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
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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