title: Inverse solvent effects in the heterogeneous and homogeneous epoxidation of cis-2-heptene with [2-percarboxyethyl]-functionalized silica and meta-chloroperbenzoic acid.
abstract: The rate constants for the epoxidation of cis-2-heptene with [2-percarboxyethyl]-functionalized silica (1a) and meta-chloroperbenzoic acid (mCPBA) (1b) in different solvents have been determined at temperatures in the -10 to 40 °C range. The heterogeneous epoxidation exhibits a dependence of the reaction rate on solvent polarity opposite to its homogeneous counterpart and anomalous activation parameters in n-hexane, which are interpreted in terms of the surface-promoted solvent structure at the solid-liquid interface. The results show that highly polar solvents can strongly inhibit heterogeneous reactions performed with silica-supported reagents or catalysts.
authors.affiliation: Departamento de Química Orgánica, Facultad de Farmacia, Universidad de Valencia, Avda. Vicente Andrés Estellés s.n., 46100-Burjassot, Valencia, Spain. elena.gonzalez@uv.es.
authors.forename: Rossella
authors.initials: R
authors.lastname: Mello
authors.forename: Jeymy T
authors.initials: JT
authors.lastname: Sarmiento-Monsalve
authors.forename: Diana
authors.initials: D
authors.lastname: Vargas-Oviedo
authors.forename: Rafael
authors.initials: R
authors.lastname: Acerete
authors.forename: María Elena
authors.initials: ME
authors.lastname: González-Núñez
authors.forename: Gregorio
authors.initials: G
authors.lastname: Asensio
mesh_terms: D002723:Chlorobenzoates / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D006536:Heptanes / Q000737:chemistry*; D006586:Hexanes / Q000737:chemistry*; D007700:Kinetics; D010084:Oxidation-Reduction; D012822:Silicon Dioxide / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D002723:Chlorobenzoates; D004852:Epoxy Compounds; D006536:Heptanes; D006586:Hexanes; D012997:Solvents; C026385:n-hexane; D012822:Silicon Dioxide; C000433:3-chloroperbenzoic acid