Extended Grunwald-Winstein Analysis - LFER Used to Gauge Solvent Effects in p-Nitrophenyl Chloroformate Solvolysis
Open Access
- 13 November 2008
- journal article
- research article
- Published by MDPI AG in International Journal of Molecular Sciences
- Vol. 9 (11), 2231-2242
- https://doi.org/10.3390/ijms9112231
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).This publication has 43 references indexed in Scilit:
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