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)
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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.
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.
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.