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The effects of ionic liquids on the ethanolysis of a chloroacenaphthene. Evaluation of the effectiveness of nucleofugality data to predict reaction outcome

The reaction of a chlorobenzene in mixtures containing ethanol and eight different ionic liquids was investigated in order to understand the effects of varying proportions and constituent ions of an ionic liquid on the rate constant of the process. The results were found to be generally consistent w...

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Autores principales: Hsieh, Andrew Y., Haines, Ronald S., Harper, Jason B.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10336772/
https://www.ncbi.nlm.nih.gov/pubmed/37448642
http://dx.doi.org/10.1039/d3ra04302a
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author Hsieh, Andrew Y.
Haines, Ronald S.
Harper, Jason B.
author_facet Hsieh, Andrew Y.
Haines, Ronald S.
Harper, Jason B.
author_sort Hsieh, Andrew Y.
collection PubMed
description The reaction of a chlorobenzene in mixtures containing ethanol and eight different ionic liquids was investigated in order to understand the effects of varying proportions and constituent ions of an ionic liquid on the rate constant of the process. The results were found to be generally consistent with previously studied reactions of the same type, with small proportions of an ionic liquid resulting in a rate constant increase compared to ethanol and large proportions causing a rate constant decrease. Temperature dependent kinetic studies were used to interpret the changes in reaction outcome, particularly noting an entropic cost on moving to high proportions of ionic liquid, consistent with organisation of solvent around the transition state. While attempts to use empirical solvent parameters to correlate outcome with the ionic liquid used were unsuccessful, use of recently acquired nucleofugality data for chloride and estimations for the electrofuge allowed for excellent prediction of the effects of ionic liquids, with rate constants quantitatively predicted in systems containing both different proportions of ionic liquid (mean absolute error (MAE) log(k(1)) = 0.11) and different ionic liquids (MAE log(k(1)) = 0.33). Importantly, this demonstrates the ready application of these quantitative reactivity parameters.
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spelling pubmed-103367722023-07-13 The effects of ionic liquids on the ethanolysis of a chloroacenaphthene. Evaluation of the effectiveness of nucleofugality data to predict reaction outcome Hsieh, Andrew Y. Haines, Ronald S. Harper, Jason B. RSC Adv Chemistry The reaction of a chlorobenzene in mixtures containing ethanol and eight different ionic liquids was investigated in order to understand the effects of varying proportions and constituent ions of an ionic liquid on the rate constant of the process. The results were found to be generally consistent with previously studied reactions of the same type, with small proportions of an ionic liquid resulting in a rate constant increase compared to ethanol and large proportions causing a rate constant decrease. Temperature dependent kinetic studies were used to interpret the changes in reaction outcome, particularly noting an entropic cost on moving to high proportions of ionic liquid, consistent with organisation of solvent around the transition state. While attempts to use empirical solvent parameters to correlate outcome with the ionic liquid used were unsuccessful, use of recently acquired nucleofugality data for chloride and estimations for the electrofuge allowed for excellent prediction of the effects of ionic liquids, with rate constants quantitatively predicted in systems containing both different proportions of ionic liquid (mean absolute error (MAE) log(k(1)) = 0.11) and different ionic liquids (MAE log(k(1)) = 0.33). Importantly, this demonstrates the ready application of these quantitative reactivity parameters. The Royal Society of Chemistry 2023-07-12 /pmc/articles/PMC10336772/ /pubmed/37448642 http://dx.doi.org/10.1039/d3ra04302a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Hsieh, Andrew Y.
Haines, Ronald S.
Harper, Jason B.
The effects of ionic liquids on the ethanolysis of a chloroacenaphthene. Evaluation of the effectiveness of nucleofugality data to predict reaction outcome
title The effects of ionic liquids on the ethanolysis of a chloroacenaphthene. Evaluation of the effectiveness of nucleofugality data to predict reaction outcome
title_full The effects of ionic liquids on the ethanolysis of a chloroacenaphthene. Evaluation of the effectiveness of nucleofugality data to predict reaction outcome
title_fullStr The effects of ionic liquids on the ethanolysis of a chloroacenaphthene. Evaluation of the effectiveness of nucleofugality data to predict reaction outcome
title_full_unstemmed The effects of ionic liquids on the ethanolysis of a chloroacenaphthene. Evaluation of the effectiveness of nucleofugality data to predict reaction outcome
title_short The effects of ionic liquids on the ethanolysis of a chloroacenaphthene. Evaluation of the effectiveness of nucleofugality data to predict reaction outcome
title_sort effects of ionic liquids on the ethanolysis of a chloroacenaphthene. evaluation of the effectiveness of nucleofugality data to predict reaction outcome
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10336772/
https://www.ncbi.nlm.nih.gov/pubmed/37448642
http://dx.doi.org/10.1039/d3ra04302a
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