| Project/Area Number |
10650773
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
触媒・化学プロセス
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| Research Institution | TOKYO METROPOLITAN UNIVERSITY |
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Principal Investigator |
KAWAI Tadashi Tokyo Metropolitan University, Graduate School of Engineering, professor, 工学研究科, 教授 (00087298)
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| Co-Investigator(Kenkyū-buntansha) |
IYODA Tomokazu Tokyo Metropolitan University, Graduate School of Engineering, professor, 工学研究科, 教授 (90168534)
松下 末知雄 (松下 未知雄) 東京大学, 総合文化研究科, 助手 (80295477)
鈴木 剛彦 東京都立大学, 大学院・工学研究科, 助教授 (50087300)
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| Project Period (FY) |
1998 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2001: ¥100,000 (Direct Cost: ¥100,000)
Fiscal Year 2000: ¥200,000 (Direct Cost: ¥200,000)
Fiscal Year 1999: ¥300,000 (Direct Cost: ¥300,000)
Fiscal Year 1998: ¥3,100,000 (Direct Cost: ¥3,100,000)
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| Keywords | metathesis / cross-metathesis / non-linear optical material / σ-π conjugated materials / π-conjugated materials / vinylarenes / vinylferrocene / vinylsilanes / vinylsilane / オレフィンメタセシス / クロスメタセシス / ビニル芳香族化合物 / ヘテロダイマー / Re_2O_7-Al_2O_3(レニア-アルミナ)触媒 / σ-π共役化合物 / シリレンビニレン / ビニルシラン / 6-πハイブリッド共役 / オリゴシリレンビニレン化合物 / レニア-アルミナ触媒 |
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| Research Abstract |
σ-π hybrid conjugated molecules have been expected as new organic materials with optical non-linearities with high transparency. Poly (silylene-vinylene) s are one of these candidates.
Syntheses of poly (silylene-vinylene) s by olefin metathesis were attempted for the first time. New compounds, oligo (silylene-vinylene) s (dimer〜oligomer) of linear type were synthesized by self-metathesis of tetravinylsilane and dimethyldlvinylsilane, and 1,4-bis(dimethylvinylsilyl) benzene using Re_2O_7-Al_2O_3 catalyst under mild reaction conditions. It was found they are σ-π hybrid conjugated molecules with high transparency, but higher oligomer and polymer could not be obtained. The spectroscopic studies revealed that their optical nonlinearities are weak.
Ferrocene is known as one of interesting compounds with optical non-linearities.
Novel selective synthesis of π -conjugated molecules with various interesting functional group by cross-metathesis were attempted for the two systems over Grubbs and Schrock catalyst. (1) Cross-metathesis of various kinds of vinylarene and vinylhetroaromatics with 1 -octene, and (2) Cross-metathesis reactions between vinylferrocene and a series of vinylarene. Self -metathesis of vinylferrocene was not occurred, but Interestingly cross-metathesis proceeded to yield heterodimer (cross-metathesis product) with high selectivity (73-100 %) in the presence of the Schrock catalyst. The mechanism of selective heterodimer formation was proposed.
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