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Extended Grunwald-Winstein Analysis - LFER Used to Gauge Solvent Effects in p-Nitrophenyl Chloroformate Solvolysis
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: 27 October 2008; in revised form: 9 November 2008 / Accepted: 12 November 2008 / Published: 13 November 2008
Abstract: Specific rates of solvolysis at 25oC for p-nitrophenyl chloroformate (1) are analyzed using the extended (two-term) Grunwald-Winstein equation. For 39 solvents, the sensitivities (l = 1.68±0.06 and m = 0.46±0.04) towards changes in solvent nucleophilicity (l) and solvent ionizing power (m) obtained, are similar to those previously observed for phenyl chloroformate (2) and p-methoxyphenyl chloroformate (3). The observations incorporating new kinetic data in several fluoroalcohol-containing mixtures, are rationalized in terms of the reaction being sensitive to substituent effects and the mechanism of reaction involving the addition (association) step of an additionelimination (association-dissociation) pathway being rate-determining. The l/m ratios obtained for 1, 2, and 3, are also compared to the previously published l/m ratios for benzyl chloroformate (4) and p-nitrobenzyl chloroformate (5).
Keywords: Solvolysis; addition-elimination; association-dissociation; p-nitrophenyl chloroformate; chloroformates; Grunwald-Winstein equation; LFERS; leaving group effects
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D’Souza, M.J.; Shuman, K.E.; Carter, S.E.; Kevill, D.N. Extended Grunwald-Winstein Analysis - LFER Used to Gauge Solvent Effects in p-Nitrophenyl Chloroformate Solvolysis. Int. J. Mol. Sci. 2008, 9, 2231-2242.
D’Souza MJ, Shuman KE, Carter SE, Kevill DN. Extended Grunwald-Winstein Analysis - LFER Used to Gauge Solvent Effects in p-Nitrophenyl Chloroformate Solvolysis. International Journal of Molecular Sciences. 2008; 9(11):2231-2242.
D’Souza, Malcolm J.; Shuman, Kevin E.; Carter, Shannon E.; Kevill, Dennis N. 2008. "Extended Grunwald-Winstein Analysis - LFER Used to Gauge Solvent Effects in p-Nitrophenyl Chloroformate Solvolysis." Int. J. Mol. Sci. 9, no. 11: 2231-2242.