Enol-imino−Keto-enamine Tautomerism in a Diazepine Derivative: How Decisive Are the Intermolecular Interactions in the Equilibrium?

Autores
Rocha, Mariana; Gil, Diego Mauricio; Echeverría, Gustavo Alberto; Piro, Oscar Enrique; Jios, Jorge Luis; Ulic, Sonia Elizabeth
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The strange tautomeric equilibrium behavior exhibited by a new o-hydroxyphenyl diazepine derivative when the compound is analyzed both in solution and solid state opens the structural study of the enol-imino-keto-enamine forms and the influence of the intermolecular interactions in their equilibrium. The expected enol-imino form, in which the enol is part of a phenyl system and a strong O-H···N intramolecular hydrogen bond is established, results the most stable tautomer in gas phase (theoretical calculations) and was detected by NMR spectroscopy when the compound was dissolved in aprotic solvents. Nevertheless, the keto-enamine form, in which the keto group integrates a cyclohexadienone moiety and the aromaticity of the phenol is lost, was the only tautomer in the crystal lattice according to single-crystal X-ray diffraction, vibrational spectroscopy, and diffuse reflectance results. The last form was also found as the main tautomer in UV-vis and NMR spectroscopy when a protic solvent was employed.
Puede accederse a los datos primarios de este trabajo haciendo clic en "Documentos relacionados".
Facultad de Ciencias Exactas
Instituto de Física La Plata
Planta Piloto Multipropósito - Laboratorio de Servicios a la Industria y al Sistema Científico
Centro de Química Inorgánica
Materia
Ciencias Exactas
Física
Química
diazepine derivative
tautomerism
NMR spectroscopy
molecular interactions
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/124102
Acceder
id SEDICI_25568e8fbc67fd662b35d384ab8115b6
oai_identifier_str oai:sedici.unlp.edu.ar:10915/124102
network_acronym_str SEDICI
repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Enol-imino−Keto-enamine Tautomerism in a Diazepine Derivative: How Decisive Are the Intermolecular Interactions in the Equilibrium?Rocha, MarianaGil, Diego MauricioEcheverría, Gustavo AlbertoPiro, Oscar EnriqueJios, Jorge LuisUlic, Sonia ElizabethCiencias ExactasFísicaQuímicadiazepine derivativetautomerismNMR spectroscopymolecular interactionsThe strange tautomeric equilibrium behavior exhibited by a new o-hydroxyphenyl diazepine derivative when the compound is analyzed both in solution and solid state opens the structural study of the enol-imino-keto-enamine forms and the influence of the intermolecular interactions in their equilibrium. The expected enol-imino form, in which the enol is part of a phenyl system and a strong O-H···N intramolecular hydrogen bond is established, results the most stable tautomer in gas phase (theoretical calculations) and was detected by NMR spectroscopy when the compound was dissolved in aprotic solvents. Nevertheless, the keto-enamine form, in which the keto group integrates a cyclohexadienone moiety and the aromaticity of the phenol is lost, was the only tautomer in the crystal lattice according to single-crystal X-ray diffraction, vibrational spectroscopy, and diffuse reflectance results. The last form was also found as the main tautomer in UV-vis and NMR spectroscopy when a protic solvent was employed.Puede accederse a los datos primarios de este trabajo haciendo clic en "Documentos relacionados".Facultad de Ciencias ExactasInstituto de Física La PlataPlanta Piloto Multipropósito - Laboratorio de Servicios a la Industria y al Sistema CientíficoCentro de Química Inorgánica2019-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf11042-11053http://sedici.unlp.edu.ar/handle/10915/124102enginfo:eu-repo/semantics/altIdentifier/issn/1520-6904info:eu-repo/semantics/altIdentifier/issn/0022-3263info:eu-repo/semantics/altIdentifier/pmid/31419129info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.9b01533info:eu-repo/semantics/reference/hdl/10915/124104info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-10-22T17:10:25Zoai:sedici.unlp.edu.ar:10915/124102Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-10-22 17:10:25.587SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Enol-imino−Keto-enamine Tautomerism in a Diazepine Derivative: How Decisive Are the Intermolecular Interactions in the Equilibrium?
title Enol-imino−Keto-enamine Tautomerism in a Diazepine Derivative: How Decisive Are the Intermolecular Interactions in the Equilibrium?
spellingShingle Enol-imino−Keto-enamine Tautomerism in a Diazepine Derivative: How Decisive Are the Intermolecular Interactions in the Equilibrium?
