Patent GB-288788-A (GB)
Title: New and improved azo dyestuffs
IPC: C09B29/00
Filed: 1927-03-02
Abstract: 288,788. Carpmael, W., (I. G. Farbenindustrie Akt.-Ges.). March 2, 1927. Azo dyes.-Monoazo and polyazo dyes are obtained by employing as diazo components such derivatives of 2 : 5-diaminodiphenylsulphone as are substituted in the 5-position by acidyl or alkyl groups, and in the non-amino substituted nucleus by an oxy group and a carboxylic group in ortho position to each other. The manufacture of these derivatives is described in Specification 267,366. The products may be saponified to eliminate the acidyl group, rediazotized and coupled with suitable components. In examples, (1) 2-amino-5- acetylamino-4<1>-oxy-3<1>-carboxydiphenylsulphone is diazotized and coupled with sodium methylketol sulphonate; the product dyes wool from an acid bath in fast even reddish-yellow shades slightly changed towards greenish-yellow when afterchromed. If acetoaceticanilide-4-carboxylic acid is used as coupling component, the product gives fast greenish-yellow dyeings when after-chromed, whiles the disazo dyestuff obtained by coupling two molecules of the diazo component with diacetoacetyl-o-tolidine, and the monoazo dyestuffs obtained by coupling with 1-(2<1>: 5<1>-dichlor-4<1>- sulpho)-phenyl-3-methyl-5-pyrazolone or with 1-(2' - oxy-3<1>-carboxy-5<1>-sulpho)-phenyl-3-methyl- 5-pyrazolone give yellow shades, and the product obtained by coupling with chromotropic acid gives a bordeaux shade which is converted into a fast reddish-violet by chroming. Naphthol sulphonic or carboxylic acids and 2 : 3-oxynaphthoic arylides and their sulphonic acids are also specified as components. The dyestuff from 2 : 3-oxynaphthoic anilide may be formed on the fibre in the usual manner; it gives a clear fast red and the dyeing may be treated with metal compounds. (2) The same diazo component is coupled with 2-methylaminonaphthalene-7-sulphonic acid, the product dyes wool from an acid bath in clear bluish-red shades, which are not substantially altered by subsequent chroming; it also gives clear fast red shades when chrome printed on cotton, and may be used as a pigment dyestuff and as a size or printing colour. If 2-ethylaminonaphthalene-6-sulphonic acid is used as coupling component, a, more yellow dyestuff is produced; 2: 6- and 2: 7-naphthylamine sulphonic acids, ethylbenzylaniline, and ethyl-p-sulphobenzylaniline give yellowish-red products, and 2-methylaminonaphthalene-6-carboxylic acid a red product. The following components are also specified : - 2 : 8 : 6-aminonaphtholsulphonic acid, coupled in acid solution (red shades). 2-methylamino-8-naphthol-6-sulphonic acid (violet), 2-ptolylamino-8-naphtol-6-sulphonic acid (brownishviolet) and 2-w-acetylamino-ethylamino-8-naphthol-3 : 6-disulphonic acid (brown). Other acidyl derivatives may be used as diazo components, e.g. the chloracetyl (obtained bv treating the diaminosulphone with chloracetyl chloride), oxalyl (obtained by melting the diamonisulphone with oxalic acid), carbethoxy, #-chlorethylsulpho (from #-chlorethylsulphochloride and the diaminosulphone), or urea derivatives. If the 5-benzoyl derivative is coupled in acid medium with 2 : 8 : 6- acid the product dyes wool with after-chroming in a, fast bordeaux shade, while the corresponding dyestuffs from the p-methoxybenzoyl and phthaloyl derivatives give bluer shades. The acidyl group in the 5-position may also be an arylsulpho residue, e.g. p-toluene sulpho-, salicylsupho-, or o- or p-chlor-m-nitrophenylsulpho-, 2 : 8 : 6-acid, H-acid, or naphthylamine sulphonic acids being used as coupling components. The product from 2-diazo-5-p-toluenesulphamino-4<1>-oxy-3<1> - carboxydiphenylsulphone and 2-naphthylamine-7-sulphonic acid gives pure red shades on wool, when after-chromed. Other substituents may also be present in the diazo component, thus 2-amino-5- acetylamino-4-methoxy-5<1>-methyl-4<1>-oxy-3<1>- carboxydiphenylsulphone (from 2 : 5-diaminoanisol by the method described in Specification 267,366) when diazotized and coupled with 2 : 8 : 6-acid or with 2-methylamino-8-naphthol-6-sulphonic acid yields bordeaux or violet dyestuffs which may be used as pigments or for dyeing wool. The dyestuff from 2-amino-5-acetylamino-4-methyl-4<1>-oxy- 3<1>-carboxydiphenylsulphone (obtained by acetylating the sulphone made from 2-carboxyphenol-4- sulphinic acid and methylquinone diimide by the process of Specification 267,366) and 2 : 8 : 6-acid (acid coupling) dyes wool a bluish red when afterchromed. The 2-amino-4-methoxy-5-acetylamino- and 2-amino-4-ethoxy-5-chloracetvlamino-4'-oxy- 3<1>-carboxydiphenylsulphones are also specified as diazo components. (3) 2-Amino-5-dimethylamino- 4<1>-oxy-3<1>-carboxydiphenylsulphone is diazotized and coupled with 2: 8: 6-acid in acid medium, the product dyes wool in violet shades which are rendered very fast to light and insensitive to metals by after-chroming; the diethylamino compound as diazo component gives a similar product, while if 2-methylamino-8-naphthol-6-sulphonic acid is used as coupling component, the products dye wool in reddish blue shades. The dyestuff from the diethylamino compound and chromotropic acid gives blue dyeings on wool. The dyestuffs may be converted into chromium compounds by heating with chroming agents, e.g. with chromium fluoride in the presence of acidbinding agents. (4) 2-Amino-5-formylamino-4<1>- oxy-3<1>-carboxydiphenylsulphone (by boiling the 2 : 5-diaminosulphone with strong formic acid) is diazotized and coupled with the sodium salt of 2 : 8 : 6-acid, the product dyes wool a violet shade when after-chromed. (5) 2-Amino-5-acetylamino-4<1>-oxy-3<1>-carboxydiphenylsulphone is diazotized, coupled with 1-naphthylamine-7-sulphonic acid, rediazotized and coupled with 1 : 4-naphthol sulphonic acid. The product is boiled with caustic soda solution to remove the acetyl group, and the aminodisazo dyestuff obtained is rediazotized and coupled with 2 : 6-naphthol sulphonic acid. The product dyes cotton in a glauber salt-sodium carbonates bath in blue shades, which are converted to a fast reddish-blue by subsequent treatment with a copper compound. 2-Ethylaminonaphthalene-6-sulphonic acid is obtained from ethylamine and 2-amino- or 2-oxynaphthalene-6-sulphonic acid in the presence of sulphites. 2-Methylaminonaphthalene-6-boxylic acid is similarly obtained from 2 : 6-oxynaphthoic acid. 2-Methylamino-8-naphthol-6-sulphonic acid is obtained from methylamine and 2 : 8-dioxynaphthalene-6-sulphonic acid or 2 : 8 : 6-aminonaphthol sulphonic acid in the presence of sulphites.