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Use of Empirical Correlations to Determine Solvent Effects in the Solvolysis of S-Methyl Chlorothioformate
Department of Chemistry, Wesley College, 120 N. State Street, Dover, Delaware 19901-3875, USA
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115-2862, USA
* Authors to whom correspondence should be addressed.
Received: 5 May 2010; in revised form: 12 May 2010 / Accepted: 24 May 2010 / Published: 25 May 2010
Abstract: The specific rates of solvolysis of S-methyl chlorothioformate (MeSCOCl) are analyzed in 20 solvents of widely varying nucleophilicity and ionizing power at 25.0 °C using the extended Grunwald-Winstein Equation. A stepwise SN1 (DN + AN) mechanism is proposed in the more ionizing solvents including six aqueous fluoroalcohols. In these solvents, a large sensitivity value of 0.79 towards changes in solvent nucleophilicity (l) is indicative of profound rearside nucleophilic solvation of the developing carbocation. In twelve of the more nucleophilic pure alchohols and aqueous solutions, the sensitivities obtained for solvent nucleophilicity (l) and solvent ionizing power (m) are similar to those found in acyl chlorides where an association-dissociation (AN + DN) mechanism is believed to be operative.
Keywords: solvolysis; nucleophilicity; ionizing power; S-methyl chlorothioformate; chloroformates; thioesters; thiochloroformate; Grunwald-Winstein Equation; Linear Free Energy Relationships
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MDPI and ACS Style
D’Souza, M.J.; Hailey, S.M.; Kevill, D.N. Use of Empirical Correlations to Determine Solvent Effects in the Solvolysis of S-Methyl Chlorothioformate. Int. J. Mol. Sci. 2010, 11, 2253-2266.
D’Souza MJ, Hailey SM, Kevill DN. Use of Empirical Correlations to Determine Solvent Effects in the Solvolysis of S-Methyl Chlorothioformate. International Journal of Molecular Sciences. 2010; 11(5):2253-2266.
D’Souza, Malcolm J.; Hailey, Stefan M.; Kevill, Dennis N. 2010. "Use of Empirical Correlations to Determine Solvent Effects in the Solvolysis of S-Methyl Chlorothioformate." Int. J. Mol. Sci. 11, no. 5: 2253-2266.