Rocha, Mariana
Ciencias Exactas
Física
Química
diazepine derivative
tautomerism
NMR spectroscopy
molecular interactions
title_short Enol-imino−Keto-enamine Tautomerism in a Diazepine Derivative: How Decisive Are the Intermolecular Interactions in the Equilibrium?
title_full Enol-imino−Keto-enamine Tautomerism in a Diazepine Derivative: How Decisive Are the Intermolecular Interactions in the Equilibrium?
title_fullStr Enol-imino−Keto-enamine Tautomerism in a Diazepine Derivative: How Decisive Are the Intermolecular Interactions in the Equilibrium?
title_full_unstemmed Enol-imino−Keto-enamine Tautomerism in a Diazepine Derivative: How Decisive Are the Intermolecular Interactions in the Equilibrium?
title_sort Enol-imino−Keto-enamine Tautomerism in a Diazepine Derivative: How Decisive Are the Intermolecular Interactions in the Equilibrium?
dc.creator.none.fl_str_mv Rocha, Mariana
Gil, Diego Mauricio
Echeverría, Gustavo Alberto
Piro, Oscar Enrique
Jios, Jorge Luis
Ulic, Sonia Elizabeth
author Rocha, Mariana
author_facet Rocha, Mariana
Gil, Diego Mauricio
Echeverría, Gustavo Alberto
Piro, Oscar Enrique
Jios, Jorge Luis
Ulic, Sonia Elizabeth
author_role author
author2 Gil, Diego Mauricio
Echeverría, Gustavo Alberto
Piro, Oscar Enrique
Jios, Jorge Luis
Ulic, Sonia Elizabeth
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Ciencias Exactas
Física
Química
diazepine derivative
tautomerism
NMR spectroscopy
molecular interactions
topic Ciencias Exactas
Física
Química
diazepine derivative
tautomerism
NMR spectroscopy
molecular interactions
dc.description.none.fl_txt_mv The strange tautomeric equilibrium behavior exhibited by a new o-hydroxyphenyl diazepine derivative when the compound is analyzed both in solution and solid state opens the structural study of the enol-imino-keto-enamine forms and the influence of the intermolecular interactions in their equilibrium. The expected enol-imino form, in which the enol is part of a phenyl system and a strong O-H···N intramolecular hydrogen bond is established, results the most stable tautomer in gas phase (theoretical calculations) and was detected by NMR spectroscopy when the compound was dissolved in aprotic solvents. Nevertheless, the keto-enamine form, in which the keto group integrates a cyclohexadienone moiety and the aromaticity of the phenol is lost, was the only tautomer in the crystal lattice according to single-crystal X-ray diffraction, vibrational spectroscopy, and diffuse reflectance results. The last form was also found as the main tautomer in UV-vis and NMR spectroscopy when a protic solvent was employed.
Puede accederse a los datos primarios de este trabajo haciendo clic en "Documentos relacionados".
Facultad de Ciencias Exactas
Instituto de Física La Plata
Planta Piloto Multipropósito - Laboratorio de Servicios a la Industria y al Sistema Científico
Centro de Química Inorgánica
description The strange tautomeric equilibrium behavior exhibited by a new o-hydroxyphenyl diazepine derivative when the compound is analyzed both in solution and solid state opens the structural study of the enol-imino-keto-enamine forms and the influence of the intermolecular interactions in their equilibrium. The expected enol-imino form, in which the enol is part of a phenyl system and a strong O-H···N intramolecular hydrogen bond is established, results the most stable tautomer in gas phase (theoretical calculations) and was detected by NMR spectroscopy when the compound was dissolved in aprotic solvents. Nevertheless, the keto-enamine form, in which the keto group integrates a cyclohexadienone moiety and the aromaticity of the phenol is lost, was the only tautomer in the crystal lattice according to single-crystal X-ray diffraction, vibrational spectroscopy, and diffuse reflectance results. The last form was also found as the main tautomer in UV-vis and NMR spectroscopy when a protic solvent was employed.
publishDate 2019
dc.date.none.fl_str_mv 2019-08
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/10915/124102
url http://sedici.unlp.edu.ar/handle/10915/124102
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/1520-6904
info:eu-repo/semantics/altIdentifier/issn/0022-3263
info:eu-repo/semantics/altIdentifier/pmid/31419129
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.9b01533
info:eu-repo/semantics/reference/hdl/10915/124104
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
dc.format.none.fl_str_mv application/pdf
11042-11053
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instname:Universidad Nacional de La Plata
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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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