Patent GB-478700-A (GB)
Title: Improvements in the manufacture and production of vat dyestuffs of the anthraquinoneseries
IPC: C09B5/24
Filed: 1936-07-20
Abstract: Vat dyes of the anthraquinoneoxazole series of the formula <FORM:0478700/IV/1> (in which A is the radicle of an anthraquinone, combined with the oxazole ring shown in adjacent positions, R is an atomic bridge with a non-hydrogenated aromatic ring incapable of being vatted attached to the oxazole ring, Y is an imino group or one of the groups <FORM:0478700/IV/2> or <FORM:0478700/IV/3> and Z is a cyclic radicle) are made by (a) reacting an anthraquinoneoxazole which contains on the carbon atom of the oxazole ring at least one non-hydrogenated aromatic ring incapable of vatting which contains at least one halogen atom or nitro group with cyclic compounds which contain at least one exchangeable hydrogen atom attached to nitrogen, or (b) reacting an amide of a cyclic carboxylic acid with an anthraquinoneoxazole of the said kind, or (c) reacting an anthraquinoneoxazole having at least one non-hydrogenated aromatic ring incapable of vatting attached to the oxazole ring which contains an amino group with a replaceable hydrogen atom with an acylating agent containing a cyclic radicle, or (d) reacting an anthraquinoneazole of the said kind which contains an amino group in the ring attached to the oxazole ring with an amide of a cyclic carboxylic acid in presence of an acid condensing agent, or (e) reacting a cyclic compound containing, attached by way of an amino or carboxylic amide group, at least one non-hydrogenated aromatic ring incapable of vatting, and in this ring a carboxylic, carboxylic amide, carboxylic acid halide, aldehyde, di- or tri-halogenmethyl group with an amino-anthraquinone containing halogen or a hydroxy group in o-position to the amino group.  The radicle Z may be of the benzene, naphthalene, anthracene, pyrene, perylene, anthraquinone, anthrapyrimidine, anthanthrone, pyranthrone, dibenzpyrenequinone, naphthindenone, benzanthrone, benzanthraquinone, anthrapyridone, pyrazolanthrone, thiazolanthrone, anthraquinonebenzacridone, anthraquinonethioxanthone or carbazole series.  The reaction is effected by heating in a diluent, if desired in presence of copper or a copper compound and/or acid binding agents.  In examples: (1) C-4<1>-aminophenylanthraquinone-1(N).2-oxazole is boiled with anthraquinone-2-carboxylic acid chloride in nitrobenzene (greenish-yellow shades on vegetable fibres) or 1.4-dichloranthraquinone-6-carboxylic acid chloride; (2) C-4<1>-aminophenylanthraquinone - 1(N).2 - oxazole is condensed with 1-aminoanthraquinone-2-carboxylic acid chloride (red-orange); the oxazole may be replaced by C.4<1>-aminophenylanthraquinone-3(N).2-oxazole (scarlet-red), and the 1 - aminoanthraquinone - 2 - carboxylic acid chloride may be replaced by 1-aminoanthraquinone-6-carboxylic acid chloride or 1-nitro-anthraquinone-2-carboxylic acid chloride; (3) C.4<1>-aminophenylanthraquinone-1(N).2-oxazole is reacted with anthraquinone-2(S).1-thioxanthone-6<1>-carboxylic acid chloride (greenish-yellow); the thioxanthone may be replaced by benzanthrone-6-carboxylic acid chloride, 1(N).2-pyrazoloanthraquinone - Py.3 - carboxylic acid chloride or its N - methyl derivative, Py.3-phenyl - 1(N).2-pyrazoloanthraquinone - 4<1> - carboxylic acid chloride, or a monophthaloyl-carbazole carboxylic acid chloride (yellow to yellow - red); (4) C - 4<1> - aminophenylanthraquinone-1(N).2-oxazole is reacted with anthraquinone - 1(N).2.1<1>.2<1> - benzeneacridone - 5<1>-carboxylic acid chloride (red-yellow); C-4<1>-aminophenylanthraquinone - 2(N).3 - oxazole may be used instead of the 1(N).2-oxazole (red); (5) C.4<1> - aminophenylanthraquinone - 1(N).2-oxazole is reacted with benzoyl chloride, or with benzamide in presence of hydrogen chloride, or the corresponding C.4-chlor-body may be reacted with benzamide (yellow); the benzoyl chloride may be replaced by methyl-, halogen-, nitro-, and cyano-benzoyl chlorides, diphenyl monocarboxylic acid chlorides, benzophenone carboxylic acid chlorides or quinoline-6-carboxylic acid chloride; C.4<1>-aminophenyl-anthraquinone-1(N).2-oxazole may