GB214864A - Manufacture of indigoid dyestuffs and intermediate products - Google Patents

Abstract

Thionaphthisatins are prepared by condensing a -thionaphthol, or halogenated a - or b -thionaphthols, with oxalyl chloride. In examples, 1 : 2-thionaphthisatin and 6-chlor-2 : 1-thionaphthisatin are obtained from a -thionaphthol and 6-chlor-2-thionaphthol respectively and an excess of oxalyl chloride which is afterwards distilled off, the product being heated for some hours, and extracted with sodium carbonate solution from which the thionaphthisatin is precipitated by acidifying; 1-brom-2 : 3-thionaphthisatin is obtained from 1-brom-2-thionaphthol but the condensation is completed, after removing the excess of oxalyl chloride, by means of aluminium chloride in presence of carbon bisulphide. The following compounds also are described:-1-chlor-2 : 3-thionaphthisatin, 4- and 8-chlor-1 : 2-thionaphthisatin, 5- and 8-chlor-2: 1-thionaphthisatin, 5-brom-2 : 1-thionaphthisatin. Halogenated thionaphthols are obtained from the corresponding naphthylamine sulphonic acids by diazotization and replacement of the diazo group by halogen, the halogen naphthalenesulphonic acids being then converted to their sulphonic chlorides which are reduced to the corresponding thionaphthols. Thioindigoid dyes, dyeing cotton from the vat in brown, bordeaux, grey, red-violet, blue-violet &c. shades are obtained by condensing the thionaphthisatins prepared in the above described manner with compounds containing cyclic methylene groups capable of reacting. They may be further halogenated, or in case of aminosubstituted products, acidylated. In examples dyestuffs are obtained from the following pairs of components: -1 : 2-thionaphthisatin and 1 : 2-naphthioindoxyl, 1 : 2-thionaphthisatin and oxythionaphthenecarboxylic acid followed by bromination, 1 : 2-thionaphthisatin and 6-amino-oxythionaphthene-carboxylic acid followed by bromination or benzoylation, 4-chlor-1 : 2-thionaphthisatin and indoxylcarboxylic acid, 5-brom-2 : 1-thionaphthisatin and acenaphthenone, 1-chlor-2 : 3-thionaphthisatin and oxythionaphthene-carboxylic acid. In a table the properties are given of dyestuffs obtainable from the following components:-1 : 2-thionaphthisatin, 4- or 8-chlor-1 : 2-thionaphthisatin, 5-brom-2 : 1-thionaphthisatin, 5-, 6-, or 8-chlor-2 : 1-thionaphthisatin, 1-chlor-, or 1-brom-2 : 3-thionaphthisatin; 1 : 2- and 2 : 1-naphthioindoxyl, oxythionaphthene-carboxylic acid, 6-amino-oxythionaphthene and its carboxylic acid, 6-chlorooxythionaphthene and its carboxylic acid, indoxyl, acenaphthenone: some of the products are afterwards brominated.