6533b82cfe1ef96bd128ea43
RESEARCH PRODUCT
A Theoretical Study of the Favorskii Rearrangement. Calculation of Gas-Phase Reaction Paths and Solvation Effects on the Molecular Mechanism for the Transposition of the α-Chlorocyclobutanone
Mónica OlivaVicent S. SafontRaquel CastilloAnd I. TuñónJuan AndrésVicent MolinerS. Bohnsubject
SolvationAb initioThermodynamicsGeneral ChemistryFavorskii rearrangementBiochemistryPolarizable continuum modelCatalysischemistry.chemical_compoundColloid and Surface ChemistrychemistryComputational chemistryCyclopropanoneMolecular orbitalDensity functional theorySolvent effectsdescription
The molecular mechanism of the α-chlorocyclobutanone transposition to yield cyclopropanecarboxylic acid, as a model of the Favorskii rearrangement, has been theoretically characterized in vacuo by means of ab initio molecular orbital procedures at the Hartree−Fock (HF) level of theory with the 6-31G* and 6-31+G* basis sets. The electron correlation has been estimated at the MP2/6-31G* level and calculations based on density functional theory, BLYP/6-31G*. The solvent effects are included at HF/6-31G* level by means of a polarizable continuum model. The questions related to the two accepted molecular mechanisms, the semibenzilic acid and the cyclopropanone transpositions, as well as the competition between both reaction pathways are addressed in this investigation. The dependence of the geometries of the stationary structures along the corresponding reaction pathways and the transition vectors associated with the transition structures upon theoretical methods is discussed. The analysis of the results shows...
| year | journal | country | edition | language |
|---|---|---|---|---|
| 1997-02-01 | Journal of the American Chemical Society |