HEAVY-ATOM ISOTOPE EFFECTS ON THE ALKALINE-HYDROLYSIS OF METHYL FORMATE - THE ROLE OF HYDROXIDE ION IN ESTER HYDROLYSIS

被引：63

作者：

MARLIER, JF

机构：

[1] Chemistry Department, California Polytechnic State University, San Luis Obispo

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1993年 / 115卷 / 14期

关键词：

D O I：

10.1021/ja00067a008

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Carbonyl carbon, carbonyl oxygen, and nucleophile oxygen isotope effects were measured for the alkaline hydrolysis of methyl formate in water at 25-degrees-C. The carbonyl carbon isotope effect is k12/k13 = 1.0338, the isotope effect for the carbonyl oxygen is k16/k18 = 0.999, and that for the oxygen nucleophile is k16/k18 = 1.023. These isotope effects are consistent with a stepwise mechanism in which the formation of the tetrahedral intermediate is largely rate-determining. The isotope effect on the oxygen nucleophile suggests that the attacking nucleophile in aqueous alkali is water with general base assistance from hydroxide.

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页码：5953 / 5956

页数：4

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