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Int. J. Mol. Sci. 2013, 14(4), 7286-7301; doi:10.3390/ijms14047286
Article

Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters

1,* , 1,†, 1,†, 1,†, 1,†, 1,† and 2,*
Received: 16 February 2013; in revised form: 26 March 2013 / Accepted: 28 March 2013 / Published: 2 April 2013
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Abstract: At 25.0 °C the specific rates of solvolysis for allyl and vinyl chloroformates have been determined in a wide mix of pure and aqueous organic mixtures. In all the solvents studied, vinyl chloroformate was found to react significantly faster than allyl chloroformate. Multiple correlation analyses of these rates are completed using the extended (two-term) Grunwald-Winstein equation with incorporation of literature values for solvent nucleophilicity (NT) and solvent ionizing power (YCl). Both substrates were found to solvolyze by similar dual bimolecular carbonyl-addition and unimolecular ionization channels, each heavily dependent upon the solvents nucleophilicity and ionizing ability.
Keywords: allyl chloroformate; vinyl chloroformate; mechanisms; solvolysis; nucleophilicity; ionizing power; π electron cloud; Grunwald-Winstein equation; Linear Free Energy Relationships (LFERs) allyl chloroformate; vinyl chloroformate; mechanisms; solvolysis; nucleophilicity; ionizing power; π electron cloud; 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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MDPI and ACS Style

D'Souza, M.J.; Givens, A.F.; Lorchak, P.A.; Greenwood, A.E.; Gottschall, S.L.; Carter, S.E.; Kevill, D.N. Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters. Int. J. Mol. Sci. 2013, 14, 7286-7301.

AMA Style

D'Souza MJ, Givens AF, Lorchak PA, Greenwood AE, Gottschall SL, Carter SE, Kevill DN. Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters. International Journal of Molecular Sciences. 2013; 14(4):7286-7301.

Chicago/Turabian Style

D'Souza, Malcolm J.; Givens, Aaron F.; Lorchak, Peter A.; Greenwood, Abigail E.; Gottschall, Stacey L.; Carter, Shannon E.; Kevill, Dennis N. 2013. "Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters." Int. J. Mol. Sci. 14, no. 4: 7286-7301.



Int. J. Mol. Sci. EISSN 1422-0067 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert