Next Article in Journal
Antibiotic Producing Potentials of Three Freshwater Actinomycetes Isolated from the Eastern Cape Province of South Africa
Previous Article in Journal
Sequential Events in the Irreversible Thermal Denaturation of Human Brain-Type Creatine Kinase by Spectroscopic Methods
Article Menu

Export Article

Open AccessArticle
Int. J. Mol. Sci. 2010, 11(7), 2597-2611;

Analysis of the Nucleophilic Solvation Effects in Isopropyl Chlorothioformate Solvolysis

Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901-3875, USA
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115-2862, USA
Authors to whom correspondence should be addressed.
Received: 9 June 2010 / Revised: 21 June 2010 / Accepted: 28 June 2010 / Published: 29 June 2010
(This article belongs to the Section Physical Chemistry, Theoretical and Computational Chemistry)
Full-Text   |   PDF [223 KB, uploaded 19 June 2014]


Correlation of the solvent effects through application of the extended Grunwald-Winstein equation to the solvolysis of isopropyl chlorothioformate results in a sensitivity value of 0.38 towards changes in solvent nucleophilicity (l) and a sensitivity value of 0.72 towards changes in solvent ionizing power (m). This tangible l value coupled with the negative entropies of activation observed indicates a favorable predisposition towards a modest rear-side nucleophilic solvation of a developing carbocation. Only in 100% ethanol was the bimolecular pathway dominant. These observations are very different from those obtained for the solvolysis of isopropyl chloroformate, where dual reaction channels were proposed, with the addition-elimination reaction favored in the more nucleophilic solvents and a unimolecular fragmentation-ionization mechanism favored in the highly ionizing solvents. View Full-Text
Keywords: solvolysis; Grunwald-Winstein Equations; nucleophilic solvation; chlorothioformate solvolysis; Grunwald-Winstein Equations; nucleophilic solvation; chlorothioformate
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

Share & Cite This Article

MDPI and ACS Style

D’Souza, M.J.; Mahon, B.P.; Kevill, D.N. Analysis of the Nucleophilic Solvation Effects in Isopropyl Chlorothioformate Solvolysis. Int. J. Mol. Sci. 2010, 11, 2597-2611.

Show more citation formats Show less citations formats

Related Articles

Article Metrics

Article Access Statistics



[Return to top]
Int. J. Mol. Sci. EISSN 1422-0067 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top