| Project/Area Number |
02555175
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| Research Category |
Grant-in-Aid for Developmental Scientific Research (B)
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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 |
MURAI Shinji Osaka University, Engineering, Professor, 工学部, 教授 (00029050)
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| Co-Investigator(Kenkyū-buntansha) |
OHE Koichi Osaka University, Engineering, Research assistant, 工学部, 助手 (90213636)
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| Project Period (FY) |
1990 – 1991
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| Project Status |
Completed (Fiscal Year 1991)
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| Budget Amount *help |
¥7,300,000 (Direct Cost: ¥7,300,000)
Fiscal Year 1991: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1990: ¥6,100,000 (Direct Cost: ¥6,100,000)
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| Keywords | Vinylsilane / Olefin / Iron carbonyl / Wilkinson complex / 鉄カルボニル / 触媒 / 遷移金属 / ヒドロシラン |
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| Research Abstract |
Vinylsilanes are one of important monomers for the preparation of functinalized materials such as membranes for oxygen enrichment as well as versatile synthetic intermediates in organic synthesis. Conventional method for the preparation of vinylsilanes has been the reaction of acetylenes with hydrosilanes. However, this is not practical method for the production of industrial chemicals, except for the case of the reaction of unsubstituted acetylene with trichlorosilane.
The objective of this research project is to develop and establish the highly efficient synthetic method for vinylsilanes from olefins by using new catalytic reactions developed by our group, that is dehydrogenative silylation of olefins with a hydrosilane.
1. It was found that a suitable combination of the structures of the olefin, hydrosilane, and catalyst is essential for dehydrogenative silylation to take place. For example, M_3(CO)_<12>(M = Fe, Ru, Os)showed high catalytic activity for the reaction of styrene with triethylsilane. Among them, Fe_3(CO)_<12> showed 100% selectivity, no alkylsilane being obtained as a byproduct. The similar reaction of 1, 5-dienes with triethylsilane was effectively catalyzed by Rh(PPh_3)_3Cl. -
2. Ligand effect was examined for ruthenium-catalyzed reaction of styrene with triethoxysilane. Information about the reaction mechanism was collected.
In conclusion, it was found that a suitable combination of olefin-catalyst is essential for dehydrogenative silylation to take place. Some practical methods for the preparation of vinylsilanes are established.
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