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

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

Malcolm J. D’Souza 1,* email, Jaci A. Knapp 1 email, Gabriel A. Fernandez-Bueno 1 email and Dennis N. Kevill 2,* email
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; in revised form: 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.
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)

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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.

AMA Style

D’Souza MJ, Knapp JA, Fernandez-Bueno GA, Kevill DN. 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. International Journal of Molecular Sciences. 2012; 13(1):665-682.

Chicago/Turabian Style

D’Souza, Malcolm J.; Knapp, Jaci A.; Fernandez-Bueno, Gabriel A.; Kevill, Dennis N. 2012. "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. 13, no. 1: 665-682.

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