Reactions of 1-substituted 2,2,3,4,4-pentamethylphosphetans with hexafluoroacetone and the 19F nuclear magnetic resonance spectra of the resulting 1,3,2-dioxaphospholans
作者:Robert K. Oram、Stuart Trippett
DOI:10.1039/p19730001300
日期:——
with hexafluoroacetone. The 19F n.m.r. spectra of these adducts over a range of temperatures have given values of the free energies of activation for the pseudorotation processes which place the four-membered ring diequatorial and the 1-substituents apical. The variation in these activation energies with the nature of the 1-substituent is accounted for in terms of the relative apicophilicity of groups
已经制备了一系列的1-取代的2,2,3,4,4-五甲基膦酸酯,并且在用六氟丙酮处理后将其转化为相应的1,3,2-二氧杂膦酸酯。这些加合物在一定温度范围内的19 F nmr光谱给出了伪旋转过程的活化自由能值,该伪旋转过程使四元环二甲基吡咯和1位取代基位于顶峰。在与1-取代基的性质这些活化能的变化在组既是电负性和的函数的相对apicophilicity方面占p π - d π背键。探索了该假设的一些后果。描述了1,3,2-二氧杂磷杂环戊烷和相关的1,2-氧杂磷杂环戊烷的一些不寻常的反应和异构化。