Patent GB-599722-A (GB)
Title: Aryl-dicyandiamides
IPC: C07D295/215
Filed: 1946-01-30
Abstract: N1-substituted dicyandiamides of the formula RR1N.C( : NH)NH.CN, wherein R and R1 are hydrogen or hydrocarbon radicals which may be substituted or not and may be joined to form a heterocyclic ring with the adjoining nitrogen atom, but both are not hydrogen at the same time, are prepared by reacting cyanocyanamide with an amine of the formula RR1NH. The cyanocyanamide and amine may be used in the form of their salts, or the salt of the cyanocyanamide with a weakly basic metal such as zinc or copper may be reacted with the free amine, or the amine salt of the cyanocyanamide may be used.  A solvent may be present, e.g. water, n-butanol, b -ethoxyethanol or nitrobenzene. In examples, (1) isopropylamine hydrochloride and sodium cyanocyanamide are heated in n-butanol to give N1-isopropyldicyandiamide; (2) isopropylamine hydrochloride and sodium cyanocyanamide are heated in water to give N1-isopropyldicyandiamide; (3) sodium cyanocyanamide and p-chloraniline hydrochloride (aniline, o-toluidine, p-anisidine, b -naphthylamine) are heated in water; (4) calcium cyanocyanamide (made by passing cyanogen chloride into an aqueous suspension of calcium cyanamide) and p-chloraniline hydrochloride are heated to give N1 - p - chlorphenyldicyandiamide; (5) sodium cyanocyanamide and p-toluidine hydrochloride are heated in water to give N1-p-tolyldicyandiamide; (6) N1-m-chlorophenyldicyandiamide is obtained similarly from m-chloraniline and sodium cyanocyanamide; (7) N1-p-iodophenyldicyandiamide is made from p-iodoaniline and sodium cyanocyanamide; (8) N1-(4-chloro-3-methylphenyl)-dicyandiamide is made similarly from 4-chloro-3-methylaniline; (9) p-bromoaniline hydrochloride and sodium cyanocyanamide are heated in water to give N1-p-bromophenyldicyandiamide; (10) m-bromoaniline hydrochloride and sodium cyanocyanamide are heated in water to give N1-m-bromophenyldicyandiamide; (11) 3-chloro-4-bromoaniline hydrochloride and sodium cyanocyanamide are heated in water to give N1-(3-chloro-4-bromophenyl)-dicyandiamide; (12) 3-chloro-4-iodoaniline and sodium cyanocyanamide are heated in water to give N1-(3-chloro-4-iodophenyl)-dicyandiamide; (13) methylamine hydrochloride and sodium cyanocyanamide are heated in n-butanol to give N1-methyldicyandiamide hemihydrate on recrystallization; (14) ethylamine hydrochloride is used similarly to give N1-ethyldicyandiamide; (15) n-propylamine hydrochloride is used similarly to give N1-n-propyldicyandiamide; (16) n-butylamine hydrochloride is heated with sodium cyanocyanamide in n-butanol to give N1-n-butyl dicyandiamide; (17) similarly by using iso butylamine, N1-isobutyldicyandiamide is obtained; (18) N-methylisopropylamine hydrochloride and sodium cyanocyanamide are heated in n-butanol to give N1-methyl-N1-isopropyldicyandiamide or recrystallization; (19) dimethylamine hydrochloride and sodium cyanocyanamide are heated in n-butanol to give N1-N1-dimethyldicyandiamide; (20) a -naphthylamine hydrochloride and sodium cyano cyanamide are heated in aqueous ethanol to give N1-a -naphthyldicyandiamide; (21) N - methylaniline hydrochloride and sodium cyanocyanamide are heated in water to give N1-phenyl-N1-methyldicyandiamide; (22) diphenylamine hydrochloride and sodium cyanocyanamide are heated in aqueous ethanol to give N1, N-diphenyldicyandiamide; (23) piperidine hydrochloride and sodium cyanocyanamide are heated in water to give N1, N1-pentamethylenedicyandiamide; (24) diethylamine hydrochloride and sodium cyanocyanamide are heated in n-butanol to give N1, N1-diethyldicyandiamide; (25) isopropylamine and the zinc salt of cyanocyanamide are heated in water to give N1-isopropyldicyandiamide; (26) the isopropylamine salt of cyanocyanamide, obtained by the interaction of zinc cyanocyanamide and isopropylamine is heated to give N1-isopropyldicyandiamide; (27) isopropylamine and zinc cyanocyanamide are heated in ethanol to give N1-isopropyldicyandiamide; (28) m-iodoaniline hydrochloride and sodium cyanocyanamide are heated in water to give N1-m-iodophenyldicyandiamide; (29) 4-chloro-3-bromoaniline hydrochloride and sodium cyanocyanamide are heated with water to give N1-4-chloro-3-bromophenyldicyandiamide, and (30) 3,4-dichloroaniline hydrochloride and sodium cyanocyanamide are heated in water to give N1-3,4-dichlorophenyldicyandiamide. Specifications 576,401, 577,843 and 599,713 are referred to.