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 behaviour exhibited by a new o-hydroxyphenyl diazepine derivative, when the compound is analysed both in solution and solid state, open 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-enamino form in which the keto group integrate a cyclohexadienone moiety and the aromaticity of the phenol is loss, 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.
Fil: Rocha, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Gil, Diego Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Echeverría, Gustavo Alberto. Universidad Nacional de La Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina
Fil: Piro, Oscar Enrique. Universidad Nacional de La Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina
Fil: Jios, Jorge Luis. Universidad Nacional de La Plata; Argentina. Comision de Investigaciones Cientificas de la Provincia de Buenos Aires. Unidad Plapimu Laseisic.; Argentina
Fil: Ulic, Sonia Elizabeth. Universidad Nacional de La Plata; 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
O-HYDROXYPHENYL-1,4-DIAZEPINE
ENOL-IMINO-KETO-ENAMINE TAUTOMERISM
INTERMOLECULAR INTERACTIONS
STRUCTURAL STUDY
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:11336/119057
Acceder
id CONICETDig_8e35eddadba1aaf60ae2d3ccb6167857
oai_identifier_str oai:ri.conicet.gov.ar:11336/119057
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
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 ElizabethO-HYDROXYPHENYL-1,4-DIAZEPINEENOL-IMINO-KETO-ENAMINE TAUTOMERISMINTERMOLECULAR INTERACTIONSSTRUCTURAL STUDYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The strange tautomeric equilibrium behaviour exhibited by a new o-hydroxyphenyl diazepine derivative, when the compound is analysed both in solution and solid state, open 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-enamino form in which the keto group integrate a cyclohexadienone moiety and the aromaticity of the phenol is loss, 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.Fil: Rocha, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Gil, Diego Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Echeverría, Gustavo Alberto. Universidad Nacional de La Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; ArgentinaFil: Piro, Oscar Enrique. Universidad Nacional de La Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; ArgentinaFil: Jios, Jorge Luis. Universidad Nacional de La Plata; Argentina. Comision de Investigaciones Cientificas de la Provincia de Buenos Aires. Unidad Plapimu Laseisic.; ArgentinaFil: Ulic, Sonia Elizabeth. Universidad Nacional de La Plata; 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"; ArgentinaAmerican Chemical Society2019-08info: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/11336/119057Rocha, Mariana; Gil, Diego Mauricio; Echeverría, Gustavo Alberto; Piro, Oscar Enrique; Jios, Jorge Luis; et al.; Enol-imino-keto-enamine tautomerism in a diazepine derivative: How decisive are the intermolecular interactions in the equilibrium?; American Chemical Society; Journal of Organic Chemistry; 84; 17; 8-2019; 11042-110530022-3263CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/acs.joc.9b01533info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.9b01533info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:09:10Zoai:ri.conicet.gov.ar:11336/119057instacron: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 11:09:11.224CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
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
O-HYDROXYPHENYL-1,4-DIAZEPINE
ENOL-IMINO-KETO-ENAMINE TAUTOMERISM
INTERMOLECULAR INTERACTIONS
STRUCTURAL STUDY
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 O-HYDROXYPHENYL-1,4-DIAZEPINE
ENOL-IMINO-KETO-ENAMINE TAUTOMERISM
INTERMOLECULAR INTERACTIONS
STRUCTURAL STUDY
topic O-HYDROXYPHENYL-1,4-DIAZEPINE
ENOL-IMINO-KETO-ENAMINE TAUTOMERISM
INTERMOLECULAR INTERACTIONS
STRUCTURAL STUDY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The strange tautomeric equilibrium behaviour exhibited by a new o-hydroxyphenyl diazepine derivative, when the compound is analysed both in solution and solid state, open 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-enamino form in which the keto group integrate a cyclohexadienone moiety and the aromaticity of the phenol is loss, 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.
Fil: Rocha, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Gil, Diego Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Echeverría, Gustavo Alberto. Universidad Nacional de La Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina
Fil: Piro, Oscar Enrique. Universidad Nacional de La Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina
Fil: Jios, Jorge Luis. Universidad Nacional de La Plata; Argentina. Comision de Investigaciones Cientificas de la Provincia de Buenos Aires. Unidad Plapimu Laseisic.; Argentina
Fil: Ulic, Sonia Elizabeth. Universidad Nacional de La Plata; 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 The strange tautomeric equilibrium behaviour exhibited by a new o-hydroxyphenyl diazepine derivative, when the compound is analysed both in solution and solid state, open 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-enamino form in which the keto group integrate a cyclohexadienone moiety and the aromaticity of the phenol is loss, 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
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/11336/119057
Rocha, Mariana; Gil, Diego Mauricio; Echeverría, Gustavo Alberto; Piro, Oscar Enrique; Jios, Jorge Luis; et al.; Enol-imino-keto-enamine tautomerism in a diazepine derivative: How decisive are the intermolecular interactions in the equilibrium?; American Chemical Society; Journal of Organic Chemistry; 84; 17; 8-2019; 11042-11053
0022-3263
CONICET Digital
CONICET
url http://hdl.handle.net/11336/119057
identifier_str_mv Rocha, Mariana; Gil, Diego Mauricio; Echeverría, Gustavo Alberto; Piro, Oscar Enrique; Jios, Jorge Luis; et al.; Enol-imino-keto-enamine tautomerism in a diazepine derivative: How decisive are the intermolecular interactions in the equilibrium?; American Chemical Society; Journal of Organic Chemistry; 84; 17; 8-2019; 11042-11053
0022-3263
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/acs.joc.9b01533
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.9b01533
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 American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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 12.982451

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