Table of Contents
ISRN Organic Chemistry
Volume 2011 (2011), Article ID 767141, 6 pages
http://dx.doi.org/10.5402/2011/767141
Research Article

A Study of Solvent Effects in the Solvolysis of Propargyl Chloroformate

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

Received 24 January 2011; Accepted 8 March 2011

Academic Editor: V. P. Kukhar

Copyright Β© 2011 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 specific rates of solvolysis of propargyl chloroformate (1) are analyzed in 22 solvents of widely varying nucleophilicity and ionizing power values at 25.0Β°C using the extended Grunwald-Winstein equation. Sensitivities to solvent nucleophilicity (𝑙) of 1.37 and to solvent ionizing power (π‘š) of 0.47 suggest a bimolecular process with the formation of a tetrahedral intermediate. A plot of the rates of solvolysis of 1 against those previously reported for phenyl chloroformate (2) results in a correlation coefficient (𝑅) of 0.996, a slope of 0.86, and an 𝐹-test value of 2161. The unequivocal correlation between these two substrates attests that the stepwise association-dissociation (AN + DN) mechanism previously proposed for 2 is also operative in 1.