Analysis of Tautomerism in beta-Ketobutanamides by Nuclear Magnetic Resonance: Substituent, Temperature and Solvent Effects

Autores
Laurella, Sergio Luis
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
β-ketoamides are versatile intermediates for the synthesis of several heterocycles and they are also relevant compounds in biological systems, with their tautomeric equilibria being a crucial aspect to be studied in order to understand their chemical and biological behaviour. Tautomeric equilibria of a series of β-ketobutanamides were analyzed by means of 1HNMR, determining that ketoamide and Z-enolamide are the main tautomeric species in solution, both presenting internal hydrogen bonds. Keto-enol equilibrium predominates over other possible tautomerisms (e.g. amide-imidol). The enol tautomer appears to be favoured by electron withdrawing substituents and non-protic solvents. Thermodynamic parameters ΔH and ΔS were determined in CDCl3 and DMSO-d6, showing that the keto-enol equilibria are exothermic and require a molecule order increase.
Fil: Laurella, Sergio Luis. 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. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Materia
BETA-KETOAMIDES
KETO-ENOL EQUILIBRIUM
NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY
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:11336/131681
Acceder
id CONICETDig_93604ddfb883712c8aed30aa3ea635da
oai_identifier_str oai:ri.conicet.gov.ar:11336/131681
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Analysis of Tautomerism in beta-Ketobutanamides by Nuclear Magnetic Resonance: Substituent, Temperature and Solvent EffectsLaurella, Sergio LuisBETA-KETOAMIDESKETO-ENOL EQUILIBRIUMNUCLEAR MAGNETIC RESONANCE SPECTROSCOPYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1β-ketoamides are versatile intermediates for the synthesis of several heterocycles and they are also relevant compounds in biological systems, with their tautomeric equilibria being a crucial aspect to be studied in order to understand their chemical and biological behaviour. Tautomeric equilibria of a series of β-ketobutanamides were analyzed by means of 1HNMR, determining that ketoamide and Z-enolamide are the main tautomeric species in solution, both presenting internal hydrogen bonds. Keto-enol equilibrium predominates over other possible tautomerisms (e.g. amide-imidol). The enol tautomer appears to be favoured by electron withdrawing substituents and non-protic solvents. Thermodynamic parameters ΔH and ΔS were determined in CDCl3 and DMSO-d6, showing that the keto-enol equilibria are exothermic and require a molecule order increase.Fil: Laurella, Sergio Luis. 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. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaLifescience Global2012-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/131681Laurella, Sergio Luis; Analysis of Tautomerism in beta-Ketobutanamides by Nuclear Magnetic Resonance: Substituent, Temperature and Solvent Effects; Lifescience Global; Journal of Applied Solution Chemistry and Modeling; 1; 1; 8-2012; 1-71929-5030CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.lifescienceglobal.com/pms/index.php/JASCM/article/view/527info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:48:19Zoai:ri.conicet.gov.ar:11336/131681instacron: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:34982025-10-22 11:48:19.802CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Analysis of Tautomerism in beta-Ketobutanamides by Nuclear Magnetic Resonance: Substituent, Temperature and Solvent Effects
title Analysis of Tautomerism in beta-Ketobutanamides by Nuclear Magnetic Resonance: Substituent, Temperature and Solvent Effects
spellingShingle Analysis of Tautomerism in beta-Ketobutanamides by Nuclear Magnetic Resonance: Substituent, Temperature and Solvent Effects
Laurella, Sergio Luis
BETA-KETOAMIDES
KETO-ENOL EQUILIBRIUM
NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY
title_short Analysis of Tautomerism in beta-Ketobutanamides by Nuclear Magnetic Resonance: Substituent, Temperature and Solvent Effects
title_full Analysis of Tautomerism in beta-Ketobutanamides by Nuclear Magnetic Resonance: Substituent, Temperature and Solvent Effects
title_fullStr Analysis of Tautomerism in beta-Ketobutanamides by Nuclear Magnetic Resonance: Substituent, Temperature and Solvent Effects
title_full_unstemmed Analysis of Tautomerism in beta-Ketobutanamides by Nuclear Magnetic Resonance: Substituent, Temperature and Solvent Effects
title_sort Analysis of Tautomerism in beta-Ketobutanamides by Nuclear Magnetic Resonance: Substituent, Temperature and Solvent Effects
dc.creator.none.fl_str_mv Laurella, Sergio Luis
author Laurella, Sergio Luis
author_facet Laurella, Sergio Luis
author_role author
dc.subject.none.fl_str_mv BETA-KETOAMIDES
KETO-ENOL EQUILIBRIUM
NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY
topic BETA-KETOAMIDES
KETO-ENOL EQUILIBRIUM
NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv β-ketoamides are versatile intermediates for the synthesis of several heterocycles and they are also relevant compounds in biological systems, with their tautomeric equilibria being a crucial aspect to be studied in order to understand their chemical and biological behaviour. Tautomeric equilibria of a series of β-ketobutanamides were analyzed by means of 1HNMR, determining that ketoamide and Z-enolamide are the main tautomeric species in solution, both presenting internal hydrogen bonds. Keto-enol equilibrium predominates over other possible tautomerisms (e.g. amide-imidol). The enol tautomer appears to be favoured by electron withdrawing substituents and non-protic solvents. Thermodynamic parameters ΔH and ΔS were determined in CDCl3 and DMSO-d6, showing that the keto-enol equilibria are exothermic and require a molecule order increase.
Fil: Laurella, Sergio Luis. 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. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
description β-ketoamides are versatile intermediates for the synthesis of several heterocycles and they are also relevant compounds in biological systems, with their tautomeric equilibria being a crucial aspect to be studied in order to understand their chemical and biological behaviour. Tautomeric equilibria of a series of β-ketobutanamides were analyzed by means of 1HNMR, determining that ketoamide and Z-enolamide are the main tautomeric species in solution, both presenting internal hydrogen bonds. Keto-enol equilibrium predominates over other possible tautomerisms (e.g. amide-imidol). The enol tautomer appears to be favoured by electron withdrawing substituents and non-protic solvents. Thermodynamic parameters ΔH and ΔS were determined in CDCl3 and DMSO-d6, showing that the keto-enol equilibria are exothermic and require a molecule order increase.
publishDate 2012
dc.date.none.fl_str_mv 2012-08
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/11336/131681
Laurella, Sergio Luis; Analysis of Tautomerism in beta-Ketobutanamides by Nuclear Magnetic Resonance: Substituent, Temperature and Solvent Effects; Lifescience Global; Journal of Applied Solution Chemistry and Modeling; 1; 1; 8-2012; 1-7
1929-5030
CONICET Digital
CONICET
url http://hdl.handle.net/11336/131681
identifier_str_mv Laurella, Sergio Luis; Analysis of Tautomerism in beta-Ketobutanamides by Nuclear Magnetic Resonance: Substituent, Temperature and Solvent Effects; Lifescience Global; Journal of Applied Solution Chemistry and Modeling; 1; 1; 8-2012; 1-7
1929-5030
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.lifescienceglobal.com/pms/index.php/JASCM/article/view/527
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
dc.publisher.none.fl_str_mv Lifescience Global
publisher.none.fl_str_mv Lifescience Global
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
_version_ 1846782189650313216
score 12.982451

Publicaciones similares