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

基本信息

批准号：
07640726
负责人：
SONODA Takaaki
金额：
$ 1.47万
依托单位：
KYUSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07640726/
关键词：
Trifyl-substituted Heteroatom Functional Group Phenyl Cations Structure and reactivity Molecular Orbital Method Calculation Analysis of Substituent effects Solvolysis Reactions Weakly-Coordinating Polyfluorinated Organic Anions 反応性炭素陽イオン中間体

项目摘要

Various alkali metal, alkali-earth metal, and transition metal ions ion-paired with weakly-coordinating polyfluorinated organic anions such as OSO_2CF_3, N (SO_2CF_3) _2, and C (SO_2CF_3) _3 were examined as strong Lewis acids in catalytic Diels-Alder reactions and halochromism of azo-dye compounds in nonpolar organic solvents to investigate the coordinating and leaving abilities of the organic anions.The photosolvolysis of aryl triflates in fluorinated alcohols was proved to proceed via aryl cation intermediates, while the photo-and thermal-solvolysis of aryl ester ArOS (O) (CF_3)=C (SO_2CF_3) _2 gave the products derived from the ArO-S (O) bond cleavage.The experimental relative rate-constant for the dediazoniation reactions of para- and meta-substituted benzenediazonium ions in solution was good correlated with the computational relative stabilizing energy of the corresponding phenyl cations with para- and meta-substituents, respectively. The phenyl cations with electron-donating substituents on meta-position are highly stabilized by novel direct-conjugation with the meta-substituents.Experimental evidences of this novel effect of meta-substituent for stabilizing phenyl cation intermediates in the thermal-solvolysis of the aryl triflate with piperidinyl groups at 3,5-positions were demonstrated : exclusive formation of solvent-substituted products and solvent polar effect in the solvolysis in TFE,HEIP,and aqueous HFIP indicated the S_N1 mechanism of the solvolysis to proceed via ary1 cations highly stabilized by the meta-substituents.

各种碱金属，碱金属和过渡金属离子离子与弱配位的多氟有机阴离子（例如OSO_2CF_3，N（SO_2CF_3）_2）和C（SO_2CF_3）_3 _3 _3 _3 _3 _3 _3，是cat-lahis-peaction conty and cat-peactions和c conty _3非极性有机溶剂中的化合物研究有机阴离子的配位和离开能力。证明了偶然醇中的芳基三烯酸盐的光溶解是通过芳基阳离子中间体进行的，而芳基酯（cf_3）（cf_3）= cf_3）的照片和热溶剂分析（cf_3）= cf_3 c（so_3cfff）粘结裂解。溶液中para-和元取代的苯二氮锌离子的实验相对速率 - 固定反应分别与与para-和meta-替代物的相应苯基阳离子的计算相对稳定能相关。元位上具有含电子取代基的苯基阳离子通过新型的直接缀合用元叠加量高度稳定。元素在3.-ryal-triflate of piperiperions在3.-prosimed contriperive contriperive contriperive contriperive contrusizy of piperiperions中的元素稳定中元基因中间元素中的新作用的证据是在3.---稳定中的3.-列表： TFE，HEIP和HFIP水溶液中的溶剂取代的产物和溶剂极性效应表明，溶剂溶解的S_N1机制是通过由元含量高度稳定的Ary1阳离子进行的。