Patent GB-487380-A (GB)
Title: The manufacture of vat dyestuffs
IPC: C09B43/36
Filed: 1936-12-15
Abstract: Vat dyestuffs are manufactured by condensing halides of carboxylic acids of mono- or poly-nuclear carbocyclic or heterocyclic ring systems containing one or more azo or azoxy groups in the molecule with amines of vattable ring systems, either or both components, if desired, containing further substituents but no solubilizing groups. The amines may be capable of forming an azole ring during the condensation reaction by virtue of the presence, in o-position to the amino group, of a further amino group or a hydroxy or mercapto group. The acid halides may be produced in situ.  The products dye vegetable fibres from the vat in various shades.  In examples: (1) azobenzene-4 : 41-dicarboxylic acid is treated with thionyl chloride in o-dichlorobenzene, and, after distilling off excess thionyl chloride, the resulting solution of the dichloride is heated with 1-aminoanthraquinone; the product dyes cotton from a red vat greenish yellow shades; (2) and (3) 1-amino-5- and 4-benzoylaminoanthraquinone similarly yield products which dye cotton yellow and orange-red shades respectively; (4) azoxybenzene-4 : 41-dicarboxylic acid is reacted as in (2), yielding a dyestuff of similar properties; (5) azobenzene-4-carboxylic acid is converted into its chloride, which is reacted with 1-amino-5-benzoylaminoanthraquinone; the product dyes cotton from a dark red vat yellow shades; (6) azobenzene-3 : 31-dicarboxylic acid dichloride is reacted as in (2); the product dyes cotton from a dark red vat yellow shades; (7) azobenzene-4 : 41-dicarboxylic acid dichloride is heated with 5- or 4-aminoanthrapyrimidine in o-dichlorobenzene; the products dye cotton yellow shades; (8) 4 - amino - 1 : 2 - (21 - chlorophenylimidazole) - anthraquinone similarly yields a product which dyes cotton from a red vat yellow-orange shades; (9) azobenzene-4 : 41 - dicarboxylic acid dichloride is heated in o-dichlorobenzene with 1 molecular proportion each of 1-amino-5-and 4-benzoylaminoanthraquinone; the product dyes cotton from a red-violet vat orange shades; the 1-amino-4-benzoylaminoanthraquinone may be replaced by 1-aminoanthraquinone, the product yielding yellow shades; (10) azobenzene-4 : 41-dicarboxylic acid dichloride is heated in nitrobenzene with the product of alkaline condensation of 1-(Bzl-benzanthronylamino)-5-aminoanthraquinone (khaki shades), or with other vattable amines, e.g. amines or diamines of the dibenzanthrone or anthanthrone series; (11) 3 : 31-dimethoxyazobenzene-4 : 41-dicarboxylic acid is employed in the process of (2); the product dyes cotton from a red-violet vat yellow shades; (12) 4-methoxyazobenzene-31 : 51-dicarboxylic acid dichloride is condensed in o-dichlorobenzene with 1-amino-5-benzoylaminoanthraquinone (yellow shades from a red-violet vat); (13) azobenzene-4 : 31 : 51-tricarboxylic acid trichloride is heated in o-dichlorobenzene with 1-aminoanthraquinone (greenish yellow shades from a violet-red vat); (14) azo- and azoxybenzene-3 : 5 : 31 : 51-tetracarboxylic acid tetrachlorides are similarly reacted (greenish yellow shades from dark red vats); (15) diphenylazodiphenyl-4 : 41-dicarboxylic acid dichloride is heated in o-dichlorobenzene with 1-aminoanthraquinone (yellow shades from a violet vat) or with 1-amino-6-chloroanthraquinone; (16) 1-amino-5- and 4-benzoylaminoanthraquinones are similarly reacted (yellow and orange shades respectively from violet vats); (17) diphenylazoxydiphenyl-4 : 41-dicarboxylic acid dichloride is heated in monochlorobenzene with 1-amino-5-benzoylaminoanthraquinone; the product is similar to that of (16); (18) diphenylene-oxide-azodiphenylene-oxide-2 : 21-dicarboxylic acid dichloride is heated in o-chlorotoluene with 1 - amino - 5 - benzoylaminoanthraquinone (orange-yellow shades); 1-amino-4-benzoylaminoanthraquinone and 1-aminoanthraquinone may be similarly employed; (19) 1 : 11-azonaphthalene-5 : 51-dicarboxylic acid dichloride is heated in trichlorobenzene with 1-amino-5-benzoylaminoanthraquinone (reddish yellow shades from a red-violet vat); (20) the dicarboxylic acid dichloride of the formula <FORM:0487380/IV/1> (obtainable by reducing 2-(41-nitrophenyl)-benzthiazole-6-carboxylic acid by means of grape sugar and treating the product with phosphorus pentachloride) is heated in o-dichlorobenzene with 1-amino-5-benzoylaminoanthraquinone (greenish yellow shades from a violet vat); (21) 3 : 31-azocinnamic acid dichloride is heated in 