Patent GB-544887-A (GB)
Title: Manufacture of dyestuffs becoming green when chromed
IPC: C09B29/06
Filed: 1940-10-25
Abstract: 544,887. Dyes. GEIGY, AKT.-GES., J. R. Oct. 25, 1940, No. 15686. Convention date, June 20. Addition to 535,110. [Class 2 (iii)] Monoazo dyes, giving, especially on wool, fast dyeings which are green when after-chromed, are obtained by coupling with 2:3-aminonaphthoic acid a diazotized 2-aminophenol-4-or 5-phenylsulphone or 2-aminophenol-4-or 5- sulphonamide, N-alkyl-or N-aralkyl-substituted in the sulphamido group, such diazo component carrying outside the aminophenol nucleus a group, e.g. a sulphonic or carboxylic acid group, imparting solubility in water. Examples relate to the production of the dyestuffs, (1) 2- aminophenol - 4 - (3<SP>1</SP> - sulpho)phenylsulphone of Specification 324,090, [Class 2 (iii)], # 2:3- aminonaphthoic acid ; (2) the 4'-sulphobenzylamide or the N-methyl-N-#-sulphoethyl-amide of 2-aminophenol-4-sulphonic acid # 2:3-aminonaphthoic acid. A table is also given showing the shades of the direct and after-chromed dyeings on wool with the use as diazo components of the carboxymethylamide, 4<SP>1</SP>-sulpho- N-methyl-or ethyl-anilide and 3<SP>1</SP>-sulpho-N- ethylanilide of 2-aminophenol-4- sulphoniacid, the 3<SP>1</SP>-sulpho-N-ethylanilide of 5-chloroc 2-aminophenol-4-sulphonic acid, the 4<SP>1</SP>-sulpho- N-ethylanilide of 5- or 6-nitro-2-aminophenol-4- sulphonic acid and the 4<SP>1</SP>-sulpho-N-ethylanilide of 2-aminophenol-5-sulphonic acid. - The 4<SP>1</SP>-sulpho-benzylamide and the N-methyl- N-#-sulphaethyl-amide of 2-aminophenol-4-aulphonic acid are obtained by condensing benzylamine-4-sulphonic acid and N-methyl-taurine respectively with 2-nitro-chlorobenzene-4-sulphonic acid chloride in aqueous sodium carbonate solution, boiling a solution of the condensation product in aqueous caustic soda and reducing the nitro group. ' The carboxymethylamide of 2-aminophenol-4- sulphonic acid is obtained by condensing the hydrochloride of glycine ethyl ester with 2- nitrochlorobenzene-4-sulphonic acid chloride in presence of anhydrous pyridine, boiling a solution of the condensation product in aqueous caustic soda and reducing the nitro group. The 4<SP>1</SP>-sulpho- N -methylanilide of 2-aminophenol-4-sulphonic acid is obtained by condensing N-methylaniline-4-sulphonic acid with 2- nitrochlorobenzene-4-sulphonic acid chloride in aqueous sodium carbonate solution, boiling a solution of the condensation product in aqueous caustic soda and reducing the nitro group. The 41- and 3<SP>1</SP>-sulpho- N-ethylanilides of 2- aminophenol-4-sulphonic acid are similarly obtained from N-ethylaniline-4- and 3-sulphonic acids respectively. The 3<SP>1</SP>-sulpho-N-ethylanilide of 5-chloro-2- aminophenol-4-sulphonic acid is similarly obtained by way of the condensation product from N-ethylaniline-3-sulphonic acid and 1:3- dichloro - 6 - nitrobenzene - 4 - sulphonic acid chloride (obtained by the action of phosphorus pentachloride on the sulphonic acid).  The 4<SP>1</SP>-sulpho- N-ethylanilide of 5-nitro-2- aminophenol-4-sulphonic acid is obtained by saponifying in a boiling alkaline solution the product of nitration of the sulpho-N-ethylanilide of a benzoxazolonesulphonic acid obtained by the action of phosgene in caustic soda solution on the 4<SP>1</SP>-sulpho-N-ethylanilide of 2-aminophenol-4-sulphonic acid. The 4<SP>1</SP>-sulpho-N-ethylanilide of 6-nitro-2- aminophenol-4-sulphonic acid is obtained by nitrating the 4<SP>1</SP>-sulpho-N-ethylanilide of 2- acetylaminophenol-4-sulphonic acid and deacetylating the product with boiling alkali. The 4<SP>1</SP>-sulpho- N -ethylanilide of 2-aminophenol-5-sulphonic acid is obtained by heating in alkaline solution the product of re-action of N-ethylaniline-4-sulphonic acid with the chloride of benzoxazolone-6-sulphonic acid obtained by treating benzoxazolone with chlorosulphonic acid. The Specification as open to inspection under Sect. 91 comprises also the similar use as diazo component of (a) the corresponding 2-aminophenol-4- or 5-sulphonamides in general, (b) the 31-chloro-, 3<SP>1</SP>-methyl- and 31-methoxyderivatives of 2-aminophenol-4-(5<SP>1</SP>-sulpho) phenylsulphone, (c) the 2<SP>1</SP>- and 3<SP>1</SP>-carboxyanilides of 2-aminophenol-4-sulphonic acid and the 2<SP>1</SP>-carboxyanilide of 2-aminophenol-5- sulphonic acid.  The 3<SP>1</SP>-carboxyanilide of 2-aminophenol-4- sulphonic acid is obtained by condensing aniline-3-carboxylicacid with 2-nitrochlorobenzene-4-sulphonic acid chloride in aqueous sodium carbonate solution, boiling a solution of the condensation product in aqueous caustic soda and reducing the nitro group. The 2<SP>1</SP>-carboxyanilide of 2-aminophenol-4- sulphonic acid is obtained by heating in alkaline solution the product of reaction of aniline-2-carboxylic acid with the chloride of benzoxazolone-6-sulphonic. acid. This subject-matter does not appear in the Specification as accepted.