Patent GB-802681-A (GB)
Title: New anthraquinone vat dyestuffs and process for their manufacture
IPC: C09B3/06
Filed: 1955-01-28
Abstract: The invention comprises vat dyes which contain at least one anthraquinone nucleus substituted in 1-position by an amino group, in 4-position by an amino group which is substituted by the residue of a carboxylic acid, a triazine, or a quinazoline, and in 2-position is attached directly to a carbon atom of a 5- or 6-membered hetero ring, which ring contains as further ring members two hetero atoms attached to the mentioned carbon atom, including a nitrogen atom having its valencies entirely occupied in ring formation, together with 2-3 further carbon atoms which are at the same time ring members of a further non-vattable ring system which can itself be attached to any other ring system.  The hetero ring may be an oxazole, imidazole, N-alkylimidazole, N-arylimidazole or thiazole ring, or it may be a 6-membered hetero ring having three adjacent carbon atoms common to a non-vattable ring and therefore attached in para-position thereto. The dyestuffs may be built up by customary methods of acylation, ring-formation, and introduction of amino groups.  The products may be used as such or as their leuco ester salts for the dyeing or printing of wool, silk, cotton, linen, artificial silk, regenerated cellulose, nylon.  In examples of the acylation method, (1) 1 mol. 2-[11 : 41-diaminoanthraquinonyl-(21)]-benzoxazole is reacted with (a) 1 mol. benzoyl chloride or its 4-chlor, 4-cyano-, or 3-isopropylsulphonyl derivative, or with 1 : 11-diphenyl-4-carboxylic acid chloride, 1-aminoanthraquinone-2-carboxylic acid chloride, 1 - amino - 4 - benzoylaminoantraquinone-2-carboxylic acid chloride or with (b) 1 mol. of the chlorquinazoline of the formula <FORM:0802681/IV (c)/1> (obtained by condensation of 2-amino-3-cyanoanthraquinone with anthraquinone-2-carboxylic acid chloride and reaction with phosphorus pentachloride), or with (c) 1/2 mol. isophthaloyl chloride, terephthalyl chloride, 1,11-diphenyl-4,41-dicarboxylic acid dichloride, naphthalene-2,6-dicarboxylic acid dichloride, 1,11-azobenzene-3,31- or 4,41-dicarboxylic acid dichloride, thianthrene dicarboxylic dichloride, 1,5-diaminoanthraquinone-2,6-dicarboxylic acid dichloride, or with (d) 1 mol. of isophthaloyl chloride followed by reaction of the product with 1 mol. 4-aminoanthraquinone - 1(N)2 - benzacridone, or with (e) 1/2 mol. cyanuric chloride, followed by reaction of the residual chlorine with ammonia, or (f) 1/2 mol. 2-methyl-4,6-dichloro-1,3,5-triazine, (2) 4,5,6,7-tetrachloro-2-[11,41-diaminoanthraquinonyl - (21)] - benzoxazole or the 4,5,7-trichloro body is reacted with benzoyl chloride, (3) the compound of formula <FORM:0802681/IV (c)/2> (made by reaction of 1-amino-4-bromanthraquinone-2-carboxylic acid chloride with 2-(31-hydroxy - 41 - amino - phenyl) - 5,6 - phthaloylbenzoxazole, ring-closure, and replacement of the 4-bromine atom by amino by reaction with p-toluenesulphonic acid amide and hydrolysis) is reacted with 4-chlorbenzoyl chloride, (4) isophthaloyl chloride is reacted with compounds of the formula <FORM:0802681/IV (c)/3> where R1 is a 2-benzoxazolyl radical having a 6-methyl, 6-methoxy, 6-chloro-, 6-phenylsulphonyl, or 6-sulphodiethylamido substituent, a 2-benzthiazolyl radical, a 2-benzimidazolyl radical, or a 2-naphthoxazolyl radical (a  or b  or peri), (5) 2 mols. benzoyl chloride is reacted with 1 mol. of the compound of the formula <FORM:0802681/IV (c)/4> or with the corresponding compounds having no amino groups in the right-hand anthraquinone radical or only the amino group ortho to the oxazole ring linkage, which compounds are prepared in two stages from 2,5-diamino-3,6-dichlor-benzoquinone and a 1-aminoanthraquinone-2-aldehyde to give an intermediate e.g. of the formula <FORM:0802681/IV (c)/5> (the bromine may be absent) which is further reacted with an anthraquinone-2-carboxylic chloride followed by ring-closure, and introduction of amino groups by nitration and reduction or by reaction of halogen with p-toluene sulphonamide and hydrolysis, as necessary; (6) 2 mols. benzoyl chloride is reacted with 1 mol. of a compound of the formula <FORM:0802681/IV (c)/6> which is prepared from 3,31-dihydroxybenzidine hydrochloride and 2 mols. 1-amino-4-nitroanthraquinone-2-carboxylic chloride, followed by reduction and ring-closure.  As examples of the ring-closure method, (7) 1-amino-4-benzoylaminoanthraquinone-2-carboxylic acid chloride is condensed with o-aminophenol and the product ring-closed, and (8) 2 mols. 1-amino - 4 - nitroanthraquinone - 2 - carboxylic acid chloride is condensed with 1 mol. of 1,3-diamino-4,6-dibromobenzene or 1 mol. 1,4-diamine-2,5-dibromobenzene followed in each case by double ring-closure.  Examples of dyeing and printing on cotton are given. 2 - [11,41 - Diamino - anthraquinonyl - (21)-benzoxazole is prepared from 1-amino-4-nitroanthraquinone-2-carboxylic acid chloride and o-aminophenol followed by ring-closure and reduction.