title: A Kinetic Study of the Thermal Decarboxylation of alpha,alpha-Difluoro beta-Lactones.
abstract: The rates of thermolysis of alpha,alpha-difluoro beta-lactones 1, leading to CO(2) and 1,1-difluoro olefins, have been obtained in the gas phase and in solution, and the activation parameters are reported. Ab initio calculations on the fluoro and nonfluorinated beta-lactone systems are also reported. The gas-phase kinetic and theoretical results are discussed in terms of a probable concerted, asynchronous, nonpolar mechanism, whereas the solution kinetics, which include extensive solvent effect studies, are discussed in terms of a polar mechanism which probably involves formation of a zwitterionic intermediate.
authors.affiliation: Department of Chemistry, University of Florida, Gainesville, Florida 32611, Departamento de Quimica, Universidad de Caldas, Colombia, and Departamento de Quimica, Universidad del Valle, Colombia.
authors.forename: Rogelio
authors.initials: R
authors.lastname: Ocampo
authors.forename: William R.
authors.initials: WR
authors.lastname: Dolbier
authors.forename: Michael D.
authors.initials: MD
authors.lastname: Bartberger
authors.forename: Rodrigo
authors.initials: R
authors.lastname: Paredes