be replaced by C.2<1>.4<1>-diaminophenylanthraquinone-1(N).2-oxazole; (6) C.4<1>-chlorphenylanthraquinone-1(N).2-oxazole is reacted with 1-aminoanthraquinone (brown-red); (7) C.4<1>-chlorphenyl-anthraquinone-1(N).2-oxazole is reacted with 1 - amino - 5 - benzoylaminoanthraquinone (red-brown); the latter may be replaced by 1-amino-4 - benzoylaminoanthraquinone (olive) or 5-amino - 1.9 - anthrapyrimidine (chocolate-brown) or by an aminoanthanthrone, -dibenzpyrenequinone, -dibenzanthrone or -pyrazolanthrone; (8) C.3<1>-nitrophenylanthraquinone-1(N).2-oxazole is reacted with 1-aminoanthraquinone (yellow-olive) or 1-amino-5-benzoylaminoanthraquinone (olive); the C.3<1>-nitrophenylanthraquinone-1(N).2 - oxazole may be replaced by oxazoles obtained by reacting 1-amino-2-hydroxyanthraquinone or 2-amino-3-hydroxyanthraquinone with nitrodiphenyl carboxylic acid chlorides, 5-chlorquinoline-8-carboxylic acid chloride, nitro- or halogen-methylbenzoyl chlorides or nitro- or halogen-naphthoyl chlorides; (9) C.2<1>.4<1>-dichlorphenyl-anthraquinone-1(N).2-oxazole is reacted with 1 - amino - 5 - benzoylaminoanthraquinone (brown); the 2<1>.4<1> - dichlor - body may be replaced by the 3<1>.4<1>-dichloro body (brown-red) or the 2<1>.5<1>-dichloro body (currant brown); the 1-amino-5-benzoylaminoanthraquinone may be replaced by 1 - aminoanthraquinone (more reddish dyestuffs) or by 1-amino-4-benzoyl-aminoanthraquinone (grey to olive dyestuffs); (10) 1-amino-2-hydroxyanthraquinone is reacted with 4<1> - (1 - anthraquinonylamino) - benzoyl chloride in presence of a little p-toluenesulphonic acid to give the 1(N).2-anthraquinone-oxazole; if 2-hydroxy-3-aminoanthraquinone be used, the 2.3(N)-anthraquinoneoxazole is obtained; (11) 1 - amino - 2 - hydroxyanthraquinone is reacted with 4<1>-(anthraquinone-2-carbamido)-benzoyl chloride in presence of a little p-toluene sulphonic acid to give the same product as in (1); the 1-amino-2-hydroxy-anthraquinone may be replaced by other o - aminohydroxyanthraquinones or o - amino-halogenanthraquinones such as 1.5-diamino-2-hydroxyanthraquinone or 1.4 - dihydroxy - 2 - aminoanthraquinone; (12) 1-amino-2-hydroxy-anthraquinone is condensed with the reaction product from 1 mol. each of 1-aminoanthraquinone and isophthaloyl chloride in presence of a little p-toluenesulphonic acid.  C - 4<1> - aminophenylanthraquinone - 1(N).2-oxazole is obtained by reacting 1-amino-2-hydroxyanthraquinone with p - nitrobenzoyl chloride to give C-4<1>-nitrophenylanthraquinone-1(N).2-oxazole, followed by reduction of the nitro group.  1(N).2 - Pyrazolo - anthraquinone - Py.3 - carboxylic acid chloride is obtained by diazotizing 1-amino-2-ethylanthraquinone and boiling the diazo compound in aqueous sodium bicarbonate to give Py.3-methyl-1(N).2-pyrazolo-anthraquinone (see Specification 471,389) which is then oxidized with pyrolusite in presence of dilute sulphuric acid to the carboxylic acid, which is treated with thionyl chloride.  C.4<1>-aminophenylanthraquinone-2(N).3-oxazole is prepared by reacting p-nitrobenzoyl chloride with 2-amino-3-hydroxyanthraquinone to give C.4<1>-nitrophenylanthraquinone-2(N).3-oxazole, which is then reduced.  C.2<1>.4<1>-diaminophenylanthraquinone - 1(N).2-oxazole is obtained by reacting 1-amino-2-hydroxyanthraquinone with 2.4-dinitrobenzoyl chloride in 1-chlornaphthalene, and reduction of the resulting C.2<1>.4<1> - dinitrophenylanthraquinone-1(N).2-oxazole with alkaline hydrosulphite. C.4<1>-chlorphenylanthraquinone-1(N).2-oxazole is obtained from 1-amino-2-hydroxyanthraquinone and p-chlorbenzoyl chloride. C.2<1>.4<1> - dichlorphenylanthraquinone - 1(N).2-oxazole is obtained from 1-amino-2-hydroxy-anthraquinone and 2.4-dichlorbenzoyl chloride. 4<1>-(1-Anthraquinonylamino) - benzoyl chloride is obtained by reacting p-aminobenzoic acid with 1-chloranthraquinone and treating the resulting 4<1> - (1 - anthraquinonylamino)-benzoic acid with thionyl chloride.  4<1> - (Anthraquinone - 2 - carbamido) - benzoyl chloride is obtained from p-aminobenzoic acid by acylation with anthraquinone-2-carboxylic acid chloride, and treatment of the resulting 4<1>-(anthraquinone-2-carbamido)-benzoic acid with thionyl chloride.