Patent GB-249489-A (GB)
Title: Manufacture of intermediate products of the anthraquinone and anthracene series and dyestuffs therefrom
IPC: C09B7/00
Filed: 1926-02-19
Abstract: 249,489. Soc. of Chemical Industry in Basle. March 18, 1925, [Convention date]. Addition to 210,413. 1 : 2- and 2 : 1-Mercaptoanthracenecarboxylic acids; 1 : 2- and 2: 1-anthracenethioglycolcarboxylic acids; 1:2- and 2 : 1-mercaptoanthraquinonecarboxylic acids; anthroqninone-2-thioglycol-1-carboxylic acid.-1 : 2 and 2: 1-Anthracenethioglycolcarboxylic acids are obtained from 1 : 2- and 2 : 1-halogenanthraquinonecarboxylic acids by exchanging the halogen for -SH by means of alkali sulphide, reducing to the corresponding anthracene derivatives, and condensing with monohalogen acetic acid. Anthraquinone- 2-thioglycol-1-carboxylic acid is obtained either by condensing a 2-halogenanthraquinone-1-carboxylic acid with thioglycollic acid, or by condensing the 2-mercaptoanthraquinone-1-carboxylic acid with monohalogen acetic acid. The anthracene-2-thioglycol-1-carboxylic acid may also be obtained by reducing the corresponding anthraquinone derivative. According to examples: -(1) 1-chloranthraquinone-2-carboxylic acid and 2-bromanthroquinone-1-carboxylic acid are respectively converted into the corresponding mercaptans by boiling with sodium hydrosulphide and purifying by solution in alkali with addition of a little hydrosulphite and reprecipitating; (2) 1 : 2- and 2 : 1-mecaptoanthraquinonecarboxylic acids are reduced to the corresponding anthracene derivatives with zinc dust and aqueous ammonia followed by addition of a little hydrosulphite; (3) the mercaptoanthracenecarboxylic acids and the 2-mercaptoanthraquinone-carboxylic acid are respectively condensed with chloracetic acid to obtain the corresponding thioglycollic acids; (4) 2-bromanthraquinone-1-carboxylic acid is condensed with thioglycollic acid: (5) anthraquinone- 2-thioglycol-1-carboxylic acid is reduced to the anthracene derivative with zinc dust and ammonia. Anthracene. and anthraquinone-oxythiophenes; thiodindigoid dyes.-The above described anthracene- and anthraquinone-thioglycol-carboxylic acids are converted into the corresponding oxythiophene derivatives by treating with condensing agents. Symmetrical thioindigoid dyestuffs are obtained by oxidizing the oxythiophene derivatives or the thioglycol-carboxylic acids; unsymmetrical thioindigoid dyes result on condensing the thioglycol-carboxylic acids or the oxythiophene derivatives with the usual indigoid dye components such as isatin or thioisatin or their anils or halides, acenaphthenequinone, naphthoquinone, or a derivative or substitution product thereof; the dyestuffs may subsequently he halogenized. The products dye cotton from the vat chiefly in shades of brown, but bordeaux. yellow-green, and helitrope products are also described. According to examples :-(1) 2 : 1- and 1 : 2-anthraceneoxythiophenes and 2: 1-anthroquinoneoxythiophene are obtained bv heating the corresponding thioglycol carboxylic acids with acetic anhydride and sodium acetate and saponifying the acetyl derivatives formed; by oxidation with nitrobenzene, or with air in alkaline solution, they yield the corresponding thioindigo ; the 2 : 1-anthraquinonethioglycolcarboxylic acid sodium salt also yields the thioindigo by heating in an autoclave with water at 180-190‹ C. and extracting the residue with water and nitrobenzene, (2) isatin anilide is condensed with anthracene-l-thioglvcol-2-carboxylic acid in acetic anhydride or with anthracene-1 : 2-oxythiophene in benzene or toluene : (3) the dyestuff from anthraquinone-2-thioglycol-1-carboxylic acid and acenaphthenequinone is' brominated in nitrobenzene. A table is given showing the dyeing properties of products from the oxythiophenes or the thioglycolcarboxylic acids and isatin, isatin anilide, dibromisatin, acenaphthenequinone, 2 : 3-anthraquinonethiosatin-p-dimethylaminoanil, and 2 : 3-anthracenethiosatin-p-dimethylaminoanil. Specification 246,156 is referred to.