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Journal of Chemistry
Volume 2013 (2013), Article ID 248534, 9 pages
http://dx.doi.org/10.1155/2013/248534
Research Article

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

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

Received 15 June 2012; Accepted 27 June 2012

Academic Editor: Theocharis C. Stamatatos

Copyright © 2013 Malcolm J. D’Souza et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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 𝑁 1 mechanisms.