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Grunwald-Winstein Analysis - Isopropyl Chloroformate Solvolysis Revisited

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Department of Chemistry, Wesley College, 120 N. State Street, Dover, Delaware 19901-3875, USA
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Department of Chemistry and Applied Chemistry, Hanyang University, Ansan, Kyunggi-do, 425-791, Korea
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Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115-2862, USA
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Authors to whom correspondence should be addressed.
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Kevin J. Erdman completed a part of this research under the direction of Dr. Malcolm J. D’Souza, while an undergraduate at the University of Wisconsin-Waukesha County, Waukesha, Wisconsin, USA
Int. J. Mol. Sci. 2009, 10(3), 862-879; https://doi.org/10.3390/ijms10030862
Received: 9 February 2009 / Revised: 20 February 2009 / Accepted: 27 February 2009 / Published: 2 March 2009
(This article belongs to the Section Physical Chemistry, Theoretical and Computational Chemistry)
Specific rates of solvolysis at 25 °C for isopropyl chloroformate (1) in 24 solvents of widely varying nucleophilicity and ionizing power, plus literature values for studies in water and formic acid, are reported. Previously published solvolytic rate constants at 40.0 °C are supplemented with two additional values in the highly ionizing fluoroalcohols. These rates are now are analyzed using the one and two-term Grunwald-Winstein Equations. In the more ionizing solvents including ten fluoroalcohols negligible sensitivities towards changes in solvent nucleophilicity (l) and very low sensitivities towards changes in solvent ionizing power (m) values are obtained, evocative to those previously observed for 1-adamantyl and 2-adamantyl chloroformates 2 and 3. These observations are rationalized in terms of a dominant solvolysis-decomposition with loss of the CO2 molecule. In nine of the more nucleophilic pure alchohols and aqueous solutions an association-dissociation mechanism is believed to be operative. Deficiencies in the acid production indicate 2-33% isopropyl chloride formation, with the higher values in less nucleophilic solvents. View Full-Text
Keywords: Solvolysis; solvolysis-decomposition; nucleophilicity; ionizing power; isopropyl chloroformate; chloroformates; Grunwald-Winstein Equation; Linear Free Energy Relationships Solvolysis; solvolysis-decomposition; nucleophilicity; ionizing power; isopropyl chloroformate; chloroformates; Grunwald-Winstein Equation; Linear Free Energy Relationships
MDPI and ACS Style

D’Souza, M.J.; Reed, D.N.; Erdman, K.J.; Kyong, J.B.; Kevill, D.N. Grunwald-Winstein Analysis - Isopropyl Chloroformate Solvolysis Revisited. Int. J. Mol. Sci. 2009, 10, 862-879.

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