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A density functional theory study on the mechanism of simultaneous trifluoromethylation and oximation of aryl-substituted ethylenes.
- Source :
-
Journal of Chemical Research . May/Jun2022, Vol. 46 Issue 3, p1-17. 17p. - Publication Year :
- 2022
-
Abstract
- The effects of different substituents, located at the para position of the aromatic ring and at the β-carbon atom of styrenes, on difunctionalizations involving trifluoromethylation and oxime formation are investigated, showing that the difunctionalization reaction has a good adaptability to such reactants containing a range of substituents. This is important in the actual production process. It was found that proton transfer in the final tautomerism step involving transformation of a nitroso intermediate into an oxime is the rate-limiting step. The solvent effect did not influence the rate-limiting step significantly. Compared with direct proton transfer in a vacuum, the energy barrier of the final tautomerism step decreased from 57.80 kcal mol−1 in vacuum to 12.98 kcal mol−1 in water occurring via mediated proton transfer, which declines by 77.5%. When water participates in the 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. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 17475198
- Volume :
- 46
- Issue :
- 3
- Database :
- Academic Search Index
- Journal :
- Journal of Chemical Research
- Publication Type :
- Academic Journal
- Accession number :
- 157770799
- Full Text :
- https://doi.org/10.1177/17475198221104006