European Journal of Chemistry

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



Main Article Content

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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Supporting Agencies

National Center for Research Resources-NCRR (5P20RR016472-12) and the National Institute of General Medical Sciences - NIGMS (8 P20 GM103446-12) from the National Institutes of Health (NIH), a National Science Foundation (NSF)
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