| Project/Area Number |
61303003
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| Research Category |
Grant-in-Aid for Co-operative Research (A)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | Kyushu University |
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Principal Investigator |
TSUNO Yuho Kyushu Univ., Prof., 理学部, 教授 (10029845)
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| Co-Investigator(Kenkyū-buntansha) |
FUENO Takayuki Osaka Univ., Prof., 基礎工学部, 教授 (60029387)
ANDO Takashi Shiga Univ. of Medical Science, Prof., 教授 (70029867)
HAYAMI Jun-ichi Kyoto Univ., Prof., 教養部, 教授 (30025283)
MISHIMA Masaaki Kyushu Univ., Research Associate, 理学部, 助手 (20037279)
TANIGUCHI Hiroshi Kyushu Univ., Prof., 工学部, 教授 (10037715)
西本 吉助 大阪市立大学, 理学部, 教授 (20046949)
竹下 斉 九州大学, 生産研, 教授 (70004281)
藤尾 瑞枝 九州大学, 理学部, 助手 (10029887)
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| Project Period (FY) |
1986 – 1987
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| Project Status |
Completed (Fiscal Year 1987)
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| Budget Amount *help |
¥15,000,000 (Direct Cost: ¥15,000,000)
Fiscal Year 1987: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 1986: ¥11,000,000 (Direct Cost: ¥11,000,000)
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| Keywords | Reactive intermediate / Structure-reactivity relationships / Yukawa-Tsuno equation / Winstein-Grunwald equation / Gas phase reactivity / レフラー-ハモンド原理 / 気相炭素陽イオン / イオンサイクロトロン共鳴(法) / 置換基効果 / 基質-試薬会合錯体 / プロトン移動反応 / シグマトロピー / 芳香族求核置換反応 |
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| Research Abstract |
Intensive studies have been made for the followin four important subjects. 1). Reaction intermediates and their characteristic behavior: New chemistry was explored particularly on the unstable vinyl cations and highly electron-deficient -CF_3 or -COR substituted carbocations. 2) Structure-reactivity relationships: Yukawa-Tsuno equation was applied successfully to a wide series of solvolysis reactions, constructing a continuous spectrum of resonance demands up to r=1.5 for -CF_3-substituted benzylic system. 3) Intermolecular interactions and solvent effects: Apparent failure of Winstein-Grunwald equation was pointed out even for nucleophilically solvent-unassisted solvolyses and the importance of the anion-solvation effect and of the different cation solvation effect in the highly delocalized carbocation systems. 4) Transition states and reaction coordinate: Heavy atom isotope effects in the Menschutkin reactions were interpreted reasonably in terms of variation of transition state structures in the reaction coordinate. Gas phase stabilities of benzylic cations led to the closeness of the position of transition state to the inermediate in the solvolysis.
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