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马来酰亚胺碱性水解的动力学及机理

Kinetics and mechanism of the alkaline hydrolysis of maleimide.

作者信息

Khan M N

出版信息

J Pharm Sci. 1984 Dec;73(12):1767-71. doi: 10.1002/jps.2600731227.

DOI:10.1002/jps.2600731227
PMID:6527252
Abstract

The kinetics of hydrolysis of maleimide was carried out within the [OH-] range of 2.46 X 10(-6) to 2.0 M at 30 degrees C. The observed pseudo-first-order rate constants, kobs, follow the empirical equation: kobs = (A1[OH-] + A2[OH-]2)/(1 + A3[OH-]). Both ionized and un-ionized forms of maleimide have been suggested to be involved in hydrolysis. The nucleophilic attacks by hydroxide ion at the carbonyl carbon of both ionized and un-ionized maleimide and by water at the carbonyl carbon of ionized maleimide to form tetrahedral intermediates are considered to be the rate-determining steps. The observed results obtained at different 1,4-dioxane-water compositions have revealed an increase in kobs with a decrease in 1,4-dioxane content which could be attributed to the higher polarity of the transition state compared with the reactant state.

摘要

在30℃下,在[OH-]范围为2.46×10(-6)至2.0 M内进行了马来酰亚胺的水解动力学研究。观察到的伪一级速率常数kobs遵循经验方程:kobs = (A1[OH-] + A2[OH-]2)/(1 + A3[OH-])。有人认为马来酰亚胺的离子化形式和非离子化形式都参与了水解反应。氢氧根离子对离子化和非离子化马来酰亚胺的羰基碳的亲核攻击以及水对离子化马来酰亚胺的羰基碳的亲核攻击以形成四面体中间体被认为是速率决定步骤。在不同的1,4 - 二氧六环 - 水组成下获得的观察结果表明,随着1,4 - 二氧六环含量的降低,kobs增加,这可能归因于过渡态与反应物态相比具有更高的极性。

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