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Understanding Solvent Effects in the Solvolyses of 4-Fluorophenyl Chlorothionoformate
Mj D'Souza1, Sm Hailey, Bp Mahon
1Department of Chemistry, Wesley College, 120 N. State Street, Dover, Delaware 19901-3875, USA.
Abstract:
The solvolyses of 4-fluorophenyl chlorothionoformate (1) are studied in fifteen binary aqueous organic mixtures of widely varying nucleophilicity and ionizing power values. The specific rates of solvolyses of 1 are plotted against the specific rates of solvolysis observed for phenyl chloroformate (2) and deviations from the line-of-best-fit are observed in some of the highly ionizing aqueous fluoroalcohol mixtures. An analysis of the solvolytic data accumulated using the extended (two-term) Grunwald-Winstein equation confirms this deviant behavior and shows that dual bimolecular addition-elimination and unimolecular ionization channels occur in the solvolyses of 1.
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A solution is a homogeneous mixture composed of a solvent, the major component, and a solute, the minor component. The physical state of a solution—solid, liquid, or gas—is typically the same as that of the solvent. Solute concentrations are often described with qualitative terms such as dilute (of relatively low concentration) and concentrated (of relatively high concentration).
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