RATE AND MECHANISM OF THE KETENE HYDROLYSIS IN AQUEOUS-SOLUTION
RATE AND MECHANISM OF THE KETENE HYDROLYSIS IN AQUEOUS-SOLUTION
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DOI：
10.1021/j100461a027
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发表时间：
1980-01-01
影响因子：
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通讯作者：
SCHULTEFROHLINDE, D
中科院分区：
文献类型：
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作者：
BOTHE, E;DESSOUKI, AM;SCHULTEFROHLINDE, D
乙烯酮在水溶液中的水合速率常数在 25 C 时为 44 s” 1，与 4.4-9.85 范围内的 pH 值无关。该反应显示出溶剂动力学同位素效应 kn20/kD} 0= 1-9 - 测得的活化焓和熵分别为 10. 3 kcal mol” 1 和 -16 eu。在二恶烷/水和乙腈/水混合物中，发现速率常数与水含量大致成正比。结论是水解的第一步是水与未取代的烯酮的亲核反应。
The hydration of ketene in aqueous solution has a rate constant of 44 s” 1 at 25 C which is independent of pH in the range 4.4-9.85. The reaction shows a solvent kinetic isotope effect of kn20/kD} 0= 1-9-Activation enthalpy and entropy were measured to be10. 3 kcal mol” 1 and-16 eu, respectively. In dioxane/water and acetonitrile/water mixtures the rateconstants were found to be approximately proportional to the water content. It is concluded that the first step in the hydrolysis is the nucleophilic reaction of water with the unsubstituted ketene.