Patent GB-466184-A (GB)
Title: Improvements in the manufacture and production of vat dyestuffs
IPC: C09B5/30
Filed: 1935-11-28
Abstract: Vat dyes are made by reacting 1(N).2-pyrazoloanthraquinone carboxylic acids of the formula <FORM:0466184/IV/1> in which R1 is hydrogen or an alkyl or aryl group and R2 a carboxylic group or an aryl nucleus containing a carboxylic group as a substituent or their halogen-containing derivatives, preferably in the form of their chlorides, with aromatic amino compounds containing at least one cyclic bound keto group and if desired acylamino groups.  The products may be alkylated if this is possible, or acylated if they contain further amino groups.  When the amino compounds contain in o-position to the amino group a hydroxyl, mercapto, or further amino group, there may be obtained carboxylic acid amides or, by elimination of water, the corresponding azoles.  When the amino compound contains two or more amino groups not in o-position, the carboxylic acid may be introduced into the molecule a corresponding number of times.  Alkylated products may also be produced by alkylating the carboxylic acids used as starting materials, saponifying the carboxylic group if the latter becomes simultaneously esterified. The formation of the dyes, which dye cotton yellow shades, is preferably carried out in an organic diluent such as nitrobenzene or trichlorbenzene.  In examples, the chloride of 1(N).2-pyrazoloanthraquinone-PyC-carboxylic acid is reacted with (1) 1-aminoanthraquinone, (2) 1-amino-5-benzoylaminoanthraquinone, (3) 1-amino-5-(p-methylbenzoyl)-aminoanthraquinone, (4) 1-amino-5-(p-chlorbenzoyl)-aminoanthraquinone, (5) 1-amino-5-(2<1>.5<1>-dichlorbenzoyl)-aminoanthraquinone, (6) 1.5-diaminoanthraquinone, (7) 4- or 5-amino-1.9-anthrapyrimidine, (8) 2-amino-3-hydroxyanthraquinone; (9) a methylated 1(N).2-pyrazoloanthraquinone-Py.C-carboxylic acid is reacted with 1-aminoanthraquinone or 1-amino-5-benzoylaminoanthraquinone; the chloride of Py.C-phenyl-1(N).2-pyrazoloanthraquinone - 4<1> - carboxylic acid is reacted with (10) 1-aminoanthraquinone, (11) 1 - amino - 4(or 5) - benzoylaminoanthraquinone, (12) 1.5-diaminoanthraquinone (one or two molecules of acid chloride to one of the anthraquinone), (13) 4 (or 5)-amino-1.9-anthrapyrimidine; the dyestuff obtained from 1 mol. each of Py.C-phenyl-1(N).2-pyrazoloanthraquinone-4<1>-carboxylic acid chloride and 1.5-diaminoanthraquinone is treated with (14) benzoyl chloride, (15) p.-chlorbenzoyl chloride, (16) p-toluyl chloride, (17) 2.5-dichlorbenzoyl chloride; the chloride of N-methyl-Py.C-phenyl - 1(N).2 - pyrazoloanthraquinone - 4<1>-carboxylic acid is reacted with (18) 1-aminoanthraquinone, (19) 1-amino-4 (or 5)-benzoylaminoanthraquinone, (20) 4-amino-1.9-anthrapyrimidine, (21) 1-mercapto-2-aminoanthraquinone; (22) the dyestuff derived from Py.C-phenyl - 1(N).2 - pyrazoloanthraquinone - 4<1>-carboxylic acid and 1-amino-5-benzoylaminoanthraqiuinone is methylated with p-toluene sulphonic acid methyl ester or methyl chloride; 1 - amino - 5 - benzoylaminoanthraquinone is condensed with the chlorides of (23) 4-chlor-1(N).2 - pyrazoloanthraquinone - Py.C - phenyl-4<1>-carboxylic acid, (24) a 1(N).2-pyrazoloanthraquinone - Py.C - chlorphenyl - carboxylic acid, (25) 1(N) .2-pyrazoloanthraquinone-Py.C-phenyl-2<1>.4<1> -dicarboxylic (or its methyl compound prepared by reaction with dimethyl sulphate in alkaline solution), (26) N-phenyl-1(N).2 - pyrazoloanthraquinone - Py.C - phenyl-4<1>-carboxylic acid.  1(N).2 - pyrazoloanthraquinone - Py.C - carboxylic acid is obtained by condensing 1-chlor-2-acetylanthraquinone with hydrazine hydrate and oxidizing the Py.C-methyl-1(N).2-pyrazoloanthraquinone thus obtained with pyrolusite in sulphuric acid solution.  It may be converted to its acid chloride by thionyl chloride, or methylated by p-toluene sulphonic acid methyl ester and saponification of the resulting ester, followed again by conversion to the acid chloride.  1(N).2 - Pyrazoloanthraquinone carboxylic acids containing an aryl nucleus between the Py.C atom and the carboxylic group may be prepared by reacting a 1-halogenanthraquinone-2-carboxylic acid halide with an aromatic hydrocarbon having at least one alkyl side-chain in presence of aluminium chloride, oxidizing the resulting compound, and either reacting the ketocarboxylic acid obtained with hydrazine or primary alkyl or aryl hydrazines, or reacting with ammonia, diazotizing the resulting amino compound, and heating the diazonium salt with sodium bisulphite solution.,  Py.C - Phenyl - 1(N).2 - pyrazoloanthraquinone -4<1>-carboxylic acid is obtained from 1-chlor-2-p-toluylanthraquinone by oxidation or by complete chlorination, followed by saponification with sulphuric acid, and reacting the resulting 1 - chlor - 2 - benzoylanthraquinone - 4<1>-carboxylic acid with hydrazine hydrate.  The acid may be converted to its acid chloride by thionyl chloride, or methylated by p-toluene sulphonic acid methyl ester, saponification of the resulting ester, followed again by conversion to the acid chloride. 1(N).2 - Pyrazoloanthraquinone - Py.C phenyl-2<1>.4<1>-dicarboxylic acid is obtained by oxidation of 1-chlor-2-(2<1>.4<1>-dimethylbenzoyl)-anthraquinone with chromic acid and reaction of the pyrazole dicarboxylic acid with hydrazine hydrate.  The acid may be converted to the chloride.  N - Phenyl - 1(N).2 - pyrazoloanthraquinone-Py.C - phenyl - 4<1> - carboxylic acid is obtained by reacting 1 - chlor - 2 - benzoylanthraquinone-4<1>-carboxylic acid methyl ester with phenylhydrazine, and saponification of the ester; it may be converted to the acid chloride.  4 - Chlor - 1(N).2 - pyrazoloanthraquinone-Py.C - phenyl - 4<1> - carboxylic acid is obtained by diazotizing 4-chlor-1-amino-2 (p-carboxybenzoyl)-anthraquinone, and heating with sodium bisulphite solution; the acid may be converted to its chloride.  A 1(N).2 - pyrazoloanthraquinone - Py.C-chlorphenyl-carboxylic acid is obtained by oxidation of the ketone obtained from 1-chloranthraquinone-2-carboxylic acid chloride and p-chlortoluene and reaction with hydrazine hydrate; it may be converted to the acid chloride.