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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

1,* , 1
,
1
 and
2,*
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.
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 which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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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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