ELECTRON-SPIN RESONANCE OF OXIRANYL RADICALS IN SOLUTION - CONFIGURATIONAL STABILITIES AND REARRANGEMENT REACTIONS
ELECTRON-SPIN RESONANCE OF OXIRANYL RADICALS IN SOLUTION - CONFIGURATIONAL STABILITIES AND REARRANGEMENT REACTIONS
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DOI：
10.1002/hlca.19760590318
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发表时间：
1976-01-01
影响因子：
1.8
通讯作者：
FISCHER, H
中科院分区：
文献类型：
--
作者：
ITZEL, H;FISCHER, H
通过ESR光谱在溶液中观察到由环氧乙烷的氢提取衍生的几个烷基取代的环氧乙烷基。ESR谱表明环氧乙烷基自由基在自由基碳原子处具有金字塔构型并进行反转。烷基取代的环氧乙烷基通过开环重排为α-酮基烷基。随着烷基取代度的增加，转化率降低，重排率增加。这些过程的活化参数给出了几种情况下，并与自由基结构。由反转引起的谱线增宽效应允许确定γ-CH 3-耦合常数的相对符号。
Several alkyl substituted oxiranyl radicals derived by hydrogen abstraction from oxiranes are observed in solution by ESR.‐spectroscopy. The ESR.‐spectra demonstrate that oxiranyl radicals have pyramidal configurations at the radical carbon atom and undergo inversion. Alkyl substituted oxiranyls rearrange by ring opening to α‐keto alkyl radicals. The rates of inversion decrease and the rates of rearrangement increase with alkyl substitution. The activation parameters of these processes are given for several cases and are related to radical structure. Line broadening effects caused by inversion allow the determination of relative signs of γ‐CH3‐coupling constants.