Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids

Autores
Mancini, Pedro M. E.; Della Rosa, Claudia D.; Ormachea, Carla; Kneeteman, Maria Nelida; Domingo, Luis R.
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The reactions between 1-nitronaphthalene 1 and two nucleophilic dienes, Danishefsky´s diene 2 and 1-trimethylsilyloxy-1,3-butadiene 3, to yield phenanthrenols 7 and 8 developed in protic and aprotic ionic liquids (ILs) with an imidazolium cation base permit to conclude that the reactions occur in better experimental conditions than in molecular solvents. The yields obtained with protic ILs are better than those observed with aprotic ILs. In this sense, the higher yields obtained with aprotic ILs, (working at 60ºC, 48 h) are comparable with the lower yields observed in protic ILs (60 ºC, 24 h). DFT calculations for the reaction of 1-nitronaphthalene 1 with diene 3, in the absence and in the presence of tetrafluoroborate of 1-metilimidazolium [HMIM] [BF4] as protic ILs, indicate that this reaction is a domino process that comprises two consecutive processes: i) a polar Diels-Alder (P-DA) reaction between 1 and 3, and ii) an elimination of nitroso acid 5 to yield dihydrophenanthrene 11. Thermodynamic calculations indicate that while the first reaction is the rate-determining step of this domino process, the nitroso acid elimination is the driving force responsible for the formation of dihydrophenanthrene 11. Implicit and explicit solvent effects indicate that while the hydrogen bond formation between HMIM and one oxygen atom of the nitro groups favour the two reactions, implicit solvent effects modelled by PCM decelerate the P-DA reaction by a large solvation of reagents. Finally, DFT analysis of reagents offers an explanation of the catalytic role of protic ILs in these P-DA reactions.
Fil: Mancini, Pedro M. E.. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina
Fil: Della Rosa, Claudia D.. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina
Fil: Ormachea, Carla. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Kneeteman, Maria Nelida. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Domingo, Luis R.. Universidad de Valencia; España
Materia
Diels-Alder
Nitronaphthalenes
Ionic Liquid
Dft
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:11336/15997
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/15997
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquidsMancini, Pedro M. E.Della Rosa, Claudia D.Ormachea, CarlaKneeteman, Maria NelidaDomingo, Luis R.Diels-AlderNitronaphthalenesIonic LiquidDfthttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The reactions between 1-nitronaphthalene 1 and two nucleophilic dienes, Danishefsky´s diene 2 and 1-trimethylsilyloxy-1,3-butadiene 3, to yield phenanthrenols 7 and 8 developed in protic and aprotic ionic liquids (ILs) with an imidazolium cation base permit to conclude that the reactions occur in better experimental conditions than in molecular solvents. The yields obtained with protic ILs are better than those observed with aprotic ILs. In this sense, the higher yields obtained with aprotic ILs, (working at 60ºC, 48 h) are comparable with the lower yields observed in protic ILs (60 ºC, 24 h). DFT calculations for the reaction of 1-nitronaphthalene 1 with diene 3, in the absence and in the presence of tetrafluoroborate of 1-metilimidazolium [HMIM] [BF4] as protic ILs, indicate that this reaction is a domino process that comprises two consecutive processes: i) a polar Diels-Alder (P-DA) reaction between 1 and 3, and ii) an elimination of nitroso acid 5 to yield dihydrophenanthrene 11. Thermodynamic calculations indicate that while the first reaction is the rate-determining step of this domino process, the nitroso acid elimination is the driving force responsible for the formation of dihydrophenanthrene 11. Implicit and explicit solvent effects indicate that while the hydrogen bond formation between HMIM and one oxygen atom of the nitro groups favour the two reactions, implicit solvent effects modelled by PCM decelerate the P-DA reaction by a large solvation of reagents. Finally, DFT analysis of reagents offers an explanation of the catalytic role of protic ILs in these P-DA reactions.Fil: Mancini, Pedro M. E.. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; ArgentinaFil: Della Rosa, Claudia D.. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; ArgentinaFil: Ormachea, Carla. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Kneeteman, Maria Nelida. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Domingo, Luis R.. Universidad de Valencia; EspañaRoyal Society of Chemistry2013info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/vnd.openxmlformats-officedocument.wordprocessingml.documentapplication/pdfhttp://hdl.handle.net/11336/15997Mancini, Pedro M. E.; Della Rosa, Claudia D.; Ormachea, Carla; Kneeteman, Maria Nelida; Domingo, Luis R.; Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids; Royal Society of Chemistry; RSC Advances; 33; 2013; 13825-138342046-2069enginfo:eu-repo/semantics/altIdentifier/doi/10.1039/C3RA42042Finfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/-/content/articlelanding/2013/ra/c3ra42042f#!divAbstractinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:04:16Zoai:ri.conicet.gov.ar:11336/15997instacron: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 10:04:16.755CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids
title Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids
spellingShingle Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids
Mancini, Pedro M. E.
