title: Analysis of the nucleophilic solvation effects in isopropyl chlorothioformate solvolysis.
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.
authors: Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901-3875, USA.
authors: Malcolm J
authors: MJ
authors: D'Souza
authors: Brian P
authors: BP
authors: Mahon
authors: Dennis N
authors: DN
authors: Kevill
mesh_terms: D006868:Hydrolysis; D012997:Solvents / Q000737:chemistry*
chemical_list: D012997:Solvents