Analysis of the Nucleophilic Solvation Effects in Isopropyl Chlorothioformate Solvolysis

International Journal of Molecular Sciences

Malcolm J. D’Souza¹  Brian P. Mahon¹ 

[1] Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901-3875, USA

关键词: solvolysis;    Grunwald-Winstein Equations;    nucleophilic solvation;    chlorothioformate;   

DOI  :  10.3390/ijms11072597

来源: mdpi

【 摘 要 】

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.

【 授权许可】

CC BY   
© 2010 by the authors; licensee Molecular Diversity Preservation International, Basel, Switzerland.