天然丰度氘核磁共振测定一级和二级动力学氘同位素效应(Ⅲ)——对Grignard试剂水解反应的应用

Measurement of Primary and Secondary Kinetic Deuterium Isotope Effects by Natural Abundance 2H NMR(Ⅲ)——Application to the Hydrolysis of Some Grignard Reagents

本文报道了用天然丰度^2HNMR测定一级动力学氘同位素效应的方法。这种方法与现有方法不同，它要求在反应时授氢反应物大大过量于受氢底物，在计算时要考虑由^2HNMR测定的反应物和产物的特定部位同位素比率（D／H）i或化合物的平均同位素比率（D／H）。我们用这种方法研究了一些Grignard试剂水解的同位素效应。

We established a method of using natural-abundance 2HNMR for the study of kinetic deuterium isotope effects (KDIE) which is based on the determination of site-specific isotope ratios of hydrogen in the molecules involved in the reaction. It was applied to the KDIE study of the hydrolysis of two Grignard reagents, benzylmagnesium chloride and phenylmagnesium bromide for which kH/kD= 1.52( ±0.03) and 1.50(±0.04), respectively.