European Journal of Chemistry

Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism



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Jin Burm Kyong
Yelin Lee
Malcolm John D'Souza
Brian Patrick Mahon
Dennis Neil Kevill

Abstract

The “parent” tertiary alkyl chloroformate, tert-butyl chloroformate, is unstable, but the tert-butyl chlorothioformate (1) is of increased stability and a kinetic investigation of the solvolyses is presented. Analyses in terms of simple and extended Grunwald-Winstein equations are carried out. The original one-term equation satisfactorily correlates the data with sensitivity towards changes in solvent ionizing power of 0.73±0.03. When the two-term equation is applied, the sensitivity towards changes in solvent nucleophilicity of 0.13±0.09 is associated with a high (0.17) probability that the term that it governs is not statistically significant.

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Kyong, J. B.; Lee, Y.; D’Souza, M. J.; Mahon, B. P.; Kevill, D. N. Correlation of the Rates of Solvolysis of Tert-Butyl Chlorothioformate and Observations Concerning the Reaction Mechanism. Eur. J. Chem. 2012, 3, 267-272.

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