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Int. J. Mol. Sci. 2008, 9(11), 2231-2242; doi:10.3390/ijms9112231
Article

Extended Grunwald-Winstein Analysis - LFER Used to Gauge Solvent Effects in p-Nitrophenyl Chloroformate Solvolysis

1,* , 1, 1 and 2,*
Received: 27 October 2008; in revised form: 9 November 2008 / Accepted: 12 November 2008 / Published: 13 November 2008
(This article belongs to the Special Issue Grunwald-Winstein Equations – 60 Years & Counting)
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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 Solvolysis; addition-elimination; association-dissociation; p-nitrophenyl chloroformate; chloroformates; Grunwald-Winstein equation; LFERS; leaving group effects
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.; 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.

AMA Style

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.

Chicago/Turabian Style

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.



Int. J. Mol. Sci. EISSN 1422-0067 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert