| Project/Area Number |
05804032
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
Organic chemistry
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| Research Institution | KYUSHU UNIVERSITY |
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Principal Investigator |
SONODA Takaaki Kyushu University, Institute of Advanced Material Study Associate Professor, 機能物質科学研究所, 助教授 (90108770)
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| Co-Investigator(Kenkyū-buntansha) |
KOBAYASHI Hiroshi Kyushu University, Institute of Advanced Material Study, Professor, 機能物質科学研究所, 教授 (10037731)
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| Project Period (FY) |
1993 – 1994
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| Project Status |
Completed (Fiscal Year 1994)
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| Budget Amount *help |
¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1994: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1993: ¥900,000 (Direct Cost: ¥900,000)
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| Keywords | Phenyl cations / Photo-solvolysis reactions / Substituent effects / Mechanism of conjugative stabilization / Structure and reactivity |
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| Research Abstract |
This is a fundamental research to investigate the structure-reactivity relationship of phenyl cations, which are highly reactive and important intermediates for synthesis, with respect to the mechanism of the conjugative stabilization of phenyl cations.
1)Semi-empirical and ab initio calculations on the optimized structures of substituted phenyl cations revealed that highly stabilized phenyl cations with electron-donating groups at meta position have "non-planar" structures, whose stability and nonplanality are closely related.
2)Photosolvolysis of 2-propylphenyl chloride gave rise to the products via 2-propylphenyl cation intermediate which were similarly obtained in the thermal decomposition of 2-propylbenzenediazonium ions.
3)The effects of solvents, electron-donating ability of meta-substituents, and electron-affinity of leaving grous on the ratio of two products via aryl radical and aryl cation intermediates were investigated in the photo-solvolysis of aryl triflates and chlorides, where hydrogen abstraction of aryl radicals from solvent and nucleophilic attach of solvent on aryl cations occured competitively.
4)In the photo-solvolysis of ortho-hydroxyphenyl chloride ring contraction of the intermediate oxido-phenyl cations occured competitively with the nucleophilic solvent attack on the hydroxyphenyl cations. The experimental results were investigated by computational calculations.
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