The Study on the Mechanism of Conjugative Stabilization of Phenyl Cations

苯基阳离子共轭稳定机理的研究

基本信息

  • 批准号:
    05804032
  • 负责人:
  • 金额:
    $ 1.02万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for General Scientific Research (C)
  • 财政年份:
    1993
  • 资助国家:
    日本
  • 起止时间:
    1993 至 1994
  • 项目状态:
    已结题

项目摘要

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.
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通过芳基自由基和芳基阳离子中间体的两种产物的比率在芳基三叶酸盐和氯化物的光溶解中进行了研究,其中在芳香阳离子上,溶剂和亲核的溶剂附着的芳基自由基在竞争性上进行了芳基阳离子的溶剂和亲核附着。氧化 - 苯基阳离子与羟基苯基阳离子的亲核溶剂发作有竞争性。通过计算计算研究了实验结果。

项目成果

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科研奖励数量(0)
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数据更新时间:2024-06-01

SONODA Takaaki的其他基金

STUDY ON THE ACIDITY OF POLYFLUORINATED CARBON COMPOUNDS
多氟碳化合物酸性的研究
  • 批准号:
    19550045
    19550045
  • 财政年份:
    2007
  • 资助金额:
    $ 1.02万
    $ 1.02万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
    Grant-in-Aid for Scientific Research (C)
DEVELOPMENT OF NEW CATALYSIS REACTIONS WITH METAL SALTS OF FLUORINATED WEAKLY COORDINATED ANIONS
含氟弱配位阴离子金属盐新催化反应的开发
  • 批准号:
    12640572
    12640572
  • 财政年份:
    2000
  • 资助金额:
    $ 1.02万
    $ 1.02万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
    Grant-in-Aid for Scientific Research (C)
Reorganization of the citizenship education in Russia under the period of shifting regime
政权更迭时期俄罗斯公民教育的重组
  • 批准号:
    11610274
    11610274
  • 财政年份:
    1999
  • 资助金额:
    $ 1.02万
    $ 1.02万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
    Grant-in-Aid for Scientific Research (C)
The Study of Generating Stabilized Phenyl Cations by Using New Super-Leaving Groups
利用新型超离去基团生成稳定苯基阳离子的研究
  • 批准号:
    07640726
    07640726
  • 财政年份:
    1995
  • 资助金额:
    $ 1.02万
    $ 1.02万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
    Grant-in-Aid for Scientific Research (C)
The Study on the Development of New Types of Lithium Battery Electrolyte Solution with Highly Lipophilic Fluorinated Organic Lithium Salts
高亲油性含氟有机锂盐新型锂电池电解液的开发研究
  • 批准号:
    05555241
    05555241
  • 财政年份:
    1993
  • 资助金额:
    $ 1.02万
    $ 1.02万
  • 项目类别:
    Grant-in-Aid for Developmental Scientific Research (B)
    Grant-in-Aid for Developmental Scientific Research (B)
A New Type of Nonbenzenoid Aromatic Carbocation : 1, 6-Methano[10]AnnulenylCation.
一种新型非苯环芳香族碳正离子:1, 6-甲醇[10]环烯基阳离子。
  • 批准号:
    02804041
    02804041
  • 财政年份:
    1990
  • 资助金额:
    $ 1.02万
    $ 1.02万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (C)
    Grant-in-Aid for General Scientific Research (C)
NUCLEOPHILIC SUBSTITUTION REACTION OF ARYL TRIFLATES VIA ARYL CATIONS
芳基三氟甲磺酸酯通过芳基阳离子的亲核取代反应
  • 批准号:
    60550614
    60550614
  • 财政年份:
    1985
  • 资助金额:
    $ 1.02万
    $ 1.02万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (C)
    Grant-in-Aid for General Scientific Research (C)