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.

这是一项基础研究，旨在研究苯基阳离子的结构反应关系，就苯基阳离子的偶联稳定机制而言，这是高度反应性和重要的中间体。取代苯基阳离子的优化结构表明，具有元位位置的电子献给电子基团的高度稳定的苯基阳离子具有“非平面”结构，其稳定性和非平面性密切相关。 2-丙基苯基阳离子阳离子中间体，在2-丙酰苯二苯二甲二氮化离子的热分解中类似地获得。3）溶剂的影响，元亚衍生物的电子脱糖能力，以及剩下的含量对通过芳基对两种产物的电子 - 亲和力对两种产物的电子 - 研究了自由基和芳基阳离子阳离子中间体，在芳基三磷酸盐和氯化物的光溶解中，其中芳烃从溶剂和溶剂上的芳基自由基在芳基阳离子上的溶剂和亲核附着的附着在芳基阳离子上进行了竞争性。4）中间氧化苯基阳离子的收缩与亲核溶剂对羟基苯基阳离子的攻击进行了竞争性。通过计算计算研究了实验结果。