European Journal of Chemistry

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

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Published: Sep 30, 2012
DOI: https://doi.org/10.5155/eurjchem.3.3.267-272.624
Keywords:
Solvolysis, Ionization, Addition-elimination, Activation parameters, tert-Butyl chlorothioformate, Grunwald-Winstein equations
Section
Research Article
Issue
Vol. 3 No. 3 (2012): September 2012
Dates
Received 2012-04-24
Accepted 2012-05-19
Published 2012-09-30


Main Article Content

Jin Burm Kyong
Department of Chemistry and Applied Chemistry, Hanyang University, Ansan-si, Gyeonggi-Do, 426-791, Korea
Yelin Lee
Department of Chemistry and Applied Chemistry, Hanyang University, Ansan-si, Gyeonggi-Do, 426-791, Korea
Malcolm John D'Souza
Department of Chemistry, Wesley College, Dover, DE, 19901, USA
Brian Patrick Mahon
Department of Chemistry, Wesley College, Dover, DE, 19901, USA
Dennis Neil Kevill
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL, 60115, USA

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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