Patent GB-398053-A (GB)
Title: Manufacture of intermediate products and dyestuffs
IPC: C09B7/00
Filed: 1932-11-11
Abstract: Indoxyl, thioindoxyl, isatin and thioisatin derivatives.--A mercaptonaphthalene-carboxylic acid or an aminonaphthalene carboxylic acid or an N-monosubstitution product thereof is converted by a known method into a naphthothioindoxyl or a naphthindoxyl containing at least one carboxyl group in the naphthalene nucleus, or a reactive a -derivative thereof, or a corresponding naphthothioisatin or naphthisatin containing at least one carboxyl group.  In examples: (1) 2-mercaptonaphthalene-3-carboxylic acid is condensed with chloracetic acid, the product treated with phosphorus pentachloride and converted to 2 : 1-naphthothioindoxyl-3-carboxylic acid chloride in presence of aluminium chloride; (2) 2-mercaptonaphthalene-4-carboxylic (prepared by converting 1-aminonaphthalene-3-sulphonic acid to the 1-cyanonaphthalene-3-sulphonic acid and the latter to the 3-sulphochloride which is reduced with simultaneous saponification of the cyano group) is treated as in (1) to give 2 : 1-naphthothioindoxyl-4-carboxylic acid; (3) 2-mercaptonaphthalene-5-carboxylic acid (prepared from 1-aminonaphthalene-6-sulphonic acid in an analogous manner to the above) is treated as in (1) to give 2 : 1-naphthothioindoxyl - 5 - carboxylic acid; (4) 2 - aminonaphthalene-3-carboxylic acid is condensed with monobromomalonic acid diethyl ester to give a product which is converted to 3-carboxy2 : 1-naphthindoxyl-a -carboxylic acid ethyl ester by heating at 220 DEG ; the a -carboxy group is easily split off by saponification; (5) 2-naphthothioglycol-1-carboxylic acid is treated with phosphorus pentachloride and ring-closed by means of aluminium trichloride to give 2 : 3-naphthothioindoxyl-1-carboxylic acid; (6) the product of (1) is treated with p-nitrosodimethylaniline to give the dimethylaniline anil of 2 : 1-naphthothioindoxyl-3-carboxylic acid; this product, on treatment with 50 per cent sulphuric acid, yields 2 : 1-naphthothioisatin-3-carboxylic acid; the corresponding naphthisatin is obtained by treating 2 - aminonaphthalene - 3 - carboxylic acid with oxalyl chloride and ring-closing by means of aluminium chloride. Reference is made to the preparation of the naphthindoxyls from aminonaphthalene carboxylic acids generally by the Blank synthesis (cf. Specification 19946/96, [Class 2, Acids and Salts, Organic &c.]), to the conversion of mercaptonaphthalene carboxylic acids, aminonaphthalene-carboxylic acids or N-monosubstituted derivatives thereof to naphthisatins and naphthothioisatins by treatment with oxalyl chloride or by the Sandmeyer synthesis, and to the production of the a -oximes and a -halides of naphthothioindoxyl-3-carboxylic acid or naphthindoxyl-3-carboxylic acid by the action of nitrous acid or a halogen respectively.  Anthraquinonyl derivatives of indigoid amides are prepared by condensing a naphthindoxyl or a naphthothioindoxyl containing a carboxy group in the naphthalene nucleus, or a reactive a -derivative thereof, or a corresponding naphthisatin or naphthothioisatin containing a carboxy group in either order with a component suitable for producing indigoid dyes and with an aminoanthraquinone or substitution product thereof.  Or such dyes are obtained by reacting these intermediates in either order with an oxidizing agent and an aminoanthraquinone, and, if desired, halogenating the product.  In examples, (7) the product of (3) is air-oxidized in sodium carbonate solution to 2 : 1 : 2<1> : 1<1> - naphthothioindigo - 5 : 5<1>-dicarboxylic acid which in the form of its acid chloride is condensed with 1-amino-4-benzoyl-aminoanthraquinone (dyes red-brown); by condensing this component with 2-(p-dimethylamino)-anil of 4-methyl-6-chloro-3-oxythionaphthene and the resulting acid derivative with 1 - amino - 4 - benzoylaminoanthraquinone or by condensing with 2-(p-dimethylamino)-anil of 2 : 1-naphthothioindoxyl and proceeding similarly, other dyes giving red-brown shades are obtained; (8) 2 : 1-naphthothioindoxyl-4-carboxylic acid is condensed with 2-(p-dimethylamino)-anil of 2 : 1-naphthothioindoxyl and the product in the form of its acid chloride is condensed with 1-amino-4- or 5-benzoylaminoanthraquinone, 1-aminoanthraquinone or 1 - amino - 4 - methoxyanthrquinone (dyeing brown shades); (9) the symmetrical thioindigo dye of (7) is brominated in nitrobenzene (dyes red-brown); (10) a table describes the dyes obtained by condensing 2 : 1-naphthothioindoxyl-3-carboxylic acid with the following pairs of components : 2-(p-dimethylamino)-anil of 2 : 3-naphthothioindoxyl and 1-amino-4- and 5-benzoylaminoanthraquinones (dyes olive green and heliotrope); 2-(p-dimethylamino)-anil of 2 : 1-naphthothioindoxyl-3-carboxylic acid and 1-amino-5-benzoylaminoanthraquinone (yellow-brown); acenaphthenequinone and 1-amino-4- and 5-benzoylaminoanthrauyinones (brick-red and orange); 2-(p-dimethylamino)-anil of 4-methyl-6-chloro-3-oxythionaphthene and 1-amino-4- and 5-benzoylaminoanthraquinones (reddish-brown); 2-(p-dimethylamino)-anil of 6-ethoxy-3-oxythionaphthene and 1-amino-4- and 5-benzoylaminoanthraquinones (bordeaux and yellow-brown), and with 1 - amino - 4 - methoxyanthraquinone (yellow-bordeaux); 2 - (p - dimethylamino)-anil of 2 : 1-naphthothioindoxyl and 1-amino-4- and 5-benzoylaminoanthraquinones (yellow-brown and red-brown). Further examples illustrate the dyeing of cotton with these products, and mention is made of their application to wool, silk and artificial silk.  Specifications 354,716 and 360,349 also are referred to.