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DFT study on the mechanism of simultaneous trifluoromethylation and oximation of aryl-substituted ethylene.
  • +5
  • Sen Wang,
  • Ao He,
  • Xuan Meng,
  • Xiao wei Lan,
  • Xianfu Wei,
  • Wenjie Jing,
  • Kui Lu,
  • Yujie Dai
Sen Wang
Tianjin University of Science and Technology
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Ao He
Tianjin University of Science and Technology
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Xuan Meng
Tianjin University of Science and Technology
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Xiao wei Lan
Tianjin University of Science and Technology
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Xianfu Wei
Tianjin University of Science and Technology
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Wenjie Jing
Tianjin University of Science and Technology
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Kui Lu
Tianjin University of Science and Technology
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Yujie Dai
Tianjin University of Science and Technology
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Abstract

The effects of different substituents located at the para position of the aromatic ring and β carbon atom of the styrene on the reaction were investigated. The results showed that the reaction steps with higher energy barriers changed a little with the substituents of the reactants, which indicates that the reaction has a good adaptability to reactants containing different substituents. It was found the proton transfer in the final tautomerism step of nitroso intermediate to oxime is the rate limiting step under anhydrous conditions. Although the solvent effect did not influence the the rate limiting step significantly, the water mediated proton transfer significantly decreased the energy barrier of final tautomerism step. Compared with the direct proton transfer in vacuum, the energy barrier of the final tautomerism step decreased from 57.80kcal/mol in vacuum to 12.98kcal/mol with the water mediated proton transfer in water, which declined by 77.5%. When water participates in rate-limiting steps in organic solvents, the energy barrier also decreases significantly, which indicates that a small amount of water in the organic solvent is conducive to the reaction. This study is of great significance for the application of bifunctionalized reaction in the synthesis of organic fluoride compounds with different substituents.

Peer review status:IN REVISION

21 Sep 2021Submitted to International Journal of Quantum Chemistry
23 Sep 2021Assigned to Editor
23 Sep 2021Submission Checks Completed
01 Oct 2021Reviewer(s) Assigned
01 Oct 2021Review(s) Completed, Editorial Evaluation Pending
01 Oct 2021Editorial Decision: Revise Minor