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被检查为强级lewis Acid cat-cat-cat-Alalder，非极性有机溶剂中偶氮-DYE化合物的反应和半色素化研究了有机阴离子的协调和离开能力。证明了荧光醇中芳基三烯酸盐的照片通过芳基阳离子中间体进行，而光和热溶解的含量则可以通过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溶液分别与与para-和meta-叠生的相应苯基阳离子的计算相对稳定能相关。具有元位置上具有电子粉化取代基的苯基阳离子通过与元取代物的新型直接缀合高度稳定。在稳定苯基阳离子阳离子中间体中，这种新型效果的元素证据证明了这种新的效果。证明了在3,5位处的哌啶基组：在TFE，HEIP和HFIP水溶液中的溶剂溶解产物的独家形成和溶剂极性效应表明，溶液的S_N1机制通过ARY1阳离子进行了由ARY1阳离子进行的S_N1机制。元取代。