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Int. J. Mol. Sci. 2010, 11(5), 2253-2266; doi:10.3390/ijms11052253
Article

Use of Empirical Correlations to Determine Solvent Effects in the Solvolysis of S-Methyl Chlorothioformate

1,* , 1 and 2,*
Received: 5 May 2010; in revised form: 12 May 2010 / Accepted: 24 May 2010 / Published: 25 May 2010
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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 solvolysis; nucleophilicity; ionizing power; S-methyl chlorothioformate; chloroformates; thioesters; thiochloroformate; Grunwald-Winstein Equation; Linear Free Energy Relationships
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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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.

AMA Style

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.

Chicago/Turabian Style

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.


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