Patent GB-436951-A (GB)
Title: Improvements in the manufacture and production of vat dyestuffs of the anthraquinone series
IPC: C09B5/32
Filed: 1934-04-16
Abstract: Vat dyes are prepared by reacting chlorides or bromides of cyclic carboxylic acids with aminoanthraquinoneoxazoles, - thiazoles or -imidazoles of the formula <FORM:0436951/IV/1> wherein X stands for O, S or NH and R for the radicle of an anthraquinone and which may contain further amino groups in at least one of the anthraquinone radicles.  The starting materials may in part be prepared according to Specification 420,359.  In examples 1-amino-4-nitro - 2 - anthraquinonyl - 2<1> . 3<1> - anthraquinoneoxazole (prepared by condensing 1-amino - 4 - nitroanthraquinone - 2 - carboxylic acid chloride with 2 - amino - 3 - oxyanthraquinone and ring-closure by treatment with p-toluenesulphonic acid) is reduced by means of sodium sulphide, or hydrazine hydrate, dimethylaniline, aniline, toluidine or b -naphthylamine; this product (which may also be prepared by reducing with hydrazine hydrate the condensation product of 1-amino-4-nitroanthraquinone - 2 - carboxylic acid chloride and 2 - amino - 3 - oxyanthraquinone prior to ring-closure as above) is acylated with benzoyl chloride (dyes blue shades) or bromobenzoylchlorides, cyanobenzoyl chlorides, methoxybenzoyl chlorides, diphenyl-p-carboxylic acid chloride, toluyl acid chlorides, anthraquinone-2-carboxylic acid chloride (grey-blue), 1-chloranthraquinone-2-carboxylic acid chloride (grey-blue), 1 . 4 - dichloranthraquinone - 2 - and 6-carboxylic acid chlorides (grey-blue), 1-aminoanthraquinone-2-carboxylic acid chloride (violet), terephthaloyl chloride, and isophthaloyl chloride (blue shades), quinoline-2-carboxylic acid chloride (blue), quinoline-5.8-dicarboxylic acid chloride, naphthoquinoline carboxylic acid chlorides, anthraquinone 1(N).2.1<1>.2<1>(N)-benzacridone-3<1>- and 5<1>-carboxylic acid chlorides (reddish-grey), 1.9-pyrazolanthrone-2-carboxylic acid chloride, anthraquinone 1(S).2.1<1>. 2<1>(S)-benzthioxanthone-3-carboxylic acid chloride (bluish-grey) and 1.9-thiazolanthrone-2-carboxylic acid chloride; (2) 1-amino-4-nitro-2-anthraquinonyl - 6<1> - chlor - 2<1> . 3<1> - anthra quinoneoxazole (prepared by condensing 1-amino-4-nitroanthraquinone-2-carboxylic acid chloride with 2 - amino - 3 - oxy - 6-chloranthra quinone and ring-closing the product by means of p-toluenesulphonic acid in nitrobenzene) is reduced by means of sodium sulphide and treated with p-chlorbenzoyl chloride (reddish blue); (3) 1.5-dinitro-2-anthraquinonyl-2<1>.3<1> -anthraquinoneoxazole (prepared by condensing 1.5 - dinitroanthraquinone - 2 - carboxylic acid chloride with 2-amino-3-oxyanthraquinone and ring-closing the product by means of sulphuric acid) is reduced by means of sodium sulphide and benzoylated (ruby-red); (4) 1-amino-4-nitro - 2 - anthraquinonyl - 1<1>(N)2<1> - anthraquinoneoxazole and the 3<1>-chloro derivative thereof (prepared by condensing 1-amino-4-nitroanthraquinone-2-carboxylic acid chloride with 1-amino-2-oxyanthraquinone and with 1 - amino - 2 - oxy - 3 - chloranthraquinone respectively followed by ring-closure as above) are reduced by means of sodium sulphide or hydrosulphite (dye greenish-blue shades) and acylated with a  - or b  - naphthoyl chloride, anthracene-2-carboxylic acid chloride, brombenzoyl chlorides, cyanobenzoyl chlorides, methoxybenzoyl chlorides, diphenyl-p-carboxylic acid chloride or toluyl acid chlorides (blue to grey shades); (5) 1-amino-4-nitro-2-anthraquinonyl - 2<1> . 3<1> - and - 1<1> . 2<1> - anthraquinoneimidazoles (prepared by condensing 1-amino-4-nitroanthraquinone-2-carboxylic acid chloride with 2.3- and 1.2-diaminoanthraquinones respectively at 180--200 DEG  C. in nitrobenzene) are acylated with anthraquinone-2-carboxylic acid chloride (grey shades); (6) 1-amino-4-nitro - 2 - anthraquinonyl - 1<1> . 2<1>(N) - anthraquinonethiazole (prepared by condensing 1-amino - 4 - nitroanthraquinone - 2 - carboxylic acid chloride with 1-mercapto-2-aminoanthraquinone at 180--200 DEG  C. in nitrobenzene) is reduced by means of hydrazine hydrate and acylated with benzoyl chloride (bluish-green shades) and anthraquinone 1(S)2.1<1>.2<1>(S)-benzthioxanthone-3<1>-carboxylic acid chloride; (7) 1-amino - 4 - nitro - 2 - anthraquinonyl - 1<1>(N).2-anthraquinonethiazole (prepared from 1-amino-4-nitroanthraquinone-2-carboxylic acid chloride and 1-amino-2-mercaptoanthraquinone) is reduced and acylated with o-chlorbenzoyl chloride and anthraquinone 1(S) . 2 . 1<1> . 2<1>(S) - benzthioxanthone-3-carboxylic acid chloride; (8) 1.4-diamino - 2 - anthraquinonyl - 2<1>(N).3<1>-anthraquinonethiazole (prepared by reducing 1-amino 4 - nitroanthraquinone - 2 - carbonylamino - 2<1> . 3<1> - bromanthraquinone with hydrazine hydrate, heating the product in phenol, adding sodium sulphite and sulphur and further heating; dyes greenish-blue) is acylated with benzoyl chloride (greenish-blue), 1.4-dichloranthraquinone-2-carboxylic acid chloride (blue-grey), 1.4 - dichloranthraquinone - 6 - carboxylic acid chloride (greenish-grey) and anthraquinone-1(S) . 2 . 1<1> . 2<1>(S) - benzthioxanthone - 3 - carboxylic acid chloride.  Reference is also made to the preparation of the starting material of (1) by (a) condensing 1-amino-4-halogenanthraquinone-2-carboxylic acid chloride with 2 - amino - 3 - oxyanthraquinone and treating the product with ammonia or p-toluenesulphonamide (with saponification) prior or subsequent to ring-closure by means of acid condensing agents, (b) condensing 1-amino-4-nitroanthraquinone-2-aldehyde with 2-amino-3-oxyanthraquinone in nitrobenzene followed by reduction, (c) nitrating 1 - amino - 2 - anthraquinonyl - 2<1> . 3<1> - anthraquinoneoxazole followed by reduction.  1 - Amino -4 nitroanthraquinone - 2 - aldehyde is prepared by treating 1-aminoanthraquinone-2-aldehyde with nitrating agents in presence of paraformaldehyde and concentrated sulphuric acid.  2 - Amino - 3 - oxy - 6 - chloranthraquinone is prepared by condensing 4-chlorphthalic acid with chlorbenzene by means of aluminium chloride, the product nitrated in presence of sulphuric acid, reduced by means of metallic iron, treated with phosgene in presence of alkali and finally heated with fuming sulphuric acid at 125 DEG  C.