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Int. J. Mol. Sci. 2012, 13(1), 665-682; doi:10.3390/ijms13010665

Use of Linear Free Energy Relationships (LFERs) to Elucidate the Mechanisms of Reaction of a γ-Methyl-β-alkynyl and an ortho-Substituted Aryl Chloroformate Ester

1
Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901, USA
2
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA
*
Authors to whom correspondence should be addressed.
Received: 20 December 2011 / Revised: 5 January 2012 / Accepted: 5 January 2012 / Published: 10 January 2012
(This article belongs to the Special Issue Correlation Analysis Applied to Solvolysis Reactions)
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Abstract

The specific rates of solvolysis of 2-butyn-1-yl-chloroformate (1) and 2-methoxyphenyl chloroformate (2) are studied at 25.0 °C in a series of binary aqueous-organic mixtures. The rates of reaction obtained are then analyzed using the extended Grunwald-Winstein (G-W) equation and the results are compared to previously published G-W analyses for phenyl chloroformate (3), propargyl chloroformate (4), p-methoxyphenyl choroformate (5), and p-nitrophenyl chloroformate (6). For 1, the results indicate that dual side-by-side addition-elimination and ionization pathways are occurring in some highly ionizing solvents due to the presence of the electron-donating γ-methyl group. For 2, the analyses indicate that the dominant mechanism is a bimolecular one where the formation of a tetrahedral intermediate is rate-determining. View Full-Text
Keywords: solvolysis; nucleophilicity; ionizing power; γ-Methyl-β-alkynyl chloroformate; 2-butyn-1-yl-chloroformate; aryl chloroformate; 2-methoxyphenyl chloroformate; Grunwald-Winstein equation; Linear Free Energy Relationships (LFERs) solvolysis; nucleophilicity; ionizing power; γ-Methyl-β-alkynyl chloroformate; 2-butyn-1-yl-chloroformate; aryl chloroformate; 2-methoxyphenyl chloroformate; Grunwald-Winstein equation; Linear Free Energy Relationships (LFERs)
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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MDPI and ACS Style

D’Souza, M.J.; Knapp, J.A.; Fernandez-Bueno, G.A.; Kevill, D.N. Use of Linear Free Energy Relationships (LFERs) to Elucidate the Mechanisms of Reaction of a γ-Methyl-β-alkynyl and an ortho-Substituted Aryl Chloroformate Ester. Int. J. Mol. Sci. 2012, 13, 665-682.

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