KINETIC APPLICATIONS OF ELECTRON-PARAMAGNETIC RESONANCE SPECTROSCOPY .41. DIETHOXYPHOSPHONYL RADICALS
KINETIC APPLICATIONS OF ELECTRON-PARAMAGNETIC RESONANCE SPECTROSCOPY .41. DIETHOXYPHOSPHONYL RADICALS
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DOI：
10.1021/ja00349a037
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发表时间：
1983-01-01
影响因子：
15
通讯作者：
INGOLD, KU
中科院分区：
文献类型：
--
作者：
ANPO, M;SUTCLIFFE, R;INGOLD, KU
已通过 EPR 光谱法使用竞争方法测定了二乙氧基膦酰基自由基从某些有机卤化物中夺取卤素原子的速率常数。环境温度下，在二叔丁基过氧化物/亚磷酸二乙酯（4:1，v/v）作为溶剂中的一些典型速率常数（M-1 s-1 单位）如下：叔丁基氯，3.5 X 102；正丁基溴，1.0 X 104； íe/7-丁基溴，3.0 X 105；苄基溴，1.2 X 106。二乙氧基膦酰基在卤素原子夺取反应中的反应性比三乙基甲硅烷基或三正丁基锡基低。
Rate constants for the abstraction of halogen atoms by diethoxyphosphonyl radicals from some organic halides have been determined by EPR spectroscopy using competitive methods. Some typical rate constants (M-1 s-1 units) at ambient temperatures in di-Zerf-butyl peroxide/diethyl phosphite (4: 1, v/v) as solvent follow: zerz-butyl chloride, 3.5 X 102;«-butyl bromide, 1.0 X 104; íe/7-butyl bromide, 3.0 X 105; benzyl bromide, 1.2 X 106. Diethoxyphosphonyl radicals are less reactive in halogen atom abstractions than triethylsilyl or tri-«-butyltin radicals.