The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydes

Autores
Ruiz, Danila Luján; Schiavoni, Maria de Las Mercedes; Laurella, Sergio Luis; Giussi, Juan Martín; Furlong, Jorge J.P.; Allegretti, Patricia E.
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Mass spectra of selected aldehydes and thioaldehydes have been analyzed and specific fragmentation assignments have been done to keto and enol tautomers, although many peaks can be assigned to both forms (i.e. mass spectra are superimposed on one another). The enolization rate for aldehydes is generally favored by the increase in the steric effect caused by α substitution to the carbonyl group. The analysis of the corresponding mass spectra has allowed to establishing an acceptable correlation between selected ion abundances ratios and approximate enolization equilibrium constants (carried out by means of DFT calculations). The influence of temperature on the enol/keto selected fragments abundance ratios (for different aldehydes and thioaldehydes and for different pair of ions of the same compound whenever possible) is studied in order to estimate the enthalpy difference for the tautomeric equilibria. The results indicate that the thioketo–thioenol equilibrium can be studied by mass spectrometry and the ionization in the ion source have negligible effect on the position of that equilibrium.
Fil: Ruiz, Danila Luján. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Schiavoni, Maria de Las Mercedes. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina
Fil: Laurella, Sergio Luis. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina
Fil: Giussi, Juan Martín. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Furlong, Jorge J.P.. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina
Fil: Allegretti, Patricia E.. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina
Materia
Tautomerization
Aldehydes
Mass spectrometry
Theoretical calculations
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/95099
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/95099
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydesRuiz, Danila LujánSchiavoni, Maria de Las MercedesLaurella, Sergio LuisGiussi, Juan MartínFurlong, Jorge J.P.Allegretti, Patricia E.TautomerizationAldehydesMass spectrometryTheoretical calculationshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Mass spectra of selected aldehydes and thioaldehydes have been analyzed and specific fragmentation assignments have been done to keto and enol tautomers, although many peaks can be assigned to both forms (i.e. mass spectra are superimposed on one another). The enolization rate for aldehydes is generally favored by the increase in the steric effect caused by α substitution to the carbonyl group. The analysis of the corresponding mass spectra has allowed to establishing an acceptable correlation between selected ion abundances ratios and approximate enolization equilibrium constants (carried out by means of DFT calculations). The influence of temperature on the enol/keto selected fragments abundance ratios (for different aldehydes and thioaldehydes and for different pair of ions of the same compound whenever possible) is studied in order to estimate the enthalpy difference for the tautomeric equilibria. The results indicate that the thioketo–thioenol equilibrium can be studied by mass spectrometry and the ionization in the ion source have negligible effect on the position of that equilibrium.Fil: Ruiz, Danila Luján. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Schiavoni, Maria de Las Mercedes. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; ArgentinaFil: Laurella, Sergio Luis. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; ArgentinaFil: Giussi, Juan Martín. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Furlong, Jorge J.P.. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; ArgentinaFil: Allegretti, Patricia E.. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; ArgentinaPergamon-Elsevier Science Ltd2011-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/95099Ruiz, Danila Luján; Schiavoni, Maria de Las Mercedes; Laurella, Sergio Luis; Giussi, Juan Martín; Furlong, Jorge J.P.; et al.; The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydes; Pergamon-Elsevier Science Ltd; Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy; 78; 5; 5-2011; 1397-14021386-1425CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S1386142511000333info:eu-repo/semantics/altIdentifier/doi/10.1016/j.saa.2011.01.017info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:10:52Zoai:ri.conicet.gov.ar:11336/95099instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 10:10:52.86CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydes
title The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydes
spellingShingle The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydes
Ruiz, Danila Luján
Tautomerization
Aldehydes
Mass spectrometry
Theoretical calculations
title_short The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydes
title_full The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydes
title_fullStr The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydes
title_full_unstemmed The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydes
title_sort The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydes
dc.creator.none.fl_str_mv Ruiz, Danila Luján
Schiavoni, Maria de Las Mercedes
Laurella, Sergio Luis
Giussi, Juan Martín
Furlong, Jorge J.P.
