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

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...

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Autores principales: D’Souza, Malcolm J., Givens, Aaron F., Lorchak, Peter A., Greenwood, Abigail E., Gottschall, Stacey L., Carter, Shannon E., Kevill, Dennis N.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Molecular Diversity Preservation International (MDPI) 2013
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3645686/
https://www.ncbi.nlm.nih.gov/pubmed/23549265
http://dx.doi.org/10.3390/ijms14047286
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author D’Souza, Malcolm J.
Givens, Aaron F.
Lorchak, Peter A.
Greenwood, Abigail E.
Gottschall, Stacey L.
Carter, Shannon E.
Kevill, Dennis N.
author_facet D’Souza, Malcolm J.
Givens, Aaron F.
Lorchak, Peter A.
Greenwood, Abigail E.
Gottschall, Stacey L.
Carter, Shannon E.
Kevill, Dennis N.
author_sort D’Souza, Malcolm J.
collection PubMed
description 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 (N(T)) and solvent ionizing power (Y(Cl)). 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.
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spelling pubmed-36456862013-05-13 Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters D’Souza, Malcolm J. Givens, Aaron F. Lorchak, Peter A. Greenwood, Abigail E. Gottschall, Stacey L. Carter, Shannon E. Kevill, Dennis N. Int J Mol Sci Article 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 (N(T)) and solvent ionizing power (Y(Cl)). 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. Molecular Diversity Preservation International (MDPI) 2013-04-02 /pmc/articles/PMC3645686/ /pubmed/23549265 http://dx.doi.org/10.3390/ijms14047286 Text en © 2013 by the authors; licensee MDPI, Basel, Switzerland http://creativecommons.org/licenses/by/3.0 This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/3.0/).
spellingShingle Article
D’Souza, Malcolm J.
Givens, Aaron F.
Lorchak, Peter A.
Greenwood, Abigail E.
Gottschall, Stacey L.
Carter, Shannon E.
Kevill, Dennis N.
Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters
title Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters
title_full Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters
title_fullStr Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters
title_full_unstemmed Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters
title_short Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters
title_sort kinetic studies that evaluate the solvolytic mechanisms of allyl and vinyl chloroformate esters
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3645686/
https://www.ncbi.nlm.nih.gov/pubmed/23549265
http://dx.doi.org/10.3390/ijms14047286
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