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Thermodynamics of the Isomerization of Monoterpene Epoxides
[Image: see text] In this contribution, the thermodynamic analysis of α- and β-pinene epoxide isomerization over Fe and Cu supported on MCM-41 is presented using computational chemistry and group contribution methods (GCMs). Some physical–chemical data (T(c), P(c), v(c), Z(c), ω, T(b), T(fus)) and t...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8697005/ https://www.ncbi.nlm.nih.gov/pubmed/34963907 http://dx.doi.org/10.1021/acsomega.1c03049 |
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author | Sánchez-Velandia, Julián E. Becerra, Jaime-Andrés Mejía, Sol M. Villa, Aída L. Martínez O, Fernando |
author_facet | Sánchez-Velandia, Julián E. Becerra, Jaime-Andrés Mejía, Sol M. Villa, Aída L. Martínez O, Fernando |
author_sort | Sánchez-Velandia, Julián E. |
collection | PubMed |
description | [Image: see text] In this contribution, the thermodynamic analysis of α- and β-pinene epoxide isomerization over Fe and Cu supported on MCM-41 is presented using computational chemistry and group contribution methods (GCMs). Some physical–chemical data (T(c), P(c), v(c), Z(c), ω, T(b), T(fus)) and thermodynamic (S°(298.15), C(p,298.15)(°), C(v,298.15)(°), ΔH(f,298.15)(°), ΔG(f,298.15)(°), ΔH(vb)(°), ΔH(fus), C(pL)) properties obtained by different GCMs are reported for several monoterpenes and monoterpenoids, which significantly contribute to the knowledge of the properties of these compounds. Density functional theory (DFT), PBE-D3/6-311G(d,p), was employed for determining the Gibbs free energy and the heat of reaction associated with the transformation of monoterpene epoxides into aldehydes, ketones, and related oxygenated compounds in the presence of different solvents and at several temperatures. The calculations were compared with available data reported and the experimental results of the catalytic reactions. The transformation of α- and β-pinene epoxides into aldehydes appears to be more spontaneous and favorable than their transformations into alcohols in a wide range of temperatures. These results are in agreement with the experiments over Fe/MCM-41 and Cu/MCM-41, where α-pinene epoxide isomerization yields campholenic aldehyde (50–80% selectivity) as the main product. The 1.7Fe/MCM-41 material was more active in all solvents than 1.3Cu/MCM-41 for both α- and β-pinene epoxide isomerization. However, perillyl alcohol (20–70% selectivity) was the most favored for the isomerization reaction, except when ethyl acetate was the solvent. Enthalpy and Gibbs free energy of the studied reactions estimated by both GCMs and DFT calculations did not show large differences for most of the reactions at evaluated temperatures. |
format | Online Article Text |
id | pubmed-8697005 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-86970052021-12-27 Thermodynamics of the Isomerization of Monoterpene Epoxides Sánchez-Velandia, Julián E. Becerra, Jaime-Andrés Mejía, Sol M. Villa, Aída L. Martínez O, Fernando ACS Omega [Image: see text] In this contribution, the thermodynamic analysis of α- and β-pinene epoxide isomerization over Fe and Cu supported on MCM-41 is presented using computational chemistry and group contribution methods (GCMs). Some physical–chemical data (T(c), P(c), v(c), Z(c), ω, T(b), T(fus)) and thermodynamic (S°(298.15), C(p,298.15)(°), C(v,298.15)(°), ΔH(f,298.15)(°), ΔG(f,298.15)(°), ΔH(vb)(°), ΔH(fus), C(pL)) properties obtained by different GCMs are reported for several monoterpenes and monoterpenoids, which significantly contribute to the knowledge of the properties of these compounds. Density functional theory (DFT), PBE-D3/6-311G(d,p), was employed for determining the Gibbs free energy and the heat of reaction associated with the transformation of monoterpene epoxides into aldehydes, ketones, and related oxygenated compounds in the presence of different solvents and at several temperatures. The calculations were compared with available data reported and the experimental results of the catalytic reactions. The transformation of α- and β-pinene epoxides into aldehydes appears to be more spontaneous and favorable than their transformations into alcohols in a wide range of temperatures. These results are in agreement with the experiments over Fe/MCM-41 and Cu/MCM-41, where α-pinene epoxide isomerization yields campholenic aldehyde (50–80% selectivity) as the main product. The 1.7Fe/MCM-41 material was more active in all solvents than 1.3Cu/MCM-41 for both α- and β-pinene epoxide isomerization. However, perillyl alcohol (20–70% selectivity) was the most favored for the isomerization reaction, except when ethyl acetate was the solvent. Enthalpy and Gibbs free energy of the studied reactions estimated by both GCMs and DFT calculations did not show large differences for most of the reactions at evaluated temperatures. American Chemical Society 2021-12-09 /pmc/articles/PMC8697005/ /pubmed/34963907 http://dx.doi.org/10.1021/acsomega.1c03049 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/). |
spellingShingle | Sánchez-Velandia, Julián E. Becerra, Jaime-Andrés Mejía, Sol M. Villa, Aída L. Martínez O, Fernando Thermodynamics of the Isomerization of Monoterpene Epoxides |
title | Thermodynamics of the Isomerization of Monoterpene
Epoxides |
title_full | Thermodynamics of the Isomerization of Monoterpene
Epoxides |
title_fullStr | Thermodynamics of the Isomerization of Monoterpene
Epoxides |
title_full_unstemmed | Thermodynamics of the Isomerization of Monoterpene
Epoxides |
title_short | Thermodynamics of the Isomerization of Monoterpene
Epoxides |
title_sort | thermodynamics of the isomerization of monoterpene
epoxides |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8697005/ https://www.ncbi.nlm.nih.gov/pubmed/34963907 http://dx.doi.org/10.1021/acsomega.1c03049 |
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