC: C09B29/20
Filed: 1932-10-22
Abstract: Azo dyes are made in substance or on the fibre by coupling diazo compounds of o-nitroamines of the general formula <FORM:0409014/IV/1> in which X = NH, NR (R = hydrocarbon residue), S, SO2, O, CH2 or CO with arylides of 2 : 3-oxynaphthoic acid, whereby the components may be substituted by groups which do not cause solubility in water.  In examples, the following dyestuffs are produced on cotton: (1) 2-nitro-3-aminodiphenyleneoxide --> the 2.4-dimethoxy-5-chloranilide or b -naphthalide; (2) 2-nitro-3-aminocarbazole --> the 2-methyl-4-methoxyanilide, 2-methyl-4-chloranilide or b -naphthalide; (3) 2-amino-3-nitrofluorenone --> p-anisidide or m-nitranilide; (4) 2-amino-3-nitrofluorene --> the 3-chlor-4 : 6-dimethoxyanilide; (5) 2-amino-3-nitrodiphenylenesulphide --> 2-methyl-4-chloranilide or b -naphthalide; (6) 2 - amino - 3 - nitrodiphenylenesulphone --> 2-methyl-4-chloranilide.  Substituents such as alkyl, aralkyl, alkoxy, aryl, aryloxy, aralkyloxy, halogen, the nitro group, acylamino, sulphonamide, sulphonalkyl, sulphonaralkyl, sulphonaryl and aryl or alkylketone groups may also be present. Other diazo compounds specified are 3-amino-2-nitro-, 1-amino-2-nitro-, 2-amino-3 - nitro - 6 - bromo-, 2 - amino - 3 : 7 - dinitro-, 2 - amino - 3 - nitro - 6 - sulphodiethylamino -, 2 - amino - 3 - nitro - 6 - ethylsulphone-, 2 - amino - 3 - nitro - 7 - methoxy - and 1 - methyl - 2 - amino - 3 - nitro - diphenyleneoxides, 3 - amino - 4 - nitro-, 2 - amino - 3 - nitro-, 1 - amino - 2 - nitro-, 3 - nitro - 2 - amino - 6 - chloro-, 2 - amino - 3 - nitro - 7 - sulphodimethylamino-, 3 - amino - 2 - nitro - 6 - methoxy-, 3 - amino - 2 : 6 - dinitro-, 3 - amino - 2 - nitro - 7 - methylketone-, 3 - amino - 2 - nitro - 9 - methyl-, 3 - amino - 4 - nitro - 9 - ethyl -, 2 - amino - 3 - nitro - 9 - benzyl-, and 9 - phenyl - 3 - amino - 2 - nitro - 6 - chloro - carbazoles, 2 - amino - 3 - nitro - 7 - bromo - and 2-amino-3 : 7-dinitro-fluorenone, 2-amino-3 - nitro - 7 - bromofluorene, 2 - amino - 3 - nitro - 7 - bromodiphenylenesulphide, 2-amino-3-nitro-7 - sulphodiethylaminodiphenylenesulphide, 2 - amino - 3 - nitro - 7 - bromodiphenylenesulphone and 2 - amino - 3 - nitro - 7 - sulphodiethylamino - diphenylenesulphone.  Various shades fast to kier-boiling and light are obtained.  Specifications 282,682 and 298,697, [both in Class 2 (iii)], are referred to.  The Specification as open to inspection under Sect. 91 comprises also the use of diazo components of the above formula in which X = SO.  This subject-matter does not appear in the Specification as accepted. o-Nitroaminodiphenylene-sulphides, sulphones and oxides; o-nitroamino-fluorenes, fluorenones and carbazoles and derivatives thereof are made by diacetylation of the corresponding amine, nitration and hydrolysis.  The parent substituted amino compounds are made by introducing the substituents in question into the corresponding nitro compounds according to the usual methods followed by reduction of the amino group. 2-Amino-6-bromodiphenylene-oxide is thus obtained by brominating 2-nitrodiphenyleneoxide and reducing. 2-Amino-6-sulphodiethylaminodiphenyleneoxide is made by sulphonation of 2-nitrodiphenyleneoxide, conversion into the sulphonamide via the sulphochloride and reduction. 2-Amino-6-ethylsulphonediphenyleneoxide is made by reducing 2 - nitrodiphenyleneoxide - 6 - sulpho - chloride to the sulphinic acid, condensing with bromethyl and reducing. 6-Ethyldiphenyleneoxide or sulphide is obtained by ring closure of diazotized 4-ethyl-2<1>-aminodiphenyl-oxide or sulphide.