Studies on the Syntheses of the Aliphatic Diamines. III.:Syntheses of ω-Chloroenanthonitrile and 1, 5-Dihalopentanes using Acrolein as Starting Materials.

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The two processes of synthesis of azelonitrile from acrolein as a starting material were investigated. The routes of synthesis were as follows: (1) Acrolein → 2-formyl-3, 4-dihydro-2H-pyran → 1, 6-hexanediol 1, 6-dihalohexane → ω-chloroenanthonitrile azelonitrile. (2) Acrolein → ethyl vinyl ether → 2-ethoxy-3, 4-dihydro-2H-pyran → glutaraldehyde → 1, 5-pentanediol → 1, 5-dihalopentane → azelonitrile. The studies of those steps developed to industrial stage and reported in literatures being omitted, only the conditions for syntheses of ω-chloroenanthonitrile and 1, 5-dihalopentane were investigated. The yield of product from dimerization reaction was slightly better than those from known literatures. It was comfirmed the ring opening of the dimer by the hydrogenation put on record of P.B. Report was of an error. 1, 6-Hexanediol was synthesized, though small in amount, by another method. Reaction of hydrogen halide on 1, 5-pentanediol and 1, 6-hexanediol gave their dihalo-substituted products with high yield. Also, some knowledges on its reaction mechanism were obtained. In the mononitrilation of dihalopentane and dihalo-hexane, the formation of dinitrile was prevented and the yield of mononitrile was increased, by use of the dihalogen in excess against the sodium cyanide.
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