Patent GB-445467-A (GB)
Title: Improvements in the manufacture and production of derivatives of the anthraquinone series
IPC: C09B5/24
Filed: 1934-10-01
Abstract: 1(N).2 - Pyridonoanthraquinone derivatives are made by condensing in a neutral or basic medium a 1-amino-anthraquinone which contains an aldehyde or ketone group in the 2-position and which may contain an alkyl or aryl radicle in the amino group and any other substituents in the anthraquinone nucleus, with a compound of the general formula R.CO.CH2.R<1> in which R is halogen, OH, O-alkyl, or O-acyl and R<1> is hydrogen or a cyano or a free or esterified carboxylic group; or by ring-closing a 1-aminoanthraquinone of the kind above described which also contains an acetyl group in the 1-amino group in presence of a basic agent.  When R is halogen or O-acyl, the medium must be sufficiently basic for the acid split off in the reaction to be neutralized.  The reaction is preferably carried out in the presence of organic diluents, which may be basic such as pyridine or aniline, and in presence of basic substances such as alkali metal acetates or carbonates, or of piperidine as a catalyst.  The products are dye intermediates.  In examples, the following starting materials are specified: 1 - acetylaminoanthraquinone - 2 - aldehyde or its 4-chlor derivative, 1-acetylamino-2-acetyl - 4 - chloranthraquinone, 1 - amino - anthraquinone - 2 - aldehyde and cyano - acetic acid ethyl ester, 1-aminoanthraquinone-2-aldehyde and diethyl malonate, 1-amino-2-(4<1>-methylbenzoyl)-anthraquinone and diethyl malonate, 1 - acetylamino - 2 - (4<1> - methylbenzoyl) - anthraquinone, 1 - acetylamino - 2 - (2<1> . 4<1> - dimethylbenzoyl) anthraquinone, 1 - methylaminoanthraquinone - 2 - aldehyde and diethyl malonate, 1 - methylamino - 2 - benzoylanthraquinone, the acetyl compound of 1-methylamino - 2 - (p - carboxybenzoyl) - anthraquinone, 1 - methylamino - 2 - (p - carboxybenzoyl)-anthraquinone itself and diethyl malonate, 1 p  - methylamino - 2 - benzoyl - 4 - chloranthraquinone and diethyl malonate, and the acetyl compound of 1-(p-carbethoxyphenylamino) - 2 - (p - methylbenzoyl) - anthraquinone.  1 - Aminoanthraquinone - 2 - ketones and aldehydes.--1 - Amino - 2 - benzoylanthraquinones are made by condensing 1-chloranthraquinone-2-carboxylic acid chloride with benzene or a homologue in presence of aluminium chloride and reacting the product with an amino compound, thus replacing the chlorine by a substituted amino group.  Any methyl groups attached to the benzoyl radical may be oxidized to carboxylic groups.  The methods of preparation of the following substances are described: 1 - methylamino - 2 - benzoylanthraquinone, 1 - methylamino - 2 - p - carboxybenzoylanthraquinone, 1 - (p - carbethoxyphenylamino) - 2 - (p - methylbenzoyl - ) - anthraquinone.  1 - Methylamino - 2 - benzoyl - 4 - chloranthraquinone is made similarly using 1 : 4 - dichloranthraquinone - 2 - carboxylic acid chloride as starting material.  The acetyl compounds of 1-amino-anthraquinone-2-aldehyde, 1 - amino - 4 - chloranthraquinone - 2 - aldehyde, 1 - amino - 2 - acetyl - 4 - chloranthraquinone, 1 - amino - 2 - (4<1> - methylbenzoyl) - anthraquinone, 1 - methylamino - 2 - (p - carboxybenzoyl) - anthraquinone, and 1 - (p - carbethoxyphenylamino) - 2 - (p - methylbenzoyl) - anthraquinone are obtained by treating the parent materials with acetic anhydride in presence of concentrated sulphoric acid.  The 4-chlor derivatives of 1-aminoanthraquinone - 2 - aldehyde and 1 - amino - 2 - acetylanthraquinone are made by treating the parent materials with sulphuryl chloride in nitrobenzene.  1 - Amino - 2 - (4<1> - methylbenzoyl) - anthraquinone is made by reacting the corresponding 1-chlor compound with p-toluene sulphamide and saponifying the reaction product with sulphuric acid.