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溶剂对2-乙基己醛有氧自氧化中产物分布的影响：极性的关键作用

Solvent Effect on Product Distribution in the Aerobic Autoxidation of 2-Ethylhexanal: Critical Role of Polarity.

作者信息

Wang Zheng, Qin Yitong, Huang Huijiang, Li Guobing, Xu Yan, Jin Peng, Peng Bo, Zhao Yujun

机构信息

Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, China.

School of Materials Science and Engineering, Hebei University of Technology, Tianjin, China.

出版信息

Front Chem. 2022 Mar 25;10:855843. doi: 10.3389/fchem.2022.855843. eCollection 2022.

DOI:10.3389/fchem.2022.855843
PMID:35402373
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8989829/
Abstract

In the aerobic oxidation of aldehydes to acids, how the solvent affect the reaction remains unclear. Herein, the solvent effect in the oxidation of 2-ethylhexanal (2-ETH) to 2-ethylhexanoic acid (2-ETA) was systematically investigated. The vastly different product distributions were observed which could be ascribed to the dominant intermolecular forces. Though strong intermolecular forces in protic solvents limit the oxidation, the optimal 2-ETA yield (96%) was obtained in propanol via gradually evaporating the solvent to remove the interactions. Theoretical calculations further revealed that the hydrogen bonds between reactant and protic solvent increase the C-H bond energy (-CHO in 2-ETH). Meanwhile, the hydrogen bonds may improve 2-ETA selectivity by promoting H transfer in the oxidation rearrangement step. Our work discloses the critical role of polarity in determining the reactivity and selectivity of 2-ETH oxidation, and could guide the rational design of more desirable reaction processes with solvent effect.

摘要

在醛类有氧氧化为酸的过程中，溶剂如何影响反应仍不清楚。在此，系统地研究了2-乙基己醛（2-ETH）氧化为2-乙基己酸（2-ETA）过程中的溶剂效应。观察到了截然不同的产物分布，这可归因于主要的分子间作用力。尽管质子溶剂中强大的分子间作用力限制了氧化反应，但通过逐渐蒸发溶剂以消除相互作用，在丙醇中获得了最佳的2-ETA产率（96%）。理论计算进一步表明，反应物与质子溶剂之间的氢键增加了C-H键能（2-ETH中的-CHO）。同时，氢键可通过促进氧化重排步骤中的氢转移来提高2-ETA的选择性。我们的工作揭示了极性在决定2-ETH氧化反应活性和选择性方面的关键作用，并可为合理设计更理想的具有溶剂效应的反应过程提供指导。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e70/8989829/505235d2d39d/fchem-10-855843-g007.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e70/8989829/32f392d93b00/fchem-10-855843-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e70/8989829/505235d2d39d/fchem-10-855843-g007.jpg
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