Patent GB-485175-A (GB)
Title: Improvements in the manufacture and production of compounds of the anthraquinone series
Filed: 1936-11-13
Abstract: Anthraquinone dyes are made by condensing compounds having a carbonyl group in adjacent position to a double linkage in an open chain with an aminoanthraquinone or a derivative thereof having a ring attached to an anthraquinone nucleus, e.g. an aminobenzanthrone, anthrapyridine, anthrapyrimidine or anthraquinone oxazole.  As carbonyl compounds may be used vinylketones of the formula R.CO.CH = CH2, where R is an aliphatic, cycloaliphatic or aromatic radicle, e.g. vinyl methyl, ethyl and phenyl ketones, acrolein, crotonaldehyde and citral. Instead of vinyl methyl ketone vinylacetylene may be used in the presence of water under conditions in which the ketone is formed. The reaction may be carried out by heating in the presence of diluents, e.g. alcohols, and assistants, e.g. piperidine or chloracetic acid may be used.  Some of the products are converted into azabenzanthrones by ring closure.  In examples, (1) vinylmethylketone is heated under pressure with 1-aminoanthraquinone in the presence of ethanol and a small amount of hydroquinone (which increases the stability of the ketone), the product is g -ketobutyl-1-aminoanthraquinone; the ethanol may be replaced by pyridine, and the 1-aminoanthraquinone by 1 : 4-diaminoanthraquinone, when the 1 : 4-di(g -ketobutylamino)-anthraquinone is obtained, which dyes acetate artificial silk in blue shades, (2) 1 : 2- or 1 : 8-diamino- or 1 - amino - 4 - hydroxy - anthraquinone are heated p with vinylmethylketone in alcohol or pyridine, the products dye acetate artificial silk in red or violet shades, (3) vinylacetylene is led into a solution of 1 : 4-diaminoanthraquinone in concentrated sulphuric acid in presence of mercury sulphate to give the di-g -ketobutylamino derivative; 1-amino-, 1 : 2 : 4-triamino-, 1 : 4 : 5 : 8-tetraamino-, 1-amino - 4 - methylamino-, 1 : 4-nitroamino-, 1-amino-4-hydroxy-, and 1-amino-4-methoxyanthraquinone, and Bzl-aminobenzanthrone may be similarly treated, (4) acrolein is heated with 1 : 4-diaminoanthraquinone in butanol; the product may be converted into the corresponding azabenzanthrone by treating with ring-closing agents such as zinc chloride or concentrated sulphuric acid, (5) 1 : 4 : 5 : 8-tetraaminoanthraquinone is condensed with acrolein, (6) 1 : 4-diamino- and 1-amino-4-methoxy-anthraquinone are condensed with vinylmethylketone in the presence of concentrated sulphuric acid, and (7) 1 : 4-diaminoanthraquinone is condensed with phenylvinylketone in the presence of alcohol and hydrochloric acid. A table is given of the shades on acetate artificial silk produced by the products from vinylmethylketone and 1 - amino-, 1 - amino - 2 - and 4 - hydroxy-, 1 : 5 - diamino - 4 - hydroxy-, 1 : 5 - diamino-4 : 8 - dihydroxy-, 1 - amino - 4 - nitro-, 1 : 4 - diamino - 5 - nitro- and 3 - methoxy-, 1 - amino - 4 - methylamino-, 1 : 2-, 1 : 5-, and 1 : 8-diamino-, 1 : 2 : 4-triamino-, 1 : 4 : 5 : 8-tetraamino-, 1-amino-4-ethanolamino-, 1 - 5-diamino - 2 : 4 : 6 : 8 - tetrachlor-, 1 - amino-4- and 5-benzoylamino-, 1-amino-4- and 5-chlor-anthraquinone, Bzl-aminobenzanthrone, 5-amino-1 : 9-anthrapyrimidine, and 4-amino-1 : 9-pyrazoloanthranthrone.