| Project/Area Number |
17350018
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Kyoto University |
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Principal Investigator |
MATANO Yoshihiro Kyoto University, Graduate School of Engineering, Associate Professor (40231592)
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| Project Period (FY) |
2005 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥16,090,000 (Direct Cost: ¥15,100,000、Indirect Cost: ¥990,000)
Fiscal Year 2007: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2006: ¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 2005: ¥8,500,000 (Direct Cost: ¥8,500,000)
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| Keywords | Hypervalent / Bismuth / Bismuthonium salt / Alcohols / Oxidation / Carbonyl comnound / Photoinitiator / Polymerization / 酸化 / 光重合開始剤 / ビニルエーテル / エポキシド / カチオン重合 / 光重合 / 光反応 / カルボイル化合物 / カルボニル化合物 / 置換基効果 / 立体効果 / 水素引き抜き |
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| Research Abstract |
We have investigated three main topics to develop new reactions (oxidations and photo-induced cationic polymerizations) by utilizing the characteristic properties of the pentavalent bismuth. Firstly, various tetraarylbismuthonium salts were prepared and used as oxidants for alcohol oxidation. Primary and secondary alcohols were efficiently converted to the corresponding carbonyl compounds by treatment with the above Bi(V) oxidants in the presence of an organic base. It has been found that the introduction of ortho-substituents and/or electron-withdrawing para-substituents onto the aryl ligands enhances the oxidizing ability of the bismuthonium salts significantly. In particular, mesityltriarylbismuthonium salts exhibit high oxidizing ability and high chemoselectivity in the competitive reactions between primary and secondary alcohols. Secondary, we developed highly efficient Bi(V)-based cationic photoinitiators for the first time. Photoirradiation of triaryl(1-pyrenyl)bismuthonium salts in acetonitrile afforded triarylbismuthanes and pyrene, accompanied by the generation of protic acids. Triaryl(1-pyrenyl)bismuthonium hexafluoroantimonates have proven to behave as efficient photoinitiators for the cationic polymerization of oxiranes and a vinyl ether, affording the corresponding polymers in good yields within a short photoirradiation time. During the search of sensitizers, which were anticipated to photoinitiate the Bi-mediated cationic polymerization, we designed new classes of porphyrins bearing phosphorus and sulfur substituents at the meso position. Finally, we successfully prepared several meso-phosphorylporphyrins and meso-sulfinylporphyrins, and elucidated their structures, optical properties, and electrochemical properties in detail.
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