Patent GB-709596-A (GB)
Title: Improvements in the production of vat dyestuffs of the anthraquinone series
IPC: C09B1/42
Filed: 1952-04-04
Abstract: The invention comprises dyes of the formulae:- <FORM:0709596/IV(c)/1> in which A is -NH, -O-, or -S-, Y is hydrogen or halogen, R1 is a vattable radical of the anthraquinone series, and R2 is a hydrogen atom or an alkyl, aralkyl, or aryl group or an acyl group CO-R3 in which R3 is an aryl radical which in turn may be substituted by the radical -CONH-R4 in which R4 is an anthroquinonyl radical.  Those of formula I are prepared by heating in a solvent 1 - nitro - or 1 - amino - anthraquinone - 3 - carboxylic acid halides (which may contain halogen in 4- position and in which a hydrogen atom of the amino group may be replaced by alkyl, aralkyl, aryl, acyl, or aryl sulphonyl) with vattable amines of the anthraquinone series, replacing any nitro or aryl-sulphonylamino groups present in the resulting dyestuff by amino, alkylamino, aralkylamino, or arylamino, and, if desired, acylating free amino groups with aryl carboxylic acid halides.  Those of formula II are similarly prepared but using vattable amines of the anthraquinone series which contain in oposition to the amino group a further amino group or a hydroxy or mercapto group or a halogen atom, and ringclosing to imidazoles, oxazoles, or thiazoles by heating in concentrated sulphuric acid.  In examples, (1) 1-amino-4-benzoylamino anthraquinone is condensed with 1-nitro-anthraquinone - 3 - carboxylic acid chloride (see Specification 678,608), the nitro group is reduced with alkaline sodium hyposulphite, and the product acylated with (a) benzoyl chloride, (b) 1-nitro-anthraquinone-2- or 3-carboxylic acid chloride, (c) 2.4-, 2.5-, or 3.4-dichlorbenzoyl chloride, (d) o-, m-, or p-chlorbenzoyl chloride, (e) o-, m-, or p-methyl-benzoyl chloride, (f) diphenyl-2-, 3-, or 4-carboxylic acid chloride or certain mono- and di-bromo derivatives thereof, (g) a- or b -naphthoyl chloride; (2) 1-amino-5-benzoylamino-anthraquinone is condensed with 1-nitroanthraquinone-3-carboxylic acid chloride, the nitro group is reduced with alkaline sodium hyposulphite, and the product is acylated with (a) benzoyl, chloride, (b) anthraquinone-2, 1 (N)-1\sv, 2\sv (N)-benzacridone-5\sv-carboxylic acid chloride, (c) 1.9-anthrapyrimidine-2-carboxylic acid chloride, (d) 1.9-thiazolanthrone or pyrazol anthrone-2-carboxylic acid chloride; (3) 1.4-diaminoanthraquinone is diacylated with 1-nitroanthraquinone-3-carboxylic acid chloride, the nitro groups are reduced with alkaline sodium hyposulphite and the product acylated with o-, m-, or p-chlorbenzoyl chloride, 2.4- or 2.5- dichlorbenzoyl chlorides, or the corresponding bromo benzoyl chlorides, or o-, m-, or p-methyl benzoyl chlorides; (4) 1-(p-toluenesulphonyl) amino-anthraquinone-3-carboxylic acid chloride is condensed with (a) 2-hydroxy-3-amino-anthraquinone, (b) 1.2-diaminoanthraquinone, or (c) 1-mercapto-2-aminoanthraquinone, followed in each case by stirring with concentrated sulphuric acid, which splits off the sulphonyl group and forms the oxazole, imidazole, or thiazole ring, and then by acylation with acid chlorides such as 1-nitro- or aminoanthraquinone-2-carboxylic acid chloride, anthraquinone-2-carboxylic acid chloride, 2.4- or 2.5-dichlor- or o-, m-, or p-chlorbenzoyl chlorides or the corresponding bromo-benzoyl chlorides, o-, m-, or p-methyl benzoyl chlorides, iso- or terephthaloyl chlorides, naphthoyl chlorides, or diphenyl carboxylic acid chlorides; (5) oxazoles similar to those obtained under (4) are obtained by the same method but starting from 1-nitroanthraquinone-3-carboxylic acid chloride, with subsequent reduction of the nitro group; (6) 1-aminoanthraquinone is condensed with 1 - nitroanthraquinone - 3 - carboxylic acid chloride, the nitro group is reduced, and the product is made into a diamide with isophthaloyl chloride; (7) 1-amino-4 or 5-benzoylaminoanthraquinone is condensed with 1- nitro-4-chlor or bromanthraquinone-3-carboxylic acid chloride; (8) 1-(p-toluenesulphonyl-) aminoanthraquinone-3-carboxylic acid chloride (obtained from 1-bromanthraquinone-3-, carboxylic acid and p-toluenesulphomide) is condensed with 1-(11-aminoanthraquinone -21-carbonyl-)-aminoanthraquinone, and the sulphonyl group is split off by treatment with concentrated sulphuric acid.