Patent GB-369936-A (GB)
Title: Manufacture of metalliferous azo-dyestuffs
IPC: C09B45/02
Filed: 1930-12-23
Abstract: Azo dyes, metal compounds of; cellulose esters or ethers or regenerated celluloses, dyeing.--Metalliferous azo dyestuffs are obtained in substance by treating with an agent which yields metal an azo dyestuff of the general formula <FORM:0369936/IV/1> wherein R is a benzene or naphthalene residue carrying no substituent other than the hydroxy group, which is in o-position to the azo group, and the two sulpho groups, R1 is hydrogen, alkyl, aryl, or aralkyl, and the carbon atoms 5 and 6 form part of an aromatic ring.  The treatment with an agent yielding metal may be effected in the course of the manufacture of the parent dyestuffs, which are obtainable by coupling a diazotized o-oxyaminobenzenedisulphonic acid or o-oxyaminonaphthalenedisulphonic acid with a 2 : 4-dioxyquinoline. Specified diazo components are 2-aminophenol-4 : 6-disulphonic acid, 1-amino-2-phenol-4 : 6-disulphonic acid, 2-aminonaphthol-4 : 8-disulphonic acid, and 2-aminonaphthol-3 : 8-disulphonic acid.  The coupling components may be 2 : 4-dioxyquinoline, 1-alkyl- or 1-aryl-2 : 4-dioxyquinolines, or 5 : 6-, 6 : 7-, or 7 : 8-benzo-2 : 4-dioxyquinolines or derivatives thereof substituted in the nucleus by halogen, NO2, SO3H or O-alkyl, or may be derived from primary and secondary aromatic monamines or diamines in general; they may be capable of coupling once or several times with the diazo components. Agents yielding one or more of the metals chromium, copper, iron, cobalt, nickel, manganese, zinc, vanadium, and titanium may be employed.  The metalliferous products are readily soluble in water and are applicable for dyeing wool, loaded or unloaded silk, cotton, leather, regenerated cellulose silk, or cellulose esters or ethers and for colouring varnishes having a basis of cellulose or a natural or artificial resin.  The dyeings are well equalized pure orange and red to violet shades fast to water, washing, alkali, fulling, and light.  The following examples are specified: (1) The dyestuff 2-aminophenol-4 : 6-disulphonic acid --> 2 : 4-dioxyquinoline is boiled for 18-20 hours under reflux with an aqueous solution containing chromium sulphate and sulphuric acid; the product dyes wool from a sulphuric acid bath very even bright yellowish red shades fast to light and fulling.  (2) The dyestuff 2-aminophenol-4 : 6-disulphonic acid --> 7 : 8-benzo-2 : 4-dioxyquinoline is chromed as in (1); the product dyes wool from a sulphuric acid bath uniform blueish red shades fast to light and fulling.  (3) The dyestuff 2-aminophenol-4 : 6-disulphonic acid --> 6 : 7-benzo-2 : 4-dioxyquinoline is boiled for about 20 hours under reflux with an aqueous solution of chromium formate; the product dyes wool from a sulphuric acid bath level bordeaux red shades fast to light and fulling.  (4) The dyestuff 2-aminophenol-4 : 6-disulphonic acid --> N-phenyl-2-keto-4-oxyquinoline is boiled for about 18 hours with an aqueous solution containing chromium sulphate and sulphuric acid; the product dyes wool from a sulphuric acid bath uniform fast yellowish red shades.  Examples are also given of the dyeing processes for wool, natural or loaded silk, regenerated cellulose silk and cotton, and of the incorporation of the dyestuffs in varnishes. Specification 327,380, [Class 2 (iii), Dyes &c.], is referred to.  1 - Diazo-2-phenol-4 : 6-disulphonic acid is obtained by heating 1-chloro-2-nitrobenzene-4-sulphonic acid with ammonia under pressure, sulphanating the 1-amino-2-nitrobenzene-4-sulphonic acid so produced, diazotizing the 1-amino-2-nitrobenzene-4 : 6-disulphonic acid, and treating the product with sodium carbonate to replace the nitro group by hydroxyl.  2 : 4-Dioxyquinoline derivatives.--The simple derivatives such as the 1-alkyl- or 1-aryl-2 : 4-dioxyquinolines and 5 : 6-, 6 : 7-, or 7 : 8-benzo-2 : 4-dioxyquinolines or their derivatives substituted in the nucleus by halogen, NO2, SO3H or O-alkyl are obtainable by known methods from the corresponding acetylanthranilic acid or 2-acetylaminonaphthalene-3-carboxylic acid derivatives or naphthylamines.  Thus an o-acetylaminocarboxylic acid may be converted into the corresponding 2 : 4-dioxyquinoline by heating with an alkaline earth metal oxide, and a non-acylated naphthylamine carrying no o-carboxy group may be converted into the corresponding 2 : 4-dioxyquinoline by heating with malonic acid dialkyl esters. More complex derivatives are obtainable from o-carboxylic acids (or their esters) of benzidines, aminobenzimidazoles, aminoazobenzenes, aminobenzothiazoles, aminostilbenes, aminoarylethers, aminocarbazoles, aminodiarylmethanes, or their substitution products by heating with malonic acid dialkyl esters and an alkali ethylate.  In the case of diamines both amino groups take part in ring formation.