Allegretti, Patricia E.
author Ruiz, Danila Luján
author_facet Ruiz, Danila Luján
Schiavoni, Maria de Las Mercedes
Laurella, Sergio Luis
Giussi, Juan Martín
Furlong, Jorge J.P.
Allegretti, Patricia E.
author_role author
author2 Schiavoni, Maria de Las Mercedes
Laurella, Sergio Luis
Giussi, Juan Martín
Furlong, Jorge J.P.
Allegretti, Patricia E.
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Tautomerization
Aldehydes
Mass spectrometry
Theoretical calculations
topic Tautomerization
Aldehydes
Mass spectrometry
Theoretical calculations
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Mass spectra of selected aldehydes and thioaldehydes have been analyzed and specific fragmentation assignments have been done to keto and enol tautomers, although many peaks can be assigned to both forms (i.e. mass spectra are superimposed on one another). The enolization rate for aldehydes is generally favored by the increase in the steric effect caused by α substitution to the carbonyl group. The analysis of the corresponding mass spectra has allowed to establishing an acceptable correlation between selected ion abundances ratios and approximate enolization equilibrium constants (carried out by means of DFT calculations). The influence of temperature on the enol/keto selected fragments abundance ratios (for different aldehydes and thioaldehydes and for different pair of ions of the same compound whenever possible) is studied in order to estimate the enthalpy difference for the tautomeric equilibria. The results indicate that the thioketo–thioenol equilibrium can be studied by mass spectrometry and the ionization in the ion source have negligible effect on the position of that equilibrium.
Fil: Ruiz, Danila Luján. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Schiavoni, Maria de Las Mercedes. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina
Fil: Laurella, Sergio Luis. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina
Fil: Giussi, Juan Martín. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Furlong, Jorge J.P.. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina
Fil: Allegretti, Patricia E.. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina
description Mass spectra of selected aldehydes and thioaldehydes have been analyzed and specific fragmentation assignments have been done to keto and enol tautomers, although many peaks can be assigned to both forms (i.e. mass spectra are superimposed on one another). The enolization rate for aldehydes is generally favored by the increase in the steric effect caused by α substitution to the carbonyl group. The analysis of the corresponding mass spectra has allowed to establishing an acceptable correlation between selected ion abundances ratios and approximate enolization equilibrium constants (carried out by means of DFT calculations). The influence of temperature on the enol/keto selected fragments abundance ratios (for different aldehydes and thioaldehydes and for different pair of ions of the same compound whenever possible) is studied in order to estimate the enthalpy difference for the tautomeric equilibria. The results indicate that the thioketo–thioenol equilibrium can be studied by mass spectrometry and the ionization in the ion source have negligible effect on the position of that equilibrium.
publishDate 2011
dc.date.none.fl_str_mv 2011-05
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
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://hdl.handle.net/11336/95099
Ruiz, Danila Luján; Schiavoni, Maria de Las Mercedes; Laurella, Sergio Luis; Giussi, Juan Martín; Furlong, Jorge J.P.; et al.; The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydes; Pergamon-Elsevier Science Ltd; Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy; 78; 5; 5-2011; 1397-1402
1386-1425
CONICET Digital
CONICET
url http://hdl.handle.net/11336/95099
identifier_str_mv Ruiz, Danila Luján; Schiavoni, Maria de Las Mercedes; Laurella, Sergio Luis; Giussi, Juan Martín; Furlong, Jorge J.P.; et al.; The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydes; Pergamon-Elsevier Science Ltd; Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy; 78; 5; 5-2011; 1397-1402
1386-1425
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S1386142511000333
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.saa.2011.01.017
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Pergamon-Elsevier Science Ltd
publisher.none.fl_str_mv Pergamon-Elsevier Science Ltd
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.13397

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