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Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media

Rate constants and activations parameters are reported for solvolyses of p-Z-substituted benzoyl chlorides (1, Z = OMe, Me, H, and Cl) in 97% w/w hexafluoroisopropanol-water (97H). Additional kinetic data are reported for solvolyses in acetic and formic acids. Plots of log k vs. σ(p) in 97H are cons...

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Detalles Bibliográficos
Autores principales: Bentley, Thomas William, Harris, Haldon Carl
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Molecular Diversity Preservation International (MDPI) 2011
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3179133/
https://www.ncbi.nlm.nih.gov/pubmed/21954326
http://dx.doi.org/10.3390/ijms12084805
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author Bentley, Thomas William
Harris, Haldon Carl
author_facet Bentley, Thomas William
Harris, Haldon Carl
author_sort Bentley, Thomas William
collection PubMed
description Rate constants and activations parameters are reported for solvolyses of p-Z-substituted benzoyl chlorides (1, Z = OMe, Me, H, and Cl) in 97% w/w hexafluoroisopropanol-water (97H). Additional kinetic data are reported for solvolyses in acetic and formic acids. Plots of log k vs. σ(p) in 97H are consistent with previous research showing that a cationic reaction channel is dominant, even for solvolyses of 1, Z = NO(2). A benzoyl cation intermediate was trapped by Friedel-Crafts reaction with 1,3,5-trimethoxybenzene in hexafluoroisopropanol. The results are explained by an S(N)2-S(N)1 spectrum of mechanisms with variations in nucleophilic solvent assistance. Ab initio calculations of heterolytic bond dissociation energies of various chloro- and fluoro-substituted and other benzoyl chlorides are correlated with log k for solvolyses.
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spelling pubmed-31791332011-09-27 Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media Bentley, Thomas William Harris, Haldon Carl Int J Mol Sci Article Rate constants and activations parameters are reported for solvolyses of p-Z-substituted benzoyl chlorides (1, Z = OMe, Me, H, and Cl) in 97% w/w hexafluoroisopropanol-water (97H). Additional kinetic data are reported for solvolyses in acetic and formic acids. Plots of log k vs. σ(p) in 97H are consistent with previous research showing that a cationic reaction channel is dominant, even for solvolyses of 1, Z = NO(2). A benzoyl cation intermediate was trapped by Friedel-Crafts reaction with 1,3,5-trimethoxybenzene in hexafluoroisopropanol. The results are explained by an S(N)2-S(N)1 spectrum of mechanisms with variations in nucleophilic solvent assistance. Ab initio calculations of heterolytic bond dissociation energies of various chloro- and fluoro-substituted and other benzoyl chlorides are correlated with log k for solvolyses. Molecular Diversity Preservation International (MDPI) 2011-07-28 /pmc/articles/PMC3179133/ /pubmed/21954326 http://dx.doi.org/10.3390/ijms12084805 Text en © 2011 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
Bentley, Thomas William
Harris, Haldon Carl
Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media
title Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media
title_full Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media
title_fullStr Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media
title_full_unstemmed Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media
title_short Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media
title_sort solvolyses of benzoyl chlorides in weakly nucleophilic media
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3179133/
https://www.ncbi.nlm.nih.gov/pubmed/21954326
http://dx.doi.org/10.3390/ijms12084805
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