Patent GB-366980-A (GB)
Title: Process for the manufacture of 2-aroyl-1 : 9-isothiazoleanthrones
IPC: C09B5/10
Filed: 1930-11-11
Abstract: 2-Aroyl-1,9-isothiazoleanthrones are prepared by causing ammonia to react on a 2-aroylanthraquinone containing in the 1-position a mercapto, thiocyano or xanthate group.  Or these substances may be prepared by treating with ammonia and polysulphide in one operation a 2-aroylanthraquinone containing a negative substituent such as a halogen atom, in the 1-position. The products are dye-intermediates. Products containing a similar structure and which are dyestuffs are prepared by treating with ammonia and polysulphide in one operation a dianthraquinonoyl-aryl body containing either two 1 - halogenanthraquinone - 2 - aroyl groups, or one such group and one 2-aroylanthraquinone group substituted by a 1-amino group or a 1,9-heterocyclic ring structure, the ketone linkages being attached to different nuclei of a polynuclear aromatic compound. Such dianthraquinonoyl-aryl bodies are obtained by condensing two mols. of 1-halogenanthraquinone-2-carboxylic acid halides, or one mol. of the latter and one mol. of an anthraquinone-2-carboxylic acid halide containing either a 1-amino group or a 1.9-heterocyclic ring structure, with one mol. of a polynuclear aromatic compound containing in each of at least two aromatic nuclei at least one reactive hydrogen atom according to the process of Specification 363,740.  The resulting products are identical with those obtainable according to Specification 363,740 and dye cotton in yellow shades. In examples, (1) 1-chlor-2-anthraquinonyl-1<1>-naphthylketone (prepared by condensing together 1-chloranthraquinone-2-carboxylic acid chloride and naphthalene in nitrobenzene and in presence of aluminium chloride) is treated with polysulphide to give the corresponding 1-mercapto compound which is treated with ammonia under pressure; the same isothiazoleanthrone is produced by amination of 1 - thiocyano - 2 - anthraquinonyl - 1<1>-naphthylketone; alternatively the 1-chlor-2-anthraquinonyl - 1<1> - naphthylketone may be heated in an autoclave with ammonia and polysulphide: (2) 1-chlor-2-benzoylanthraquinone is heated in an autoclave with ammonia and polysulphide: (3) di-(1-chloro-2-anthraquinonoyl)-diphenyl (prepared according to the process of Specification 363,740) is heated in an autoclave with ammonia and polysulphide; alternatively it may be first converted to the corresponding mercapto derivative by treatment with polysulphide and this product then aminated; or the same product is obtained by starting from 2-isothiazoleanthronyl-diphenylketone, condensing this with one mol. of 1 - chloranthraquinone - 2 - carboxylic acid chloride according to the process of Specification 363,740 and treating this product with ammonia and polysulphide: (4) di-(1-chloranthraquinonoyl)-diphenylether (prepared according to the process of Specification 363,740) is treated with ammonia and polysulphide; diketones derived from 2 mols. of 1-chloranthraquinone-2-carboxylic acid chloride and 1 mol. of diphenyleneoxide, naphthalene, acenaphthene and the like, can similarly be converted to 1.9-isothiazoleanthrones: (5) the diketone derived from 1 mol. of pyrazoleanthrone-2-carboxylic acid chloride, 1 mol. of 1-chloranthraquinone-2-carboxylic acid chloride and 1 mol. of diphenyl according to the process of Specification 363,740, is treated with ammonia and polysulphide; the diketone obtained by replacing the above pyrazoleanthrone - 2 - carboxylic acid chloride by 1-aminoanthraquinone-2-carboxylic acid chloride, on similar treatment yields a reddish-orange dye. Specification 11931/09, [Class 2 (iii), Dyes &c.], is referred to.  1 - Mercapto - 2 - aroylanthraquinones are prepared by reacting 1-chlor-2-aroylanthraquinones with sodium polysulphide.  1-Thiocyano or xantho-2-aroylanthraquinones are prepared by converting 1-chlor-2-aroylanthraquinones into the corresponding 1-amino derivatives by means of p-toluenesulphonamide, diazotizing the amino compound and reacting upon the diazo compound with a thiocyanate or xanthate respectively.