Patent GB-922585-A (GB)
Title: New hydrazine derivatives and processes for their manufacture
Filed: 1959-07-17
Abstract: The invention comprises: (1) compounds of the general formula <FORM:0922585/IV(a)/1> (wherein A denotes a straight or branched alkylene chain, R1 denotes a free amino group, a monoacylated amino group, a secondary amino group or an alkylideneamino group, R2 denotes a hydrogen atom, or may also denote an acyl group if R1 is not a monoacylated amino group, R3 and R4 each denote a hydrogen atom or a C1-6 alkyl group or they jointly form with the adjacent nitrogen atom a 5- or 6-membered heterocyclic ring which may contain a further hetero atom, the total number of carbon atoms in R3, R4 and A being at least 3) and their addition salts with inorganic and organic acids; (2) 1-(11-dimethylaminobutyl-31) -1-acetyl-4-phenylthiosemicarbazide; (3) the preparation of compounds I by the following processes: (a) (when R1 is other than alkylideneamino, R2 is hydrogen and R3 and R4 are other than hydrogen) reacting a compound R11-NH2 (VII) (wherein R11 denotes a monoacylated or a secondary amino group) with an aliphatic oxo compound of the general formula <FORM:0922585/IV(a)/2> (wherein R13 and R14 have the meanings given for R3 and R4, except hydrogen, and <FORM:0922585/IV(a)/3> denotes A less a hydrogen atom) with subsequent reduction of the resulting hydrazone, or with an aminoalkyl halide of the general formula <FORM:0922585/IV(a)/4> (wherein hal denotes a chlorine, bromine or iodine atom), and in either case, if desired, splitting off the acyl group if R11 is a monoacylated amino group; (b) (when R1 is a free amino or alkylideneamino group, R2 is an acyl group and R3 and R4 are other than hydrogen) reacting an end product of (a) in which R1 is a free amino group, with an aliphatic oxo compound to convert R1 to an alkylideneamino group, or reacting a compound R11111-NH2 (XIII) wherein R11111 denotes an alkylideneamino group) with a compound of the general formula X above, and in either case treating the product with an acylating agent and, if desired, finally splitting off the alkylidene group; (c) (when R1 is other than alkylideneamino and R2, R3 and R4 are all hydrogen) reacting a compound VII above with a compound R7-CN (XVI) (wherein R7 is an alkenyl radical) to produce a compound of the general formula R11-NH-A1-CN XVII (wherein A1 denotes A less a methylene group) and reducing the cyano group to an aminomethyl group, and, if desired, splitting off the acyl group if R11 is a monoacylated amino group; (d) (when R1, R2, R3 and R4 are all hydrogen), reacting a compound XIII above with a compound XVI above to give a compound of the general formula R11111-NH-A1-CN XIX, splitting off the alkylidene group and reducing the cyano group to an aminomethyl group; (e) (when R1 is a secondary amino group and R3 and R4 are other than hydrogen) reducing a corresponding compound in which R1 is an alkylideneamino group and, if desired, splitting off R2 if it is an acyl group; (f) (as in (e) except that R2 must be hydrogen) reducing a corresponding compound in which R1 is a monoacylated amino group.  The products are useful as monoamineoxidase inhibitors in pharmacy, as intermediates for the preparation of pharmaceutical agents, or as oxidation inhibitors in motor fuels.  1-(11- Dimethylaminobutyl- 31) - 1-acetyl-4-phenylthiosemicarbazide is prepared by reacting 1-(11-dimethylaminobutyl- 31)-1- acetylhydrazine with phenyl isothiocyanate.  Phenylthiosemicarbazides are similarly prepared from 1-(dimethyl- and diethyl-aminoisopropyl)-1-acetylhydrazine also. N-Methyl-N- isopropylaminobutan-3-one is prepared by refluxing N-methyl-N-isopropylamine hydrochloride with acetone and paraformaldehyde in ethanol.