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
- Institución
- Universidad Nacional de La Plata
- OAI Identificador
- oai:sedici.unlp.edu.ar:10915/124102
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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:UNLP2025-09-29T11:29:33Zoai: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:13292025-09-29 11:29:33.7SEDICI (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 |
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openAccess |
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http://creativecommons.org/licenses/by-nc-sa/4.0/ Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0) |
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