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The Study on the Mechanism of Conjugative Stabilization of Phenyl Cations

Research Project

Project/Area Number 05804032
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field Organic chemistry
Research InstitutionKYUSHU UNIVERSITY

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)

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)
Project Period (FY) 1993 – 1994
Project Status Completed (Fiscal Year 1994)
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)
KeywordsPhenyl cations / Photo-solvolysis reactions / Substituent effects / Mechanism of conjugative stabilization / Structure and reactivity
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.

Report

(3 results)
  • 1994 Annual Research Report   Final Research Report Summary
  • 1993 Annual Research Report

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Published: 1993-04-01   Modified: 2016-04-21  

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