Z. Ryu, Young Ho Lee, Y. Oh
2005
Citations
0
Influential Citations
7
Citations
Journal
Bulletin of The Korean Chemical Society
Abstract
Solvolysis rates of isopropenyl chloroformate (3) in water, D 2 O, CH 3 OD and in aqueous methanol, ethanol, 2,2,2-trifluoroethanol (TFE), acetone, 1,4-dioxane as well as TFE-ethanol at 10 °C are reported. Additional kinetic data for pure water, pure ethanol and 80%(w7w) 2,2,2-trifuoroethanol (T)-water (W) at various temperatures are also reported. These rates show the phenomena of maximum rates in specific solvents (30% (v/v) methanol-water and 20% (v/v) ethanol-water) and, variations in relative rates are small in aqueous alcohols. The kinetic data are analyzed in terms of GW correlations, steric effects, kinetic solvent isotope effects (KSIE), and a third order model based on general base catalysis (GBC). Solvolyses based on predominately stoichiometric solvation effect relative to medium solvation are proceeding in 3 and the results are remarkably similar to those forp-nitrobenzoyl chloride (4) in mechanism and reactivity.