碘盐作为亲电活化剂对甲醇中Knoevenagel缩合反应的抑制作用

IF 1.9 4区化学 Q2 CHEMISTRY, ORGANIC

Journal of Physical Organic Chemistry Pub Date : 2025-02-14 DOI:10.1002/poc.70006

Alexandra A. Sysoeva

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引用次数: 0

摘要

卤素键给体在羰基化合物反应中被认为是亲电催化剂。本研究描述了催化剂对Knoevenagel缩合反应的意外抑制作用。为了阐明其复杂的抑制机理，利用1H NMR谱测定了反应的总顺序和速率常数，并对不同的亲核试剂进行了进一步的实验。研究结果表明，主要反应的抑制是由于涉及乙醛甲醇分解的副反应的实质性加速，这阻碍了最终烯烃产物的形成。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Unexpected Inhibition of the Knoevenagel Condensation in Methanol by Iodonium Salt Served as Electrophilic Activator

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Unexpected Inhibition of the Knoevenagel Condensation in Methanol by Iodonium Salt Served as Electrophilic Activator

Halogen bond donors are recognized as electrophilic catalysts in reactions involving carbonyl compounds. This study describes an unexpected inhibition of the Knoevenagel condensation by the catalyst. To elucidate the intricacies of the inhibition mechanism, the overall reaction order and rate constants were determined using ¹H NMR spectroscopy, and further experiments with different nucleophiles were conducted. The findings revealed that the inhibition of the primary reaction is attributed to a substantial acceleration of the side reaction involving aldehyde methanolysis, which hinders the formation of the final alkene product.

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来源期刊

Journal of Physical Organic Chemistry 化学-物理化学

CiteScore

3.60

自引率

11.10%

发文量

161

审稿时长

2.3 months

期刊介绍： The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.