Patent GB-627125-A (GB)
Title: Improvements in or relating to sulphonamidoaldehydes and lower acetals thereof
IPC: G03C7/34
Filed: 1947-05-01
Abstract: Sulphonamidoaldehydes and their acetals of the formula <FORM:0627125/IV (a)/1> (where X is hydrogen or acyl, Y1 and Y2 are together oxygen or -O-R1-O-, where R1 is alkylene of 2-4 carbon atoms, or are each -OR2, where R2 is an alkyl group of 1-4 carbon atoms, and M is hydrogen or halogen and in which other substituents may be present in the rings) are used to prepare dyes for application to textiles, fibres, filaments and films by acetal-formation with cellulose, e.g. cotton and viscose yarn, and also with casein.  The sulphonamidoaldehydes and acetals may be condensed with polyvinyl alcohols or hydrolysed vinyl ester polymers to form colour components.  The polyvinyl acetals may also be added to a fibre-forming spinning solution. Specifications 535,341 is referred to.ALSO:Sulphonamidoaldehydes and their acetals of the formula <FORM:0627125/IV (b)/1> (in which X is hydrogen or acyl, Y1 and Y2 are together oxygen or the ring -O-R1-O-, where R1 is alkylene of 2-4 carbon atoms, or are each -OR2, where R2 is alkyl of 1-4 carbon atoms, M is hydrogen or halogen, and any of the free positions in the rings may be substituted, e.g. by alkyl, aryl, alkoxy, aryloxy, halogen, nitro, amino, acylamino, sulphonic acid, carboxylic acid, sulphonamide, trifluoromethyl and b -hydroxyethyl groups) are prepared by reacting a sulphonyl halide:- <FORM:0627125/IV (b)/2> (where L is halogen) with an amine:- <FORM:0627125/IV (b)/3> in the presence of a basic reagent.  A preferred product is that prepared from a 1-naphthol-2-sulphonyl halide, e.g. m-(1-hydroxynaphthalene-2-sulphonamido) benzaldehyde.  The halides may be prepared from the naphthol sulphonic acids by treatment with phosphorous trichloride, oxychloride, &c. after protection of the hydroxyl group by acylation, e.g. with acetyl chloride, or ethyl chlorocarbonate.  The following are representative of the sulphonyl chlorides: 1-ethylcarbonatonaphthalene-2-sulphonyl chloride, 1-benzoxynaphthalene-2-sulphonyl chloride, 1-acetoxy-4-chloronaphthlene-6 - sulphonyl chloride, and 1 - acetoxy - 2 - (N-phenyl) - naphthamido - 5 - sulphonyl chloride. Other aminobenzaldehydes mentioned include the o- and p-isomers, 2-chloro-3-aminobenzaldehyde, 2 - amino - 6 - formylbenzoic acid, 3-amino - 2 - formylbenzenesulphonic acid and 5 - amino - 2 - formylbenzenesulphonamide, and their acetals.  The reaction is performed between -10 DEG  and 100 DEG  C., and preferably between 0 DEG  and 30 DEG  C., in a solvent, e.g. dioxan, water, aqueous dioxan, ether, acetone, aqueous acetone or dimethylformamide, and in the presence of a neutralizing agent, e.g. alkali metal carbonates, acetates, hydroxides, phosphates, or organic bases, e.g. pyridine, trialkylamines, or triethanolamine.  When X in the general formula is acyl, it may be hydrolysed off, e.g. with aqueous-alcoholic alkali at 90 DEG  C., or with an acid solution. When acetals are being prepared, R1 may be methyl, ethyl, propyl or butyl, or the acetal may be derived from ethylene glycol, 1 : 3-propylene glycol, 1 : 2-propylene glycol or 1 : 3-butylene glycol.  These acetal groupings may be later hydrolysed off.  In example (1) m-aminobenzaldehyde ethylene glycol acetal in an aqueous-dioxan solution of potassium carbonate is treated at 0 DEG  C. with 1-acetoxynaphthalene-2-sulphonyl chloride to give m-(1-acetoxynaphthalene-2-sulphonamido)-benzaldehyde ethylene glycol acetal, which is hydrolysed with acetone-hydrogen chloride to the free aldehyde.  The latter aldehyde is prepared via the dimethyl acetal in example (2).ALSO:Sulphonamidoaldehydes and their acetals of the formula <FORM:0627125/IV (c)/1> (where X is hydrogen or acyl, Y1 and Y2 are together oxygen or -O-R1-O-, where R1 is alkylene of 2-4 carbon atoms, or are each -OR2 where R2 is an alkyl group of 1 to 4 carbon atoms, and M is hydrogen or halogen, and in which any of the rings may be substituted) are used as a coupling component for azo dyes, which may be used for dyeing cellulosic fibres, e.g. cotton and viscose yarn, and protein fibres, e.g. wool, silk, and casein.