Patent GB-869977-A (GB)
Title: Diazacycloalkenes and the preparation thereof
IPC: C07D233/70
Filed: 1958-12-23
Abstract: The invention comprises compounds of the general formula: <FORM:0869977/IV (b)/1> the acid addition and quaternary ammonium salts thereof (the latter having an alkyl group containing up to four carbon atoms) wherein R is an alkyl or alkenyl group containing up to eighteen carbon atoms; X is oxygen or sulphur; n is an integer from three to five; R1 is a hydrogen atom or an alkyl or alkenyl group containing up to six carbon atoms, the total number of carbon atoms in R and R1 being six to twenty-four; and further compounds wherein is two or three and adjacent carbon atoms in the heterocyclic ring form a conjugated system, and the preparation thereof (1) where X is sulphur and the heterocyclic residue is imidazole or pyrimidine, by reacting an alkyl or alkenyl halide with the sodium salt of a 2-mercaptoimidazole or 2-mercaptopyrimidine in an ether solvent at between 35 to 140 DEG  C. for from about one to five hours; or (2) where X is sulphur and the heterocyclic residue is tetrahydropyrimidine, tetrahydrodiazepine, or diazacycloctene, reacting an alkyl or alkenyl halide in a polar lower aliphatic oxygenated solvent with at least an equimolar quantity of a 2-mercaptotetrahydropyrimidine, 2-mercaptotetrahydrodiazepine or 2-mercapto-diazacyclo-octene at about 60-150 DEG C. for one to sixteen hours; recovering the resulting halogen acid addition salt by evaporating the solvent in vacuo and, if desired, neutralizing said acid addition salt with an alkaline reagent; or (3) where X is oxygen and the heterocyclic residue is imidazole or pyrimidine, reacting an alkyl or alkenyl halide with the sodium salt of 2-hydroxyimidazole or 2-hydroxypyrimidine in an ether solvent at between 35-140 DEG C. for one to five hours, or (4) where X is oxygen and the heterocyclic residue is tetrahydropyrimidine, tetrahydrodiazepine or diazacyclo-octene, reacting an alkoxide or an alkenyloxide with 2-methylmercaptotetrahydropyrimidine, 2-methylmercaptotetrahydrodiazepine or 2-methylmercaptotetrahydrodiazacyclo-octene in an ether solvent at 60-140 DEG C. for one to five hours; and if desired forming an acid addition or quaternary ammonium salt of any free base so prepared. 2-Mercapto-4,5,6,7-tetrahydro-1,3-diazepine is prepared by reacting 1,4-diaminobutane with carbon disulphide.ALSO:Pharmaceutical compositions and agricultural compositions comprise a pharmaceutical carrier or an agricultural extending-agent or carrier respectively together with a compound of the general formula <FORM:0869977/VI/1> or an acid addition or quaternary ammonium salt thereof (the latter having an alkyl group containing up to four carbon atoms) wherein R is an alkyl or alkenyl group containing up to 18 carbon atoms; X is oxygen or sulphur; n is an integer from 3 to 5; R1 is a hydrogen atom or an alkyl or alkenyl group containing up to six carbon atoms, the total number of carbon atoms in R and R1 being six to twenty-four; and further compounds wherein n is 2 or 3 and adjacent carbon atoms in the heterocyclic ring form a conjugated system.  The compositions, according to their proposed use, may contain other active ingredients such as pyrethrum, streptomycin, oxytetracycline, D.D.T., malathion or chlordane, and may be in the form of dusts, powders, solutions, emulsions, suspensions, ointments and aerosols.  Examples describe the preparation of a dust comprising calcium carbonate, olein, slaked lime and 2-decylmercapto - 1,4,5,6 - tetrahydropyrimidine hydrobromide; a powder suitable for mixture with water to form a suspension comprising talcum, sodium dibutyl naphthalene sulphate, casein, sodium carbonate and 2-methylmercapto - N - hexyl - 1,4,5,6 - tetrahydropyrimidine; a solution of 2-nonylmercaptoimidazole in carbon tetrachloride; a solution suitable for the preparation of an aqueous emulsion comprising 2 - propyl - mercapto - N - butylimidazole in xylene/turkey red oil (1 : 1); a solution containing D.D.T. and either 2-octyloxypyrimidine or 2-octadecyloxy-1,4,5,6-tetrahydropyrimidine, in kerosene, aerosols containing 2-octyloxy-4,5,6,7-tetrahydro-1,3-diazepine, 2 - dodecylmercapto - 5 - ethyl - 4,5,6,7 - tetrahydro - 1,3 - diazepine hydrobromide, or 2 - (2 - octenyloxy) - 1,4,5,6 - tetrahydropyrimidine hydrobromide, dispersions of either 2-hexylmercapto - 4,5,6,7 - tetrahydro - 1,3 - diazepine hydrobromide or 2-dodecylmercapto-1,4,5,6 - tetrahydropyrimidine hydrochloride in petroleum jelly, and an aqueous mixture containing 2 - tetradecylmercapto - 1,4,5,6 - tetrahydropyrimidine hydrobromide and a surface-active agent. Salts specified in addition to hydrohalides are sulphates, nitrates, phosphates, citrates, gluconates and tartrates.