ISRN Organic Chemistry 2011-09-01

A Study of Solvent Effects in the Solvolysis of Propargyl Chloroformate.

MalcolmJ D'Souza, AnthonyM Darrington, DennisN Kevill

Index: ISRN Org. Chem. 2011 , (2011)

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Abstract

The specific rates of solvolysis of propargyl chloroformate (1) are analyzed in 22 solvents of widely varying nucleophilicity and ionizing power values at 25.0 _C using the extended Grunwald-Winstein equation. Sensitivities to solvent nucleophilicity (l) of 1.37 and to solvent ionizing power (m) 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 attest that the stepwise association-dissociation (A(N) + D(N)) mechanism previously proposed for 2 is also operative in 1.