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Reversibility of the catalytic ketonization of carboxylic acids and of beta-keto acids decarboxylation
Catalysis Communications ( IF 3.4 ) Pub Date : 2018-04-06
Alexey V. Ignatchenko, Andrew J. Cohen

Decarboxylation of beta-keto acids in enzymatic and heterogeneous catalysis has been considered in the literature as an irreversible reaction due to a large positive entropy change. We report here experimental evidence for its reversibility in heterogeneous catalysis by solid metal oxide(s) surfaces. Ketones and carboxylic acids having 13C-labeled carbonyl group undergo 13C/12C exchange when heated in an autoclave in the presence of 12CO2 and ZrO2 catalyst. In the case of ketones, the carbonyl group exchange with CO2 serves as evidence for the reversibility of all steps of the catalytic mechanism of carboxylic acids ketonic decarboxylation, i.e. enolization, condensation, dehydration and decarboxylation.



中文翻译:

羧酸催化酮化和β-酮酸脱羧的可逆性

在酶催化和非均相催化中,β-酮酸的脱羧由于大的正熵变化而被认为是不可逆的反应。我们在这里报告其固体金属氧化物表面多相催化可逆性的实验证据。当在具有12 CO 2和ZrO 2催化剂的高压釜中加热时,具有13 C-标记的羰基的酮和羧酸进行13 C / 12 C交换。在酮的情况下,羰基与CO 2交换 作为羧酸酮酮脱羧催化机理所有步骤的可逆性的证据,即烯醇化,缩合,脱水和脱羧。

更新日期:2018-04-06
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