烷氧基磷烷的合成及假旋转  

Preparation and Pseudorotation of Alkoxyphosphoranes

作　　者：刘纶祖[1] 李国炜[1] 张翱 曾兴忠[1] 付岚冰 

机构地区：[1]南开大学元素有机化学研究所

出　　处：《高等学校化学学报》1995年第3期395-398,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金

摘　　要：氢膦烷２与苯基次磺酸酯３反应，制得几种带有取代基的螺双环烷氧基磷烷４。变温^（３１）ＰＮＭＲ谱监测，观察到化合物４的假旋转，并计算出了假旋转的活化自由能。Reaction of hydridophosphoranes 2 with benzensulfenic esters 3 provides a series of substituted spirobicyclic alkoxyphosphoranes 4.The pseudorotation process of compound 4 was observed by the variable temperature ￣(31)P NMR spectra. The free energy of activation for this process was calculated. Coalescence for 4_a,4_b occurred at 130C,4_c and 4_d at 140℃.The △G￣≠ for 4_a,4_b,4_c,4_d are 81.8,81.8,85.8,84. 99kJ/mol,respectively.The results have indicated that pseudorotation process is subject to steric infltiences.

关 键 词：烷氧基磷烷 假旋转 苯基次磺酸酯 氢膦烷 

分 类 号：O627.51[理学—有机化学]