Patent GB-555055-A (GB)
Title: Manufacture of vat dyestuffs
Filed: 1941-09-17
Abstract: 555,055. Dyes. SOC. OF CHEMICAL INDUSTRY IN BASLE. Sept. 17, 1941, Nos. 11905, 11906 and 11907. Convention dates, Sept. 19, 1940, April 30, 1941, and July 18, 1941. Sample furnished. [Classes 2 (iii) and 15 (ii)] Vat dyes, giving mainly pure yellow shades, specially fast to light, when dyed or printed on cotton, linen or regenerated cellulose fibres or on wool, silk or leather, are obtained by reaction of a non-vattable carboxylic acid free from nitrogen containing at least one 6-membered heterocyclic ring containing at least one sulphur or oxygen atom linked to two ring carbon atoms, or a functional derivative of such an acid, with a vattable amino compound. Alternatively, an amide of the carboxylic acid may react with a vattable compound containing at least one exchangeable halogen atom. The components may be so selected as to carry at least one substituent, e.g. a hydroxy, mercapto, nitro or amino group or a halogen atom, adapted for heterocyclic-ring formation, whereupon such ring formation is effected. Specified carboxylic acids are those derived from thianthrene, thianthrene /monosulphoxide, thianthrene/sulphone, thioxanthone, thioxanthone sulphone, phenoxthine, phenoxthine sulphone, diphenylene/dioxide and xanthone, and benzo derivatives of any of these, e.g. benzoxanthones. Specified amino compounds are 2-aminoanthraquinone, 1-aminoanthraquinone and its methoxy, benzoyl, and acylamino substitution products, amino-dibenzanthrones, amino-pyranthrones, amino-anthrapyrimidines and aminoanthraquinone - benzacridones. Examples relate to the condensation of (1) and (2) thianthrenedicarboxylic acid dichloride with 1 - amino - 5 - benzoylaminoanthraquinone, (1) in boiling o-dichlorobenzene; (2) in boiling o-dichlorobenzene containing pyridine, picoline, quinoline or N-dimethyl-aniline ; (3) thianthrenedicarboxylic acid dichloride with 1- amino - 4 - methoxyanthraquinone in o - dichlorobenzene containing pyridine, at room temperature ; the amino compound may be replaced by the 1- or 2-amino-, 1-amino-5- methoxy, 1 - amino - 3 - benzoyl -, 1 - amino - 4 - or 8 - benzoylamino -, 1 - amino - 5 - benzoylamino - 8 - methoxy, 1 - amino - 3 - (4'-chloro) benzoyl -, 1 - amino - 5 - acetylamino -, 1 - amino - 5 - cinnamoylamino - and 1 - amino - 5 - (3<SP>1</SP> . pyridoyl)-amino - derivatives of anthraquinone, amino-dibenzanthrone, aminoisodibenzanthrone, amino - pyranthrone, 4 - or 5 - amino - 1:9 - anthrapyrimidine, 4 - or 5 - aminoanthraquinone - 1(N):2 - benzacridone or 4 - aminoanthraquinone - 1(N):2:1':2'(N) - 5<SP>1</SP> - chlorobenzacridone; (4) thianthrenedicarboxylic acid dichloride with 1 - mercapto - 2 - aminoanthraquinone in boiling nitrobenzene ; (5) and (6), dimethylthianthrenedicarboxylic acid dichloride with (5) l-amino-5-benzoylamino - anthraquinone (6) 1 - aminoanthraquinone, in boiling o-dichlorobenzene ; (7) thianthrene monosulphoxide-dicarboxylic acid dichloride with l-amino-5-benzoylamino-anthraquinone in boiling o-dichlorobenzene ; (8,) and (9) thianthrene disulphone-dicarboxylic acid dichloride with (8) l-amino-5-benzoylamino-anthraquinone, (9) 1-aminoanthraquinone or 1 - amino - 4 - benzoylaminoanthraquinone in boiling o-dichlorobenzene; (10) thianthrenedicarboxylic. acid dichloride first with 1 - amino - 5 - benzoylaminoanthraquinone in o-dichlorobenzene containing pyridine at 55- 60‹C. and then with l-amino-4-methoxyanthraquinone in the same liquid