1988 Fiscal Year Final Research Report Summary
Studies on the Electro-reductive Dinerization of 2,4-pentadienenitriles
| Project/Area Number |
62470020
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | Shizuoka University |
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Principal Investigator |
KATAGIRI Takao Shizuoka Univ.,Fac.of Engineering,Prof., 工学部, 教授 (60021995)
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| Co-Investigator(Kenkyū-buntansha) |
TAKABE Kunihiko Shizuoka Univ.,Fac.of Engineering,Asst.Prof., 工学部, 助教授 (30022239)
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| Project Period (FY) |
1987 – 1988
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| Keywords | 3-mathyl-2,4-pentadienenitrile / electro-reductive dimerization / 1,8-dicyano-2,7-dimethyl-2,6-octadiene / 3,7ージメチルー2,7ーオクタジエンー1ーオール(イソゲラニオール) |
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| Research Abstract |
Nobel syntheses of 3-hydroxy-3-methy1-4-pentenenutruke and 3-methy1-2,4-pentadienenitrile were studied. A carbanion which was generated from acetonitrile by the action of butyllithium, was reacted with methyl vinyl ketome, and the hydroxynitrile was separated purely in 90% yield. This method might be supreme than ever. The hdroxynitrile was dehydrated to the dienenitrile by using phosphorous oxy chloride-pyridine-ether at the ambient temperature for 50 hours, and the dieneitrile was prepared in 67% yield.
The dienenitrile was dimerized by electrochemical method. At the low temparerature(at -5゜c), the dimerized product was 1,8-dicyano-2,7-dimethy1-2,6-octadiene only. At the higher temperature, however, the dimer product was a mixture of an compound(double bonds were separated from cyano groups) and 1,8-dicyano-2,7-dimethy1-1,7-octadiene(double bonds were conjugated with cyanogroups). And the reaction mechanism was discussed.
Because the above hydroxynitrile was prepared in high yield, isogeraniol(3,7-dimethy1-2,7-octadien-1-ol), which was the synthetic precursor for insect feromones, was synthesized from it. The hydroxynitrile was treated with aceticacid and acetic anhydride and 5-acety1-3-methy1-3-pentenenitrile was obtained. This was connected with metallyl bromide by a reformatsky type reaction, and the main skeletom of isogeraniol was formed. A carbonyl group in the compound was reduced to methylene, and isogeraniol was obtained.
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