Patent GB-479407-A (GB)
Title: Improvements in the manufacture and production of aza compounds of high molecular weight
IPC: C09B5/02
Filed: 1937-05-21
Abstract: Aza compounds of high molecular weight are manufactured by reacting 4- or 5-aminobenzanthrones with compounds capable of forming a ring with the keto and amino groups in peri-position, viz.: amides, nitriles and esters of carboxylic acids, e.g. urea, cyanamide, formamide, acetamide, lauric acid amide amides of benzenecarboxylic acids, hexahydrobenzamide, quinolinecarboxylic acid amides and the corresponding nitriles, esters of acylacetic acids, malonic acids, cyanacetic acid, urethanes, and also ketones, e.g. acetone, methyl ethyl ketone, methyl phenyl ketone, methyl lauryl ketone and cyclohexanone.  The reaction is usually carried out with heating and in the presence of a condensing agent; when using acid amides or nitriles the condensing agent is preferably an acid substance, e.g. boric acid, ammonium chloride, ammonium bisulphate or mineral acids, in many cases with the additional employment of copper or copper compounds, whilst when using esters or ketones there are preferably used alkaline agents, e.g. alkali metal hydroxides, carbonates or acetates or alkaline-earth metal hydroxides.  The products, which are dyestuffs or intermediates for dyestuffs or medicaments, may be purified by dissolution and precipitation, by sublimation, by way of their salts with strong acids or by treatment with oxidizing agents. In examples: (1) 5-aminobenzanthrone is heated with formamide, ammonium bisulphate and nitrobenzene to produce 10 : 12-diazaperylene; the product dyes acetate artificial silk yellow shades from an acetic acid or alkaline bath; the 5-aminobenzanthrone may be replaced by its alkyl, amino, halogen, nitro, cyano, sulphonic acid or carboxylic acid derivatives, and the formamide by other acid amides, e.g. acetamide or benzamide, yielding the corresponding 11-alkyl- or 11-aryl-10 : 12-diazaperylenes; the ammonium bisulphate may be replaced by hydrochloric, boric or sulphuric acid, sulphur dioxide or ammonium chloride; 5 - aminobenzanthrone may also be reacted with benzonitrile in the presence of hydrochloric acid; (2) 5-aminobenzanthrone is heated under pressure with acetone and caustic soda solution, producing 11 - methyl - 10 - azaperylene; 4 - aminobenzanthrone similarly yields 6 : 7-benzo-9-methyl-10-azapyrene; (3) 4-aminobenzanthrone is boiled with formamide, ammonium bisulphate and nitrobenzene, yielding 6 : 7-benzo-8 : 10-diazapyrene; the 4-aminobenzanthrone may be replaced by its substitution products or its benzo- or pyridino-derivatives; (4) 5-aminobenzanthrone is boiled with malonic acid diethyl ester, sodium acetate and nitrobenzene to produce 11 - hydroxy - 10 - azaperylene-12-carboxylic acid ethyl ester; with acetoacetic ester there is similarly obtained 11-hydroxy-12-acetyl-10-azaperylene, with benzoylacetic ester the corresponding phenyl derivative and with cyanoacetic ester the corresponding cyano compound; 4-aminobenzanthrones similarly yield the corresponding 6 : 7 - benzo - 10-azapyrene derivatives; (5) 5 - aminobenzanthrone is heated with urethane or urea and nitrobenzene to yield 11-hydroxy-10 : 12-diazaperylene; the product dyes vegetable and animal fibres yellow shades; 4-aminobenzanthrones yield the corresponding 6 : 7-benzoazapyrenes.  The Specification as open to inspection under Sect. 91 refers also to the reaction of 5-aminobenzanthrone with arylmethylimide chlorides.  This subject-matter does not appear in the Specification as accepted.