Int. J. Mol. Sci. 2010, 11(7), 2597-2611; doi:10.3390/ijms11072597
Article

Analysis of the Nucleophilic Solvation Effects in Isopropyl Chlorothioformate Solvolysis

Malcolm J. D’Souza 1,* email, Brian P. Mahon 1  and Dennis N. Kevill 2,* email
1 Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901-3875, USA 2 Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115-2862, USA
* Authors to whom correspondence should be addressed.
Received: 9 June 2010; in revised form: 21 June 2010 / Accepted: 28 June 2010 / Published: 29 June 2010
(This article belongs to the Section Physical Chemistry, Theoretical and Computational Chemistry)
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Abstract: 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.
Keywords: solvolysis; Grunwald-Winstein Equations; nucleophilic solvation; chlorothioformate

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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.

AMA Style

D’Souza MJ, Mahon BP, Kevill DN. Analysis of the Nucleophilic Solvation Effects in Isopropyl Chlorothioformate Solvolysis. International Journal of Molecular Sciences. 2010; 11(7):2597-2611.

Chicago/Turabian Style

D’Souza, Malcolm J.; Mahon, Brian P.; Kevill, Dennis N. 2010. "Analysis of the Nucleophilic Solvation Effects in Isopropyl Chlorothioformate Solvolysis." Int. J. Mol. Sci. 11, no. 7: 2597-2611.

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