Patent GB-467157-A (GB)
Title: Improvements in the manufacture and production of vat dyestuffs of the anthraquinone series
IPC: C09B5/30
Filed: 1935-12-06
Abstract: Vat dyestuffs of the triazoloanthraquinone series of the general formula <FORM:0467157/IV/1> where R is a cyclic radicle having up to two isocyclic non-hydrogenated rings and A is a radicle capable of being vatted, e.g. of the anthraquinone, anthrapyrimidine, anthrapyridine, pyrazolanthrone, dibenzanthrone, azabenzanthrone, phthaloylcarbazole anthraquinonethioxanthone, dibenzpyrenequinone or anthraquinoneacridone series, which is attached to R by a group --NH--, --NH.CO--or --CO.NH--, and in which the anthraquinone nucleus shown may contain any substituents, are manufactured by exchanging the radicle X in a triazoloanthracene of the constitution <FORM:0467157/IV/2> or the corresponding triazoloanthraquinone in which X is a halogen atom (which may be part of a carboxylic halide group) or a nitro-group by reaction with an amino derivative of a compound capable of being vatted, or by introducing into a triazoloanthracene of the said constitution or the corresponding triazoloanthraquinone, in which X is an amino group, into the X the radicle of a vattable compound by acting thereon with a vattable compound substituted by a nitro or carboxylic halide group or a halogen atom, and, when a triazoloanthracene has been used, subsequently oxidizing it to the triazoloanthraquinone.  In examples: (1) the diazo compound of 1-amino-4-nitrobenzene is coupled with 2 - aminoanthracene and the product is oxidized with chromium trioxide or in stages, first with hypochlorite or with copper powder in boiling nitrobenzene to 4<1> - nitrophenyltriazoloanthracene and then with a solution of bichromate in sulphuric acid; the resulting 4<1> - nitrophenyltriazoloanthraquinone is reduced, e.g. by sodium sulphide solution, to the amino compound, which is heated with anthraquinone-2-carboxylic acid chloride or 1-aminoanthraquinone-2-carboxylic acid chloride in 1 : 2-dichlorobenzene; the products dye cotton pale yellow and brick-red shades respectively from violet vats; (2) 4<1>-aminophenyltriazoloanthraquinone is heated with anthraquinone-1(N) : 2 : 2<1>(N) :-1<1>-acridone-5<1> or 3<1>-carboxylic acid chloride or the dichloroderivative of the former or the 5<1>-chloro derivative of the latter; the products yield yellow-red dyeings; (3) 4<1>-aminophenyltriazoloanthraquinone is heated with 1-chloranthraquinone, anhydrous potassium acetate, copper acetate and naphthalene; the product dyes cotton bordeaux shades from a red vat; by treatment with hot concentrated sulphuric acid or with anhydrous aluminium chloride and sodium chloride at 140 DEG  C. it is converted into a dyestuff yielding yellow dyeings on cotton; (4) the diazo compound of 1-amino-3-nitrobenzene is coupled with 2-aminoanthracene and the product is oxidized with chromium trioxide in the presence of nitrobenzene and glacial acetic acid and reduced with sodium sulphide solution; the resulting 3<1>-aminophenyltriazoloanthraquinone is reacted with carboxylic acid chlorides of vattable compounds, e.g. the chlorides of anthraquinone-2-carboxylic acid, 1 : 9-thiazoloanthrone-2-carboxylic acid, 1 : 9-pyrazoloanthrone-2-carboxylic acid, anthraquinone - 1(N) : 2 : p  2<1>(N) : 1<1> - acridone-5<1> - carboxylic acid or anthraquinone-2(S) :-1 : 1<1>(S) : 2<1> - thioxanthone - 6 - carboxylic acid; (5) 4<1> - aminophenyltriazoloanthraquinone is heated with 1-cyano-2-bromanthraquinone, anhydrous potassium acetate, copper acetate and nitrobenzene; the product dyes cotton brown shades from a red vat; by treatment with hot concentrated sulphuric acid it is converted into a dyestuff yielding yellow dyeings on cotton; (6) the diazo compound of 4-aminobenzene-1-carboxylic acid is coupled with 2 - aminoanthracene and the product is oxidized with chromium trioxide in the presence of nitrobenzene and glacial acetic acid; the resulting phenyltriazoloanthraquinone-4<1>-carboxylic acid is converted by means of phosphorus pentachloride into its chloride, which is heated with 1-aminoanthraquinone in the presence of nitrobenzene and pyridine; the product dyes cotton reddish yellow shades from a violet-blue vat; there may alternatively be employed other vattable amino compounds, e.g. 1 : 4-diaminoanthraquinone, 1-amino-4-or 5-benzoylaminoanthraquinone, 4- or 5- amino - 1 : 9 - anthrapyrimidine or 1 : 2-(4<1>-aminophenyl)-triazoloanthraquinone; (7) 1-amino-4-chlorobenzene is diazotized and coupled with 2-aminoanthracene, and the product is oxidized with chromium trioxide; the resulting 4<1>-chlorophenyltriazoloanthraquinone is heated with 1-amino-4-or 5 - benzoylaminoanthraquinone in the presence of anhydrous sodium acetate, copper acetate and nitrobenzene; the products dye vegetable fibres grey and red-brown shades respectively; (8) 4<1>-chlorophenyltriazoloanthraquinone is similarly reacted with 5-amino-1 : 9-anthrapyrimidine, the product dyeing vegetable fibres currant shades from a red vat, or with other vattable amino compounds, e.g. 1-aminoanthraquinone, 1 : 4- or 1 : 5-diaminoanthraquinone, 1 - amino - 4 - methoxyanthraquinone, 2- or 4-amino-1 : 9-anthrapyrimidine, 4 - amino - 3<1> : 5<1> - dichloranthraquinone - 1(N) : 2 : 2<1>(N) : 1 - acridone, 1-aminoanthraquinone - 2 - aldehyde, 5 - amino-N - methylanthrapyrimidone or amino-4 : 5-8 : 9 - dibenzpyrene - 3 : 10 - quinone (obtainable from the corresponding dibenzpyrenequinone by nitration and reduction).