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

Analysis of the Nucleophilic Solvation Effects in Isopropyl Chlorothioformate Solvolysis

1,* , 1 and 2,*
Received: 9 June 2010 / Revised: 21 June 2010 / Accepted: 28 June 2010 / Published: 29 June 2010
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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 solvolysis; Grunwald-Winstein Equations; nucleophilic solvation; chlorothioformate
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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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.

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