Patent GB-719282-A (GB)
Title: Improvements in the production of vat dyestuffs of the anthraquinone series
IPC: C09B1/36
Filed: 1952-09-16
Abstract: 1,5- and 1,8-Dinitro-2-ethylanthraquinones are obtained by nitration from 2-ethylanthraquinone and separation from each other by fractional precipitation.ALSO:The invention comprises 1-amino-2-acetyl-anthraquinone having attached to at least one of the other a -positions a monosubstituted amino group, the substituent of which is an acyl group derived from a carboxylic acid or a nitrogenous heterocyclic radical containing in one of the six-membered rings at least twice the group:  <FORM:0719282/IV(c)/1> said heterocyclic radical being attached by a carbon atom of the heterocyclic ring to the nitrogen of the amino group.  The invention also includes a process of heating 1-amino-2-acetylanthraquinones which contain an amino group in at least one further a -position and which may also contain other substituents in the anthraquinone nucleus with carboxylic acid halides or with compounds which contain at least once the above grouping in a six-membered heterocyclic ring. Preferably, the reactants are combined in equimolecular proportions, and when polyfunctional acylating agents are used, unreacted functional groups thereof may be reacted with other amines, such as aniline or 1-aminoanthraquinone.  The products dye natural or regenerated cellulose or nylon red to black shades.  In examples, 1.4-diamino-2-acetylanthraquinone is reacted in dichlorbenzene or nitrobenzene with (1) benzoyl chloride, or alkyl, alkoxy or halogen derivatives thereof, (2) diphenyl-4-carboxylic chloride, (3) pyridine-3- or 4-carboxylic chloride, (4) naphthalene-2-carboxylic chloride, (5) isophthaloyl or terephthaloyl chloride, (6) diphenyl-4.41-dicarboxylic chloride, (7) naphthalene-2.6-dicarboxylic acid chloride, (8) azobenzene-4.41-dicarboxylic acid chloride, (9) anthraquinone-2-carboxylic acid chloride or its 1-amino or 1-nitro derivatives, (10) 1-amino, nitro-, or acylamino anthraquinone-3-carboxylic acid chloride, (11) 1.9-thiazolanthrone-2-carboxylic acid chloride, (12) 1.9-anthrapyrimidine-2-carboxylic acid chloride, (13) 2.4-dichlor-6-methylpyrimidine, (14) 2.4-dichlor-6-phenylpyrimidine, (15) 2.4.6-trichlorquinazoline or 2.4-dichlorquinazoline, (16) 2.4-dichlor-6.7-benzquinazoline, (17) 2.4-dichlor-6.7-benzpteridine, (18) dichlorophthalazine, (19) cyanuryl chloride, (20) 2.4-dichloroquinazoline, together with 1 mol. 1-aminoanthraquinone, (21) 2-phenyl-4-chlor-6.7-phthaloylquinazoline.  Also in examples, 1.5-diamino-2-acetylanthraquinone is similarly reacted with (22) fumaryl chloride, or chlorfumaryl chloride, (23) acetyl chloride, (24) propionyl chloride, (25) butyryl chloride, (26) iso- or terephthaloyl chloride, (27) 1-chlorisophthaloyl chloride, (28) diphenyl-3.31-dicarboxylic acid chloride, (29) 1-nitroanthraquinone-2-carboxylic acid chloride, (30) 3.4-phthaloylacridone-7-carboxylic acid chloride, (31) 2.4-dichlorquinazoline, (32) cyanuryl chloride, (33) 2-chlorquinoline-4-carboxylic acid chloride.  Also in examples (34) 1.5-diamino-4-chlor-2-acetyl-anthraquinone is reacted with isophthaloyl chloride or 2.4-dichlorquinazoline; (35) 1.4.5-triamino-2-acetylanthraquinone is reacted with benzoyl chloride; (36) 1.5-diamino-8-hydroxy-2-acetylanthraquinone is reacted with isophthaloyl chloride; (37) 1.8-diamino-2-acetylanthraquinone is reacted with isophthaloyl chloride.  Other acid halides specified are oxalyl chloride, stearic acid chloride, trimesic acid chloride, pyridine 3- and 4-carboxylic acid chlorides, quinoline-6-carboxylic acid chloride, and other compounds containing the grouping specified are 2.4-dichlor- or dibrom-pyrimidine, 2.5-dichlorpyrazine, 2.6-dichlor-4-methyl-1.3.5-triazene,2-(anthraquinonyl-2') -4-chlorquinazoline, 1.3-di (41-chlor-61, 71 phthaloylquinazoyl-21) benzene, 1.4-dichlorphthalazine, 4.41-dichlor-6.61-diphenyl-2.21-dipyrimidyl, cyanine bromide, trichlorpurine.  1.5- and 1.8-Diamino-2-acetylanthraquinone are obtained by consecutive treatment with oleum, ferrous sulphate and sodium sulphide from 1.5- and 1.8-dinitro-2-ethylantharaquinone.  A hydroxy group may be introduced in 8-position by lengthening the oleum treatment.  1-amino-4-chlor-5-nitro-2-acetyl-anthraquinone is obtained by chlorination with sulphuryl chloride of 1-amino-5-nitro-2-acetyl -anthraquinone.  1.5 Diamino-4-chlor-2-acetylanthraquinone is obtained by reduction with sodium sulphide from 1-amino-4-chlor-5-nitro-2-acetylanthraquinone. 1.4.5-Triamino-2-acetylanthraquinone is prepared from 1-amino-5-nitro-4-chlor-2-acetylanthraquinone by reaction with p-toluene sulphonamide and saponification to 1.4-diamino-5-nitro-2-acetylanthraquinone which is then reduced with sodium sulphide.