Evaluation of Electronic Effects in the Solvolyses of p-Methylphenyl and p-Chlorophenyl Chlorothionoformate Esters

Malcolm J D'Souza; Olivia N Hampton; Brett M Sansbury; Dennis N Kevill

doi:10.1155/2013/248534

Evaluation of Electronic Effects in the Solvolyses of p-Methylphenyl and p-Chlorophenyl Chlorothionoformate Esters

J Chem. 2013:2013:10.1155/2013/248534. doi: 10.1155/2013/248534.

Authors

Malcolm J D'Souza¹, Olivia N Hampton¹, Brett M Sansbury¹, Dennis N Kevill²

Affiliations

¹ Department of Chemistry, Wesley College, 120 N. State Street, Dover, Delaware 19901-3875, USA.
² Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115-2862, USA.

Abstract

The solvolyses of p-tolyl chlorothionoformate and p-chlorophenyl chlorothionoformate are studied in a variety of organic mixtures of widely varying nucleophilicity and ionizing power values. This solvolytic data is accumulated at 25.0 °C using the titration method. An analysis of the rate data using the extended (two-term) Grunwald-Winstein equation, and the concept of similarity of substrates based on their l/m ratios, shows the occurrence of simultaneous side-by-side addition-elimination and unimolecular S_N1 mechanisms.

Keywords: Grunwald-Winstein equation; Solvolysis; addition-elimination; ionization; p-chlorophenyl chlorothionoformate; p-tolyl (or p-methylphenyl) chlorothionoformate.

Abstract

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