Studies on the Syntheses of the Aliplatic Diamines. IV.

Synthesis of azelonitrile was made by condensation reaction of ω-chloroenanth onitrile or 1, 5-dihalopentane with acetonitrile in the presence of sodium amide. These reactions in nonpolar organic solvent at 20-25°c caused cyclization and polymerization there being considerable decrease in the yield of azelonitrile. The reaction in the presence of acetonitrile in excess against ω-chloroenanthonitrile and sodium amide in liquid ammonia as a solvent at -50°c was effective to suppress the foregoing side reactions and the maximum yield of azelonitrile from ω-chloroenanthonitrile was 80% The rate of reaction in a mixed solvent of liquid ammonia-ether was small. In the case of 1, 5-dihalopentane, kinds of solvent and halogen used showed much effects on the yield of product. Thus, in case of iodine and bromine at around -65°c it yielded 60-70% of azelonitrile, gave no cyclization product such as cyanocyclohexane but gave a polyamine as the by-product; in case of chlorine, the yield of azelonitrile was low and that of cyanocyclohexane was high. Liquid ammonia was superior as the solvent while single use of toluene or ether was not favorable.