Patent GB-412005-A (GB)
Title: Improvements in the manufacture and production of anthrapyrimidines
IPC: C09B5/16
Filed: 1933-03-27
Abstract: Anthrapyrimidines are prepared by treating a -acylaminoanthraquinones of the formula <FORM:0412005/IV/1> wherein R represents hydrogen or an organic radicle in presence of inert organic solvents or diluents with ammonia or salts or double compounds supplying ammonia. Ammonium chloride and carbonate and ammonium chloride-zinc chloride are specified for use in the reaction; water is split off and may be present in small amounts, but the presence of large amounts must be avoided.  Diluents specified are phenols, nitrobenzene, halogenbenzenes, toluene anisol, aniline, pyridine, quinoline, and catalysts such as copper or its compounds, oxides or salts of vanadium or tungsten may be present; pressure is preferably employed and is essential when treating a -acylaminoanthraquinones containing further replaceable halogen substituents.  In examples (1) 1-acetylaminoanthraquinone is converted to PyC-methylanthrapyrimidine by heating with ammonia in phenol in an autoclave; PyC-methyl-2-methyl-1.9-anthrapyrimidine and PyC-methyl-5-methoxy-1.9-anthrapyrimidine are similarly prepared from 1-acetylamino-2-methyl- and 1-acetylamino-5-methoxyanthraquinones; (2) 1-acetylamino-4-chloranthraquinone is converted to 4-amino-PyC-methyl-1.9-anthrapyrimidine by heating in phenol with ammonia in presence of ammonium vanadate under pressure and the corresponding 5-chloro- or 5-nitroanthraquinone derivatives and 8-chloranthraquinone derivatives yield isomeric anthrapyrimidines; (3) 1-amino-5-benzoylaminoanthraquinone is treated as in (2) to give 5-amino-PyC-phenyl-1.9-anthrapyrimidine; 1-p-chlorbenzoylamino-4-chloranthraquinone or 1-p-chlorbenzoylamino-4-nitroanthraquinone (prepared by treating 1-amino-4-nitroanthraquinone with p-chlorbenzoylchloride) yields 4-amino-PyC-p-chlorphenyl-1.9-anthrapyrimidine by heating in phenol with ammonia, and similarly 1-(quinoline-6<1>-carbamido)-4-aminoanthraquinone (prepared from 1-amino-4-chloranthraquinone and quinoline-6-carboxylic acid chloride, condensing the product with p-toluenesulphamide, and saponifying) yields 4-amino-PyC-quinolyl-1.9-anthrapyrimidine; (4) 1 - formylamino - 4 - benzoylaminoanthraquinone is treated as in (2) to give 4-benzoylamino-1.9-anthrapyrimidine; in an analogous manner 1-acetylamino-4-benzoylaminoanthraquinone (prepared by acetylating 1-amino-4-benzoylaminoanthraquinone) is converted to an acylaminoanthrapyrimidine, but under more drastic conditions PyC-methyl-PyC<1>-phenyl-1.9.4.10-anthrapyrimidine is obtained; 1.4-diacetylaminoanthraquinone, 1.4- and 1.5-dibenzoylaminoanthraquinones, and 1.5-diformylaminoanthraquinones yield mono - acylamino - 1.9-anthrapyrimidines; 1-acetylamino-4-p-toluenesulphaminoanthraquinone (prepared by condensing 1 - acetylamino - 4 - chloranthraquinone with p - toluene sulphonamide) yields 4 - p - toluenesulphamino - PyC - methyl - 1.9 - anthrapyrimidine.  Specifications 5998/09, [Class 2 (iii)], 381,942 and 385,295 are referred to.  The Specification as open to inspection under Sect. 91 refers to starting materials of the foregoing formula wherein R stands for methyl, ethyl, propyl, phenyl, naphthyl, quinolyl, pyridyl, cyclohexyl, anthraquinonyl, and radicles of anthraquinoneacridone, anthraquinonethioxanthone, benzanthrone, which radicles may be substituted by halogen, nitro, amino, hydroxy, alkoxy, or alkyl. In additional examples (5) 1-amino-4-benzoylaminoanthraquinone is heated with ammonia in phenol and the product benzoylated; (6) 1-amino-5-acetylaminoanthraquinone (prepared by partial saponification of p-toluenesulphamino-5-acetylaminoanthraquinone) is heated with ammonia in phenol under pressure to give 5-amino-PyC-methyl - 1.9 - anthrapyrimidine; in similar manner amino - 5 - b  - anthraquinonoylaminoanthraquinone yields the corresponding PyC-b -anthraquinonyl derivative; (7) 1.4-diaminoanthraquinone acylated with 1-nitroanthraquinone-2-carboxylic acid is condensed with ammonia in phenol in an autoclave to give a 1.9.4.10-anthradipyrimidine containing in PyC-positions 1-aminoanthraquinonyl-2- radicles; similarly a PyC-phenyl-PyC<1>-b -anthraquinonyl-1.9.4.10 -anthradipyrimidine is derived from PyC - phenyl - 4 - amino - 1.9 - anthrapyrimidine acylated with anthraquinone-2-carboxylic acid; 1.4-diaminoanthraquinone acylated with 5-nitroanthraquinone-2-carboxylic acid, 1-chloranthraquinone - 2 - carboxylic acid, anthraquinone-1-carboxylic acid, carboxylic acids of anthraquinoneacridone, anthraquinonethioxanthone, anthraquinoneimidazol, thiazolanthrone, anthrapyrimidone, anthrapyridone and pyrazolanthrone, may be similarly converted to 1.9.4.10-anthrapyrimidines containing PyC-substituents (anthraquinoneimidazol carboxylic acids are prepared from the amino derivatives by diazotisation, Sandmeyer replacement to a cyano derivative, and saponification); (8) 1.5 - diaminoanthraquinone acylated with anthraquinone-2-carboxylic acid is converted as in (7) to a 1.9.5.10-anthradipyrimidine derivative, and acylated 1.5-diamino-8-oxy- or 8-methoxyanthraquinones may be similarly treated; anthraquinonebenzacridone-Bz3-carboxylic acid condensed with 1-amino-5-b  - anthraquinonoylaminoanthraquinone on similar amination yields a 1.9.5.10-anthradipyrimidine containing a PyC-(b -anthraquinonyl)-radicle and a PyC<1>-(Bz3-anthraquinonebenzacridonyl)-radicle.  This subject-matter does not appear in the Specification as accepted.