Oxidation of secondary hydroperoxides via αC–H abstraction to form ketones and hydroxyl radicals: fluorene autoxidation as a model system
Abstract
Organic and biological molecules with relatively weak C–H bonds can react with O2 via a free-radical reaction called autoxidation. The primary products of these peroxyl-radical-driven reactions are hydroperoxides, R2CHOOH. If autoxidation continues, the secondary oxidation of hydroperoxides is known to form ketones, R2C═O, but this mechanism is not well characterized. Importantly, we find that ketone formation produces a highly reactive hydroxyl radical, HO•. We can trap HO• using benzene as a solvent to form quantifiable amounts of phenol. Fluorene was chosen as a model system to study this secondary oxidation in great detail. Kinetic modeling allowed the measurement of rate constants for the primary and secondary autoxidation reactions as 11.3 and 25 mol L−1s−1, respectively. Density functional theory modeling likewise predicts a faster oxidation for the secondary autoxidation. This type of kinetic measurement and modeling approach could be useful to study the autoxidation of plastics, petrochemicals, and lipids.
Graphical Abstract
Résumé
Les molécules organiques et biologiques avec des liaisons C–H relativement faibles peuvent réagir avec l'O2 via une réaction radicalaire appelée auto-oxydation. Les principaux produits de ces réactions induites par les radicaux peroxyles sont les hydroperoxydes, R2CHOOH. Si l'auto-oxydation se poursuit, l'oxydation secondaire des hydroperoxydes peut former des cétones, R2C=O, mais ce mécanisme n'est pas bien caractérisé. Nous proposons que la formation de cétone produit un radical hydroxyle hautement réactif, HO•. Nous pouvons piéger ce HO• en utilisant le benzène comme solvant pour former des quantités quantifiables de phénol. Le fluorène a été choisi comme système modèle pour étudier en détail cette oxydation secondaire. La modélisation cinétique a permis la mesure des constantes de vitesse pour les réactions d'auto-oxydation primaires et secondaires de 11,3 et 25 mol L−1s−1, respectivement. La modélisation DFT prédit également une oxydation plus rapide pour l'auto-oxydation secondaire. Cette approche de mesure et de modélisation cinétique pourrait être utilisée pour étudier l'auto-oxydation des plastiques, des produits pétrochimiques et des lipides. [Ceci est une traduction fournie par l’auteur du résumé en anglais]
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Published In
Canadian Journal of Chemistry
Volume 102 • Number 1 • January 2024
Pages: 1 - 6
History
Received: 29 March 2022
Accepted: 28 June 2022
Accepted manuscript online: 26 July 2023
Version of record online: 20 September 2023
Copyright
© 2023 The Author(s). Permission for reuse (free in most cases) can be obtained from copyright.com.
Data Availability Statement
Data available within the article and supplementary files.
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Authors
Author Contributions
Conceptualization: MF
Data curation: MS, SH, ME, ALDA, AM
Formal analysis: MS, SH, JM, ME, ALDA, AM, MF
Funding acquisition: SH, MF
Investigation: SH
Methodology: SH, ME, AM, MF
Project administration: MF
Resources: MF
Software: JM
Supervision: SH, MF
Validation: MS, SH, JM, ME, ALDA, MF
Visualization: SH, JM, MF
Writing – original draft: MS, SH, MF
Writing – review & editing: MS, SH, ME, MF
Competing Interests
The authors declare there are no competing interests.
Funding Information
NSERC: RGPIN-2016-06773
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Mélanie Sollin, Seyedehsan Hosseininasab, Jason Malenfant, Mohamed El-Akhrass, Amaia Lopez de Arbina, Alicia Montulet, and Mathieu Frenette. 2024. Oxidation of secondary hydroperoxides via αC–H abstraction to form ketones and hydroxyl radicals: fluorene autoxidation as a model system. Canadian Journal of Chemistry.
102(1): 1-6. https://doi.org/10.1139/cjc-2022-0089
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