Patent GB-210413-A (GB)
Title: Manufacture of intermediate products of the anthraquinone and anthracene series and dyestuffs therefrom
IPC: C09B7/00
Filed: 1924-01-04
Abstract: Anthraquinone-2-thioglycol-3-carboxylic acid is obtained by condensing either 2-mercaptoanthraquinone-3-carboxylic acid with a monohalogenacetic acid, or a 2-halogenanthraquinone-3-carboxylic acid with thioglycollic acid; by reduction it is converted into the corresponding anthracene derivative.  Examples are given of the production by each method of anthraquinone-2-thioglycol-3-carboxylic acid and of its reduction with zinc dust and aqueous ammonia to anthracene-2-thioglycol-3-carboxylic acid. 2-Mercaptoanthraquinone-3-carboxylic acid may be obtained by action of sodium hydrosulphide on 2-chloranthraquinone-3-carboxylic acid or from 2-aminoanthraquinone-3-carboxylic acid by the diazo reaction. Anthracene- and anthraquinone-2 : 3-oxythionaphthenes; thioindigo dyes.-The above described anthracene and anthraquinone thioglycol-carboxylic acids react, in the presence of condensing agents, with the usual indigoid dye components such as isatins, thioisatins, isatin-anilides or chlorides, acenaphthenequinones, or naphthoquinones, to yield vat-dyestuffs; the same products are obtained by converting the thioglycol-carboxylic acids into the corresponding anthracene- or anthraquinone-oxythionaphthene and then condensing with indigoid dye components.  The oxythionaphthenes yield upon oxidation the corresponding thioindigos, the anthraquinone body being also directly obtainable by condensing a 2-halogenanthraquinone-3-carboxylic acid with thioglycollic acid at a high temperature; the anthraquinone thioindigo may also be obtained by condensing 2-mercaptoanthraquinone-3-carboxylic acid with a dihalogenethylene and treating the ethylene-bis 2 : 3-thicanthraquinone carboxylic acid with chlorsulphonic acid or other agent.  The dystuffs may be halogenated.  The products dye from the vat in green shades when they contain the anthracene nucleus and in violet, blue, grey, and bordeaux shades when they contain the anthraquinone nucleus. According to examples (1) anthraquinone-2 : 3 -oxythionaphthene is prepared by heating anthraquinone-2-thioglycol-3-carboxylic acid with acetic anhydride and hydrolysing the acetyl compound; by oxidation it yields the corresponding symmetrical thioindigo: (2) anthracene-2 : 3-oxythionaphthene and the corresponding anthracene thioindigo are similarly obtained from anthracene-2-thiogycol-3-carboxylic acid: (3) anthraquinone-2-thioglycol-3-carboxylic acid or anthraquinone-2 : 3-oxythionaphthene is condensed with isatin-a -anilide, or b -naphthisatin-naphthalide, or (in the case of the carboxylic acid) with acenaphthenequinone: (4) anthracene-2-thioglycol-3-carboxylic acid is condensed with isatin or isatin-a -anilide: (5) anthracene-2 : 3-oxythionaphthene is condensed with isatin a -anilide: (6) the dyestuff from anthraquinone-2-thiogylcol-3-carboxylic acid and isatin-a -anilide is brominated in nitrobenzene or chlorsulphonic acid: (7) the dyestuff from anthracene-2-thioglycol-3-carboxylic acid and isatin-a -anilide or isatin is brominated in nitrobenzene.  A table is given showing the properties of the dyestuffs from the following pairs of components:-anthraquinone-2-thioglycol-3-carboxylic acid and isatin, with or without bromination; anthraquinone-2-thioglycol-3-carboxylic acid and dibromisatin; anthraquinone - 2 - thioglycol - 3 - carboxylic acid and acenaphthenequinone followed by bromination; anthraquinone-2-thioglycol-3-carboxylic acid and thioisatin or 2 : 1-thionaphthisatin; anthracene-2-thioglycol-3-carboxylic acid and b -naphthisatin naphthalide, dibromisatin, thioisatin, 2 : 1-thionaphthisatin, b  - naphthisatin, acenaphthenequinone, 1 : 4-naphthoquinone, or 6-brom-1 : 2-naphthoquinone.