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

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 c...

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Published inFrontiers in chemistry Vol. 10; p. 855843
Main Authors Wang, Zheng, Qin, Yitong, Huang, Huijiang, Li, Guobing, Xu, Yan, Jin, Peng, Peng, Bo, Zhao, Yujun
Format Journal Article
LanguageEnglish
Published Switzerland Frontiers Media S.A 25.03.2022
Subjects
2-ethylhexanal
Chemistry
hydrogen bond
intermolecular forces
oxidation
solvent effect
oxidation
solvent effect
2-ethylhexanal
intermolecular forces
hydrogen bond
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Summary: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.
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This article was submitted to Physical Chemistry and Chemical Physics, a section of the journal Frontiers in Chemistry
Reviewed by: Ian Richard Baxendale, Durham University, United Kingdom
Edited by: Valentina Migliorati, Sapienza University of Rome, Italy
These authors have contributed equally to this work
Rhoda Leron, Mapúa University, Philippines
ISSN:2296-2646
2296-2646
DOI:10.3389/fchem.2022.855843