Patent GB-598453-A (GB)
Title: Improvements relating to the manufacture of amidines
IPC: C07D213/78
Filed: 1945-09-04
Abstract: Compounds containing the amidine grouping are manufactured by the interaction of a nitrile of the general formula R.CN (wherein R represents an alkyl, aryl, aralkyl or alicyclic group or a heterocyclic group having nitrogen as the hetero atom or atoms, which groups may contain substituents) with ammonia, urea or a monoamine of the general formula NHR1R2 (wherein R1 and R2 each represent an alkyl, aryl, aralkyl or alicyclic group or a heterocyclic group having nitrogen as the hetero atom or atoms, which groups may contain substituents, or R1 also hydrogen, or R1 and R2 jointly a divalent polymethylene chain) in the presence of aluminium chloride, zinc chloride, ferric chloride or stannic chloride. Alternatively, a preformed double compound of the metal salt and ammonia or the amine is used instead of the substances themselves. In examples: (1) benzyl cyanide is heated with urea and anhydrous zinc chloride, and the product is treated with sodium hydroxide solution, extracted with chloroform and the extract mixed with an alcoholic solution of picric acid to produce phenylacetamidine picrate; (2) benzonitrile is heated with anhydrous aluminium chloride while passing in dry ammonia, and the product is worked p  up as in (1) to give benzamidine picrate; (3) p-nitrobenzonitrile is heated with aluminium hexamminochloride, and p-nitrobenzamidine is precipitated with sodium hydroxide solution, dissolved in dilute hydrochloric acid and treated with a solution of sodium picrate to precipitate the picrate of the amidine; (4) the aluminium hexamminochloride in (3) is replaced by anhydrous zinc chloride and dry ammonia; (5) p-nitrobenzonitrile is heated with urea and anhydrous aluminium or zinc chloride or stannic chloride, and the product is converted into p-nitrobenzamidine picrate via the free amidine; (6) anhydrous ferric chloride is used as the catalyst in (5); (7) o-nitrobenzonitrile is heated with urea and anhydrous aluminium chloride, and the product is converted to o-nitrobenzamidine picrate via the free amidine and the hydrochloride; (8) b -naphthonitrile similarly yields b -naphthamidine; (9) diethylacetonitrile is heated with cyclohexylamine and anhydrous aluminium chloride to produce N-cyclohexyl-a  : a -diethylacetamidine hydrochloride; (10) to (15) benzyl cyanide similarly yields N-cyclohexyl phenylacetamidine hydrochloride, from which the free amidine may be liberated with sodium hydroxide solution; (16) anisonitrile similarly yields N-cyclohexylanisamidine hydrochloride; (17) p-methylsulphonylbenzonitrile sl heated with diethylamine and anhydrous aluminium chloride and the product is worked up as in (1) to give p-methylsulphonyl-N : N-diethylbenzamidine picrate; (18) benzonitrile and piperidine are similarly reacted and the reaction mixture is treated with sodium hydroxide solution to liberate N : N-pentamethylenebenzamidine; (19) p - methylsulphonylbenzonitrile similarly yields p-methyl sulphonyl - N : N - pentamethylenebenzamidine; (20) benzonitrile and benzylamine are heated with anhydrous aluminium chloride, and N-benzylbenzamidine hydrochloride is isolated amine are heated with anhydrous aluminium chloride to produce N-benzylaminoamidine hydrochloride; (22) acetonitrile and aniline are heated with anhydrous aluminium chloride and the product is converted to N-phenylacetamidine picrate via the free base; (23) benzonitrile and aniline are heated with anhydrous zinc chloride, and the product is treated with sodium hydroxide solution to liberate N-phenylbenzamidine; (24) benzonitrile and o-nitraniline are heated with anhydrous aluminium chloride, and the product is converted to N-(o-nitrophenyl)-benzamidine picrate via the free base and the hydrochloride; (25) 2 : 4-dichlorobenzonitrile and aniline are heated with anhydrous aluminium chloride, and N-phenyl-2 : 4 - dichlorobenzamidine hydrochloride is isolated via the free base; (26) benzonitrile and methylaniline are heated with anhydrous aluminium chloride, and the product is treated with sodium hydroxide solution to liberated N-methyl-N-phenylbenzamidine; (27) a -cyanopyridine and diphenylamine similarly yield N : N-diphenylpicolinamidine; (28) p-methylsulphonylbenzonitrile and a  - aminopyridine similarly yield p - methylsulphonyl - N - a  - pyridylbenzamidine; (29) benzonitrile is similarly treated to produce N-a -pyridylbenzamidine; (30) p : p1-dicyanodiphenoxypropane and aniline are heated with anhydrous aluminium chloride, and the product is treated with sodium hydroxide solution, hydrochloric acid, sodium hydroxide solution again and then benzenesulphonic acid to obtain a : g -bis-(p-N-phenylamidino) - phenoxypropane benzenesulphonate.