| Project/Area Number |
60850155
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| Research Category |
Grant-in-Aid for Developmental Scientific Research
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Osaka University |
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Principal Investigator |
HURAHASHI Shun-Ichi Faculty of Engineering Science, Osaka University, 基礎工学部, 教授 (60029436)
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| Co-Investigator(Kenkyū-buntansha) |
NISHINO Masaki Toray Industries, Inc., 研究開発企画部, 主席部員
IMADA Yasushi Faculty of Engineering Science, Osaka University, 基礎工学部, 助手 (60183191)
NAOTA Takeshi Faculty of Engineering Science, Osaka University, 基礎工学部, 助手 (20164113)
HOSOKAWA Takahiro Faculty of Engineering Science, Osakta University, 基礎工学部, 助教授 (90029520)
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| Project Period (FY) |
1985 – 1987
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| Project Status |
Completed (Fiscal Year 1987)
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| Budget Amount *help |
¥17,500,000 (Direct Cost: ¥17,500,000)
Fiscal Year 1987: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1986: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1985: ¥13,500,000 (Direct Cost: ¥13,500,000)
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| Keywords | Ruthenium Catalyst / Alcohol / Dehydrogenation / Ester / Lactone / Polyester / Lactam |
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| Research Abstract |
The activation of alcohols with transition metal catalysts gives carbontl metal hydride intermediates. Capture of the intermediates with nucleophiles provedes novel catalytic ocidative transformations of alcohols to various useful compuond. Repreentative results are summatized as follows.
1. The reaction of primary alcohols with low valent ruthenium catalysts gices esters with evolution of molecular hydrogen. Similar trestment of diols affords lactones, where primaty hydroxy group is oxidized the lactonization regioselectively. From the veiwpoint of preacical use of the rteactions, some perfume esters and polyesters have been prepared from readily abailabel industrial materials. Extention of the principle of the dechdrogenation precoes of alchols disclosed vatous novel catalytic reactions. The ruthenium-catalyzed reaction of aldehydes with alcohosl affords esters. The reaction of aldehydes with water gives esters, while the same reaction in the presence of a hydrogen accepotr affords carboxylic acids. The reaction of aminoalcohols whth rethenium catalysts in the presence of a hydrogen acceptor gices the corresponging lactanms.
2. Novel catalytic oxidation of alcohols with alkyl hydroperoxides have been developed. Ruthemuin-catalyzed oxedation of alcohols with t-BuOOH preoceeds efficiently under neutral and mild conditions. The present reaction id highly useful for the ransformation of cyanohydrins to acyl cyanides which are versatile synthetic intermcdiates. Acyl cyanides thus obtained are founs to undergo pallafium-catalyzed decarbonylation reaction, which procedes an eddicient metthod for preparation of acid-sensitive nitriles from aldehydes. Acylation of aminoalcohols and polyamines with acyl cyanides have been performed chemosslectively. A short-strp syntehsis of naturally occuring polyamines has been established by using this method.
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