Patent GB-497326-A (GB)
Title: Improvements in the manufacture and production of azo dyestuffs
IPC: C09B33/147
Filed: 1937-06-10
Abstract: Azo dyes are prepared in substance or on the fibre by coupling aromatic diazo compounds with o-hydroxy aryl carboxylic acid arylides of the general formula <FORM:0497326/IV/1> wherein Ar is an aromatic radicle and X is an arylene radicle containing at least one salt-like radicle, imparting water-solubility and derived from a -COOH or -SO3H group, which radicle is attached to an alkylene radicle bound to X directly or by an oxygen atom or an amino group, -NR- (R being hydrogen or an organic radicle).  The salt-like radicles may be sulphonic, sulphuric, thiosulphuric or carboxylic acid groups neutralized by an alkali metal, ammonia, an amine or a quaternary ammonium group.  Arylides from the following amines: the sodium salts of 2.4-diaminophenylmethane-o -sulphonic acid, benzidine-3.31-di-o -methane sulphonic acid, 2.4-diaminophenylacetic acid, 2.4-diaminophenoxyacetic acid, 4.41-diamino-3.31-diphenylacetic acid, 4.41-diamino-3.31-diphenoxyacetic acid, o -hydroxyethoxyphenylenediamine acid sulphuric esters and 3.31-di-o -hydroxyethoxybenzidine acid sulphuric ester and the following acids: 2-hydroxynaphthalene-, 2 - hydroxy - 6 - methoxynaphthalene-, 2 - hydroxyanthracene-, 2-hydroxydiphenyleneoxide-, and 2-hydroxycarbazole-3-carboxylic acids and 7.8-benzocarbazole-Bz.-3-hydroxy-2-carboxylic acid are specified. Specified diazo components are aniline, nitranilines, nitroaminophenols, aminodiphenylamines and aminobenzenes which may be further substituted, e.g. by halogen, alkyl fluoralkyl, alkoxy, sulphonalkyl, carboxylic or sulphonic acid groups.  The dyes are stated to have pronounced affinity for animal fibres such as wool, silk and leather and for cellulosic fibres.  In the examples the dyes are produced on mixed fabrics of wool and viscose artificial silk, and on wool slivers, natural silk, viscose artificial silk and cellular wool by treating the material in a bath containing the arylide, with or without addition of Glauber's salt, rinsing with cold water and developing in a bath of the diazotized amine.  In examples, (1) the di-arylide from 2.3-hydroxynaphthoic acid and benzidine-3.31-di-o -methane sulphonic acid sodium salt and 4-chlor-2-nitraniline or 4-amino-41-methoxydiphenylamine; (2) the di-arylide from 2.3-hydroxynaphthoic acid and 4.41-diamino-3.31-diphenoxyacetic acid sodium salt or benzidine-3.31 - diacetic acid sodium salt, and 4-chlor-2-aminotoluene; (3) the di-arylide from 2.3-hydroxynaphthoic acid and 2.4-diaminophenylethane-o -sulphonic acid sodium salt or 2.4-diaminophenoxyethane-o -sulphonic acid sodium salt or 2.4-diaminophenoxyethane-o -thiosulphuric acid sodium salt, and p-aminodiphenylamine; (4) the diarylide from 2.3-hydroxynaphthoic acid and 2.4-diaminophenylmethane-o -sulphonic acid sodium salt or N-(2.4-diaminophenyl)-N-methyl taurine sodium salt, and m-chloraniline; (5) the diarylide from 2.3-hydroxynaphthoic acid and 4.41-diamino-3.31-di-(N-phenyltaurine) sodium salt or 4.41-diamino-3.31-diphenoxyethane-o -sulphonic acid sodium salt and nitraniline --> aminohydroquinone dimethyl ether, and the diarylide from 2 - hydroxydiphenyleneoxide - 3 - carboxylic acid and benzidine-3-31-di-o -methane sulphonic acid sodium salt and 4-chlor-2-nitraniline or 2.5-dichloraniline, are so used. 2.4-diaminophenylmethane - o  - sulphonic acid sodium salt is obtained by reacting dinitrobenzyl chloride with sodium sulphite and reducing the product.  Benzidine-3.31-di-o -methane sulphonic acid sodium salt is obtained by reacting o-nitrobenzyl chloride with sodium sulphite, reducing in alkaline medium and rearranging the hydrazo compound.  Sodium 2.4-diaminophenylacetate is obtained by reacting dinitrobenzyl chloride with potassium cyanide, saponifying the nitrile and reducing.  Sodium 2.4-diaminophenoxyacetate is obtained by reacting dinitrophenol with monochloracetic acid and reducing.  Sodium 4.41-diamino-3.31-diphenylacetate is obtained by reacting o-nitrobenzylchloride with potassium cyanide, saponifying, reducing in alkaline medium and rearranging the hydrazo compound. Sodium 4.41-diamino-3.31-diphenoxyacetate is obtained by reacting o-nitrophenol with monochloracetic acid, reducing in alkaline medium and rearranging the hydrazo compound.  Sodium o -hydroxyethoxyphenylenediamine acid sulphuric ester is obtained by reacting dinitrophenol with ethylenechlorhydrin, reducing and esterifying with sulphuric or chlorsulphonic acid.  Sodium 3.31-di-o -hydroxyethoxybenzidine acid sulphuric ester is obtained by reacting o-nitrophenol with ethylene-chlorhydrin, reducing in alkaline medium, rearranging and esterifying.  2.4 - diaminophenylethane - o  - sulphonic acid sodium salt is obtained by dinitrating the acetyl compound of phenylethyl alcohol, saponifying the acetyl group, treating with phosphorus halide, reacting the product with sodium sulphite and reducing.  2.4-diaminophenoxyethane - o  - sulphonic acid sodium salt is obtained by reacting dinitrophenoxyethyl alcohol with phosphorus halides, treating with sodium sulphite and reducing. 2.4 - diaminophenoxyethane - o  - thiosulphuric acid sodium salt is obtained by treating dinitrophenoxy ethyl-o -halide with sodium thiosulphate and reducing.  N - (2.4 - diaminophenyl) - N - methyltaurine is obtained by treating dinitrochlorbenzene with N-methyl taurine and reducing.  4.41 - diamino - 3.31 - di - (N - phenyl taurine) is obtained by reacting o-nitrochlorbenzene with taurine, reducing in alkaline medium and rearranging.  Di-arylides from the above amines are prepared by reacting the amines with the o-hydroxycarboxylic acid, its chloride or esters, the hydroxyl group of which may be acylated, the acyl group being subsequently removed. When preparing the sulphuric esters of arylides of o -hydroxyethoxy diamines, the esterification may be effected after formation of the arylide.