1 : 2 : 4-trichlorobenzene with aminodibenzanthrene (obtainable by nitrating dibenzanthrene with nitric acid in the presence of glacial acetic acid and reducing the nitro group) (blue shades from a blue vat); (22) 4 : 41-azocinnamic acid dichloride is heated in monochlorobenzene with 1-amino-5-benzoylaminoanthraquinone (orange shades from a violet vat); (23) 4 : 41-azophenoxyacetic acid dichloride is similarly reacted in o-dichlorobenzene (greenish yellow shades from a violet red vat); (24) 4 : 41-azophenylacetic acid is reacted as in (2) (yellow shades from a dark red vat); (25) benzidine is condensed with 2 molecular proportions of the methyl ester of 4-nitrosobenzoic acid, the product is saponified and treated with phosphorus pentachloride, and the resulting dicarboxylic acid dichloride is heated in o-dichlorobenzene with 1 - aminoanthraquinone (yellow shades from a dark red-violet vat); (26) the dicarboxylic acid dichloride obtained as in (25) starting from 4 : 41-diaminoazobenzene is heated in o-dichlorobenzene with 1-amino-5-benzoylaminoanthraquinone (orange - yellow shades from a violet vat); (27) 4 : 41-diaminobenzophenone is employed as the starting material in the process of (26) (yellow shades from a violet vat); alternatively the azo compound is oxidized to the corresponding azoxy compound before the final condensation; the methyl ester of 4-nitrosobenzoic acid may be replaced by that of 3-nitrosobenzoic acid; (28) 4 : 41 : 411-triaminotriphenylmethane is condensed with 3 molecular p  proportions of the methyl ester of 4-nitrosobenzoic acid, the product is saponified and treated with phosphorus pentachloride, and the resulting tricarboxylic acid trichloride is reacted as in (26).  Specification 339,396, [Class 2 (iii)], is referred to. The Provisional Specifications comprise the use of free carboxylic acids of the kind described or their functional derivatives in general.  Samples have been furnished under Sect. 2 (5) of the products of condensation of azobenzene-4 : 41-dicarboxylic acid dichloride with: (A) the sodium salt of 2-amino-1-mercaptoanthraquinone, in nitrobenzene; the product, which contains thiazole rings, dyes cotton from a violettish red vat yellow shades; (B) 1-amino-2-hydroxyanthraquinone, in nitrobenzene; the product, which contains oxazole rings, dyes cotton from a dark red vat greenish yellow shades; (C) 1-methylamino-2-amino-3-bromanthraquinone, in 1 : 2 : 4-trichlorobenzene; the product, which contains imidazole rings, dyes cotton from a red vat yellow shades.  3 : 31-Dimethoxyazobenzene-4 : 4-dicarboxylic acid is obtainable by alkaline reduction of 2-methoxy-4-nitrobenzoic acid.  4-Methoxyazobenzene-31 : 51-dicarboxylic acid dichloride is obtainable by diazotizing 5-amino-isophthalic acid, coupling with phenol, methylating the hydroxy group and treating the product with thionyl chloride. Azobenzene-4 : 31 : 51-tricarboxylic acid trichloride is obtainable by condensing the methyl ester of p-nitrosobenzoic acid with 5-aminoisophthalic acid, saponifying and treating with phosphorus pentachloride.  Azobenzene-3 : 5 : 31 : 51-tetracarboxylic acid tetrachloride is obtainable by reducing 5-nitroisophthalic acid in an alkaline medium and treating the product with phosphorus pentachloride.  Azoxybenzene-3 : 5 : 31 : 51-tetracarboxylic acid is obtainable by reducing 5-nitroisophthalic acid by means of sodium arsenite in an alkaline medium.  Diphenylazo- and -azoxydiphenyl-4 : 41-dicarboxylic acid dichlorides are obtainable by reducing 4-nitrodiphenyl-41-carboxylic acid by means of grape sugar and treating the products with phosphorus pentachloride.  Diphenylene - oxide - azo - diphenylene - oxide - 2 : 21-dicarboxylic acid dichloride is obtainable by reducing 7-nitrodiphenylene-oxide-2-carboxylic acid by means of grape sugar and sodium hydroxide solution, and treating the product with thionyl chloride.  7 - Nitrodiphenylene - oxide - 2 - carboxylic acid is obtainable by nitrating diphenylene oxide in glacial acetic acid, condensing the product with acetyl chloride in the presence of aluminium chloride, and oxidizing the acetyl group.  1 : 11-Azonaphthalene-5 : 51-dicarboxylic acid dichloride is obtainable by reducing 5-nitronaphthalene-1-carboxylic acid by means of grape sugar in an alkaline medium, and treating the product with thionyl chloride.  4 : 41-Azocinnamic acid dichloride is obtainable similarly from 4-nitrocinnamic acid. 4 : 41-Azophenoxyacetic acid dichloride is obtainable similarly from 4-nitrophenoxyacetic acid.