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

• 批准号: 05804032
• 负责人: SONODA Takaaki
• 金额: $ 1.02万
• 依托单位: KYUSHU UNIVERSITY
• 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
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05804032/
• 关键词: Phenyl cations; Photo-solvolysis reactions; Substituent effects; Mechanism of conjugative stabilization; Structure and reactivity

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。