Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile–ketenimine equilibria

The study of tautomerics equilibria is really important because the reactivity of each compound with tautomeric capacity can be determined from the proportion of each tautomer. In the present work the tautomeric equilibria in some γ,δ-unsaturated β-hydroxynitriles and γ,δ-unsaturated β-ketonitriles...

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Detalles Bibliográficos
Autores principales: Giussi, Juan Martín, Gastaca, Belén, Albesa, Alberto Gustavo, Cortizo, María Susana, Allegretti, Patricia Ercilia
Formato: Articulo
Lenguaje:Inglés
Publicado: 2011
Materias:
Ciencias Exactas
Química
Tautomerism
β-Hydroxynitriles-γ,δ-unsaturated
β-Ketonitriles-γ-δ-unsaturated
Mass spectrometry
DFT calculation
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/151310
Aporte de:
SEDICI (UNLP) de Universidad Nacional de La Plata
id I19-R120-10915-151310
record_format dspace
spelling I19-R120-10915-1513102023-04-11T20:08:18Z http://sedici.unlp.edu.ar/handle/10915/151310 issn:1386-1425 Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile–ketenimine equilibria Giussi, Juan Martín Gastaca, Belén Albesa, Alberto Gustavo Cortizo, María Susana Allegretti, Patricia Ercilia 2011-02 2023-04-11T18:46:19Z en Ciencias Exactas Química Tautomerism β-Hydroxynitriles-γ,δ-unsaturated β-Ketonitriles-γ-δ-unsaturated Mass spectrometry DFT calculation The study of tautomerics equilibria is really important because the reactivity of each compound with tautomeric capacity can be determined from the proportion of each tautomer. In the present work the tautomeric equilibria in some γ,δ-unsaturated β-hydroxynitriles and γ,δ-unsaturated β-ketonitriles were studied. The first family of compounds presents two possible theoretical tautomers, nitrile and ketenimine, while the second one presents four possible theoretical tautomers, keto-nitrile, enol (E and Z)-nitrile and keto-ketenimine. The equilibrium in gas phase was studied by gas chromatography–mass spectrometry (GC–MS). Tautomerization enthalpies were calculated by this methodology, and results were compared with those obtained by density functional theory (DFT) calculations, observing a good agreement between them. Nitrile tautomers were favored within the first family of compounds, while keto-nitrile tautomers were favored in the second family. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas Laboratorio de Estudio de Compuestos Orgánicos Articulo Articulo http://creativecommons.org/licenses/by-nc-nd/4.0/ Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) application/pdf 868-873
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Ciencias Exactas
Química
Tautomerism
β-Hydroxynitriles-γ,δ-unsaturated
β-Ketonitriles-γ-δ-unsaturated
Mass spectrometry
DFT calculation
spellingShingle Ciencias Exactas
Química
Tautomerism
β-Hydroxynitriles-γ,δ-unsaturated
β-Ketonitriles-γ-δ-unsaturated
Mass spectrometry
DFT calculation
Giussi, Juan Martín
Gastaca, Belén
Albesa, Alberto Gustavo
Cortizo, María Susana
Allegretti, Patricia Ercilia
Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile–ketenimine equilibria
topic_facet Ciencias Exactas
Química
Tautomerism
β-Hydroxynitriles-γ,δ-unsaturated
β-Ketonitriles-γ-δ-unsaturated
Mass spectrometry
DFT calculation
description The study of tautomerics equilibria is really important because the reactivity of each compound with tautomeric capacity can be determined from the proportion of each tautomer. In the present work the tautomeric equilibria in some γ,δ-unsaturated β-hydroxynitriles and γ,δ-unsaturated β-ketonitriles were studied. The first family of compounds presents two possible theoretical tautomers, nitrile and ketenimine, while the second one presents four possible theoretical tautomers, keto-nitrile, enol (E and Z)-nitrile and keto-ketenimine. The equilibrium in gas phase was studied by gas chromatography–mass spectrometry (GC–MS). Tautomerization enthalpies were calculated by this methodology, and results were compared with those obtained by density functional theory (DFT) calculations, observing a good agreement between them. Nitrile tautomers were favored within the first family of compounds, while keto-nitrile tautomers were favored in the second family.
format Articulo
Articulo
author Giussi, Juan Martín
Gastaca, Belén
Albesa, Alberto Gustavo
Cortizo, María Susana
Allegretti, Patricia Ercilia
author_facet Giussi, Juan Martín
Gastaca, Belén
Albesa, Alberto Gustavo
Cortizo, María Susana
Allegretti, Patricia Ercilia
author_sort Giussi, Juan Martín
title Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile–ketenimine equilibria
title_short Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile–ketenimine equilibria
title_full Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile–ketenimine equilibria
title_fullStr Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile–ketenimine equilibria
title_full_unstemmed Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile–ketenimine equilibria
title_sort determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and dft calculations: keto-enol versus nitrile–ketenimine equilibria
publishDate 2011
url http://sedici.unlp.edu.ar/handle/10915/151310
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