Analysis of the Nucleophilic Solvation Effects in Isopropyl Chlorothioformate Solvolysis
Open Access
- 29 June 2010
- journal article
- research article
- Published by MDPI AG in International Journal of Molecular Sciences
- Vol. 11 (7), 2597-2611
- https://doi.org/10.3390/ijms11072597
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.This publication has 56 references indexed in Scilit:
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