Patent GB-585940-A (GB)
Title: Bicyclic compounds containing the diphenylamine grouping, process of making them and their use in the colouration of textile materials other than cellulose
IPC: C09B51/00
Filed: 1944-09-01
Abstract: Mononitro diphenylamine compounds carrying on the same benzene nucleus that carries the nitro group, a sulphonamido-, N-alkylsulphonamido-, or a sulphonhydrazido group, are obtained by condensing in presence of an acid-binding agent, a monocyclic primary aromatic amine, advantageously in excess, with a monocyclic compound carrying on the nucleus a halogen atom ortho to which is a nitro group and a sulphonamido-, N-alkylsulphonamido- or a sulphonhydroazido group.  Specified monocyclic primary aromatic amines are aniline, o-anisidine, o-, m- and p-nitraniline, o-nitro-p-methoxyaniline, o-, m- and p-aminophenol, m-aminophenoxyacetic acid, o-aminophenoxyacetic acid amide, p-(b -hydroxyethoxy)-aniline, o-(b -sulphatoethoxy)-aniline, o- and m-aminoacetophenone, o-nitro-p-chloraniline, o-nitro-p-fluoraniline, N - acetyl - N - (b  - hydroxyethyl) - o - phenylenediamine and N : N - dimethyl - p - phenylenediamine.  Advantageously, chlorine-containing mononitro sulphonamido compounds are employed and one or both of the sulphonamide hydrogen atoms may be replaced by alkyl radicals, e.g. methyl, ethyl, isoamyl, b -hydroxyethyl, b -methoxyethyl, allyl, benzyl, tetrahydrofurfuryl, cyclohexyl, b -hydroxy-b -ethoxyethyl, cetyl, lauryl, b -sulphoethyl or b -sulphatoethyl.  Specified acid-binding agents are the alkali metal carbonates, and bicarbonates, alkaline earth carbonates and bicarbonates or tertiary amines.  The invention includes the dyeing of non-vegetable textile fibres, e.g. cellulose organic esters such as cellulose acetate, or cellulose ethers, with compounds having the foregoing constitution.  Numerous examples are given. 4-Chloro-3-nitrobenzenesulphonamide may be obtained either by condensing 4-chloro-3-nitrobenzenesulphonyl chloride with ammonium carbonate or by treating the former compound with dilute ammonia. 4-Chloro-3-nitrobenzenesulphonyl chloride is obtained by condensing sodium 4-chloro-3-nitrobenzenesulphonate with phosphoruspentachloride or by treating sodium 4-chloro-3-nitrobenzenesulphonate with chlorosulphonic acid at 150 DEG  C.  4-Chloro-3-nitrobenzenesulphonic acid is obtained by sulphonating o-chloronitrobenzene with fuming sulphuric acid.  4-Chloro-3-nitrobenzenesulphonmethylamide is obtained by treating 4-chloro-3-nitrobenzenesulphonyl chloride in acetone with 30 per cent aqueous methylamine at 10-20 DEG  C., and precipitating the product by water.  The following sulphonamide compounds may be prepared similarly: 4-chloro-3-nitrobenzene dimethyl-, isopropyl-, tetrahydrofurfuryl-, b  - methoxy - ethyl-, ethyl-, b -hydroxyethyl-, butyl-.  4 - Chloro - 3 - nitrobenzenesulphonhydrazide is obtained by adding 4-chloro-3-nitrobenzenesulphonyl chloride to a slight excess of aqueous hydrazine.  p-(b -Hydroxyethoxy)-aniline is obtained by reducing at 90 DEG  C. and 400-800 lbs. per sq. in. pressure commercial p-nitrophenyl-b -hydroxyethyl ether with hydrogen in presence of Raney nickel and a mixture of 95 per cent ethanol and 5 per cent methanol, and distilling the filtrate.  N - Acetyl - N - (b - hydroxyethyl) - o - phenylene - diamine is obtained by treating at 90-95 DEG  C. aqueous o-nitro-N-(b -hydroxyethyl) aniline and reducing the resulting N-acetyl derivative with hydrogen and Raney nickel in methanol at 75-90 DEG  C. and 1500 lbs. per square inch pressure.  p-Butoxyaniline is obtained by heating under reflux the sodium salt of p-nitrophenol and butyl bromide and reducing the resulting p-nitrophenyl-butyl ether in methanol with hydrogen in presence of Raney nickel under pressure.  Specified organic cellulose derivatives that can be coloured yellow by the dyes of the invention are cellulose acetate-, propionate-and butyrate; cellulose acetate propionate-and acetate butyrate; methyl-, ethyl- and benzyl cellulose.  Advantageously, the dyes are applied to a textile material as an aqueous suspension, obtained by grinding the dye to a paste, optionally in presence of a dispersing agent, e.g. a sulphonated oil or soap, and subsequent dispersion in water, and direct dyeing is effected advantageously at 75-85 DEG  C. Specification 552,190 is referred to.