The. beta.-hydrogen secondary isotope effect in acyl transfer reactions. Origins, temperature dependence, and utility as a probe of transition-state structure

…, JL Hogg, T Raben, K Halbert, J Rodgers…

Index: Kovach, Ildiko M.; Hogg, John L.; Raben, Tony; Halbert, Kevin; Rodgers, James; Schowen, Richard L. Journal of the American Chemical Society, 1980 , vol. 102, # 6 p. 1991 - 1999

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Citation Number: 22

Abstract

Abstract: The anomalous temperature dependence of the 0-deuterium (0-D) secondary isotope effect reported by Halevi and Margolin for the hydroxide-promoted hydrolysis of ethyl acetate has been observed also with methyl acetate [CHjC02CH3 vs. CD3COzCH3: k3H/k3D= 1.01 f 0.02 (0" C), 0.90 & 0.02 (25" C), 1.03 f 0.10 (50" C)]. In contrast, the 0-D effects for the rates of acidic hydrolysis of methyl acetate (0.93* 0.02, O-42" C), basic ...