at 165-170‹C. ; (11) and (12), dimethylthianthrene monosulphoxide dicarboxylic acid dichloride with (11) 1 - amino-5-benzoylaminoanthraquinone, (12) 1-aminoanthraquinone, in boiling o-dichlorobenzene; ( 13 ) to (15), (13) phenoxthinedicarboxylic acid dichloride, (14) phenoxthine sulphone-dicarboxylic acid dichloride, (15) thioxanthonedicarboxylic acid dichloride, with 1-amino-5-benzoylaminoanthraquinone in boiling o-dichlorobenzene ; (16) thioxanthone sulphone-dicarboxylic acid dichloride with 1- amino-5-benzoylaminoanthraquinone in boiling o-dichlorobenzene containing pyridine; (17) diphenylene dioxide-dicarboxylic acid dichloride with 1 - amino - 5 - benzoylaminoanthraquinone or 1-aminoanthraquinone in boiling o-dichlorobenzene ; (18) xanthone-2:7-dicarboxylic acid dichloride with l-amino-5-benzoylaminoanthraquinone in boiling o-dichlorobenzene ; (19) and (20), 1:2-benzoxanthone-8-carboxylic acid chloride with (19) 1-amino-5-benzoylaminoanthraquinone, (20) 1-aminoanthraquinone, in boiling o-dichlorobenzene. A sample is furnished under Sec. 2(5) of a condensation product of the dichloride of a partially oxidized thianthrenedicarboxylic acid (obtained by oxidizing thianthrenedicarboxylic acid with sodium hypochlorite) with 1-amino-5-benzoylaminoanthraquinone. An example is also given of the dyeing process for cotton. Thianthrenedicarboxylic acid dichloride is obtained by dibrominating thianthrene in nitrobenzene, heating the product with cuprous cyanide in pyridine at 250-255‹C. under pressure, hydrolyzing the resulting dinitrile with alcoholic potash to the dicarboxylic acid, and heating this with thionyl chloride in o-dichlorobenzene. Dimethylthianthrenedicarboxylic acid dichloride is similarly obtained from the dimethylthianthrene produced by condensing toluene with sulphur monochloride. Phenoxthine-dicarboxylic acid dichloride is similarly obtained from phenoxthine. Thioxanthone dicarboxylic acid dichloride is similarly obtained from thioxanthone. Diphenylene dioxide-dicarboxylic acid dichloride is similarly obtained from diphenylene dioxide. Thianthrene monosulphoxide-dicarboxylic acid dichloride is obtained by oxidizing dibromothianthrene with nitric acid in boiling glacial acetic acid, heating the product with cuprous cyanide in pyridine, hydrolyzing the resulting dinitrile to the dicarboxylic acid and heating this with thionyl chloride in o-dichlorobenzene. Dimethylthianthrene monosulphoxide-dicarboxylic acid dichloride is similarly obtained from dibromodimethylthianthrene. Thianthrene disulphone-dicarboxylic acid dichlorides are obtained by (a) oxidizing thianthrenedicarboxylic acid with an aqueous solution containing potassium permanganate and caustic potash or (b) oxidizing with aqueous sodium hypochlorite the product of condensation of thianthrene with chloroacetyl chloride, and in each case heating the product with thionyl chloride in o-dichlorobenzene. Phenoxthine sutphone-dicarboxylic acid di- ,chloride is obtained by oxidizing phenoxthine dicarboxylic acid with an aqueous solution containing potassium permanganate and caustic potash and heating the product with thionyl chloride in o-dichlorobenzene. Thioxanthone sulphone-dicarboxylic acid dichloride is similarly obtained from thioxanthone dicarboxylic acid. Xanthone-2:7-dicarboxylicaciddichlorideis obtained by heating 2:7-dibromoxanthone with cuprous cyanide in quinoline, hydrolyzing the resulting dinitrile and heating the dicarboxylic .acid with thionyl chloride in o-dichlorobenzene.