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

Autores
Giussi, Juan Martín; Gastaca, Belén; Albesa, Alberto Gustavo; Cortizo, María Susana; Allegretti, Patricia Ercilia
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
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
Materia
Ciencias Exactas
Química
Tautomerism
β-Hydroxynitriles-γ,δ-unsaturated
β-Ketonitriles-γ-δ-unsaturated
Mass spectrometry
DFT calculation
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-nd/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/151310
Acceder
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oai_identifier_str oai:sedici.unlp.edu.ar:10915/151310
network_acronym_str SEDICI
repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile–ketenimine equilibriaGiussi, Juan MartínGastaca, BelénAlbesa, Alberto GustavoCortizo, María SusanaAllegretti, Patricia ErciliaCiencias ExactasQuímicaTautomerismβ-Hydroxynitriles-γ,δ-unsaturatedβ-Ketonitriles-γ-δ-unsaturatedMass spectrometryDFT calculationThe 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 AplicadasLaboratorio de Estudio de Compuestos Orgánicos2011-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf868-873http://sedici.unlp.edu.ar/handle/10915/151310enginfo:eu-repo/semantics/altIdentifier/issn/1386-1425info:eu-repo/semantics/altIdentifier/doi/10.1016/j.saa.2010.12.050info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/4.0/Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-10T12:41:34Zoai:sedici.unlp.edu.ar:10915/151310Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-10 12:41:34.902SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile–ketenimine equilibria
title Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile–ketenimine equilibria
spellingShingle Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile–ketenimine equilibria
Giussi, Juan Martín
Ciencias Exactas
Química
Tautomerism
β-Hydroxynitriles-γ,δ-unsaturated
β-Ketonitriles-γ-δ-unsaturated
Mass spectrometry
DFT calculation
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
dc.creator.none.fl_str_mv Giussi, Juan Martín
Gastaca, Belén
Albesa, Alberto Gustavo
Cortizo, María Susana
Allegretti, Patricia Ercilia
author Giussi, Juan Martín
author_facet Giussi, Juan Martín
Gastaca, Belén
Albesa, Alberto Gustavo
Cortizo, María Susana
Allegretti, Patricia Ercilia
author_role author
author2 Gastaca, Belén
Albesa, Alberto Gustavo
Cortizo, María Susana
Allegretti, Patricia Ercilia
author2_role author
author
author
author
dc.subject.none.fl_str_mv Ciencias Exactas
Química
Tautomerism
β-Hydroxynitriles-γ,δ-unsaturated
β-Ketonitriles-γ-δ-unsaturated
Mass spectrometry
DFT calculation
topic Ciencias Exactas
Química
Tautomerism
β-Hydroxynitriles-γ,δ-unsaturated
β-Ketonitriles-γ-δ-unsaturated
Mass spectrometry
DFT calculation
dc.description.none.fl_txt_mv 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
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.
publishDate 2011
dc.date.none.fl_str_mv 2011-02
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://sedici.unlp.edu.ar/handle/10915/151310
url http://sedici.unlp.edu.ar/handle/10915/151310
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/1386-1425
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.saa.2010.12.050
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-nd/4.0/
Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-nd/4.0/
Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
dc.format.none.fl_str_mv application/pdf
868-873
dc.source.none.fl_str_mv reponame:SEDICI (UNLP)
instname:Universidad Nacional de La Plata
instacron:UNLP
reponame_str SEDICI (UNLP)
collection SEDICI (UNLP)
instname_str Universidad Nacional de La Plata
instacron_str UNLP
institution UNLP
repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
repository.mail.fl_str_mv alira@sedici.unlp.edu.ar
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score 12.993085

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