| Project/Area Number |
12440204
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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 |
物質変換
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| Research Institution | The University of Tokyo |
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Principal Investigator |
GOTO Kei The University of Tokyo, Graduate School of Science, Lecturer, 大学院・理学系研究科, 講師 (70262144)
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| Project Period (FY) |
2000 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥10,800,000 (Direct Cost: ¥10,800,000)
Fiscal Year 2001: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2000: ¥7,800,000 (Direct Cost: ¥7,800,000)
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| Keywords | kinetic stabilization / quinoid compounds / calixarene / benzoquinone / quinoneimine / thioquinone / X-ray crystallographic analysis / 立体保護 / 電子移動 |
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| Research Abstract |
Novel bowl-type molecular cavities have been applied to synthesis of a variety of quinoid compounds including highly reactive ones. A bridged calix[6]arene, where a 1,4-benzoquinone moiety is covalently anchored in the cavity of the calix[6]arene macrocycle with a rigid cone conformation, was synthesized and its structure was determined by X-ray analysis. The cyclic voltammogram showed 'that :its reduction potential is negatively shifted in comparison with the reference compounds without the calixarene macrocode. A stable N- unsubstituted quinoneimine was successfully synthesized by thermolysis of the corresponding p-azidophenol under basic conditions. Its crystal structure was established by X-ray analysis, presenting the first example of the crystallographic analysis of an N-unsubstituted quinoneimine. It was revealed that the imine moiety is effectively protected by the calix[6]arene macrocycle. The cyclic voltammogram indicated that the quinoneimine is subject to two-electron reduction in one step in contrast to the corresponding quinone, which is reduced by two steps. Stabilization of other reactive quinoid species such as thioquinones was also investigated.
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