Diels-Alder
Nitronaphthalenes
Ionic Liquid
Dft
title_short Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids
title_full Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids
title_fullStr Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids
title_full_unstemmed Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids
title_sort Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids
dc.creator.none.fl_str_mv Mancini, Pedro M. E.
Della Rosa, Claudia D.
Ormachea, Carla
Kneeteman, Maria Nelida
Domingo, Luis R.
author Mancini, Pedro M. E.
author_facet Mancini, Pedro M. E.
Della Rosa, Claudia D.
Ormachea, Carla
Kneeteman, Maria Nelida
Domingo, Luis R.
author_role author
author2 Della Rosa, Claudia D.
Ormachea, Carla
Kneeteman, Maria Nelida
Domingo, Luis R.
author2_role author
author
author
author
dc.subject.none.fl_str_mv Diels-Alder
Nitronaphthalenes
Ionic Liquid
Dft
topic Diels-Alder
Nitronaphthalenes
Ionic Liquid
Dft
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 reactions between 1-nitronaphthalene 1 and two nucleophilic dienes, Danishefsky´s diene 2 and 1-trimethylsilyloxy-1,3-butadiene 3, to yield phenanthrenols 7 and 8 developed in protic and aprotic ionic liquids (ILs) with an imidazolium cation base permit to conclude that the reactions occur in better experimental conditions than in molecular solvents. The yields obtained with protic ILs are better than those observed with aprotic ILs. In this sense, the higher yields obtained with aprotic ILs, (working at 60ºC, 48 h) are comparable with the lower yields observed in protic ILs (60 ºC, 24 h). DFT calculations for the reaction of 1-nitronaphthalene 1 with diene 3, in the absence and in the presence of tetrafluoroborate of 1-metilimidazolium [HMIM] [BF4] as protic ILs, indicate that this reaction is a domino process that comprises two consecutive processes: i) a polar Diels-Alder (P-DA) reaction between 1 and 3, and ii) an elimination of nitroso acid 5 to yield dihydrophenanthrene 11. Thermodynamic calculations indicate that while the first reaction is the rate-determining step of this domino process, the nitroso acid elimination is the driving force responsible for the formation of dihydrophenanthrene 11. Implicit and explicit solvent effects indicate that while the hydrogen bond formation between HMIM and one oxygen atom of the nitro groups favour the two reactions, implicit solvent effects modelled by PCM decelerate the P-DA reaction by a large solvation of reagents. Finally, DFT analysis of reagents offers an explanation of the catalytic role of protic ILs in these P-DA reactions.
Fil: Mancini, Pedro M. E.. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina
Fil: Della Rosa, Claudia D.. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina
Fil: Ormachea, Carla. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Kneeteman, Maria Nelida. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Domingo, Luis R.. Universidad de Valencia; España
description The reactions between 1-nitronaphthalene 1 and two nucleophilic dienes, Danishefsky´s diene 2 and 1-trimethylsilyloxy-1,3-butadiene 3, to yield phenanthrenols 7 and 8 developed in protic and aprotic ionic liquids (ILs) with an imidazolium cation base permit to conclude that the reactions occur in better experimental conditions than in molecular solvents. The yields obtained with protic ILs are better than those observed with aprotic ILs. In this sense, the higher yields obtained with aprotic ILs, (working at 60ºC, 48 h) are comparable with the lower yields observed in protic ILs (60 ºC, 24 h). DFT calculations for the reaction of 1-nitronaphthalene 1 with diene 3, in the absence and in the presence of tetrafluoroborate of 1-metilimidazolium [HMIM] [BF4] as protic ILs, indicate that this reaction is a domino process that comprises two consecutive processes: i) a polar Diels-Alder (P-DA) reaction between 1 and 3, and ii) an elimination of nitroso acid 5 to yield dihydrophenanthrene 11. Thermodynamic calculations indicate that while the first reaction is the rate-determining step of this domino process, the nitroso acid elimination is the driving force responsible for the formation of dihydrophenanthrene 11. Implicit and explicit solvent effects indicate that while the hydrogen bond formation between HMIM and one oxygen atom of the nitro groups favour the two reactions, implicit solvent effects modelled by PCM decelerate the P-DA reaction by a large solvation of reagents. Finally, DFT analysis of reagents offers an explanation of the catalytic role of protic ILs in these P-DA reactions.
publishDate 2013
dc.date.none.fl_str_mv 2013
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/11336/15997
Mancini, Pedro M. E.; Della Rosa, Claudia D.; Ormachea, Carla; Kneeteman, Maria Nelida; Domingo, Luis R.; Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids; Royal Society of Chemistry; RSC Advances; 33; 2013; 13825-13834
2046-2069
url http://hdl.handle.net/11336/15997
identifier_str_mv Mancini, Pedro M. E.; Della Rosa, Claudia D.; Ormachea, Carla; Kneeteman, Maria Nelida; Domingo, Luis R.; Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids; Royal Society of Chemistry; RSC Advances; 33; 2013; 13825-13834
2046-2069
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/C3RA42042F
info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/-/content/articlelanding/2013/ra/c3ra42042f#!divAbstract
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/vnd.openxmlformats-officedocument.wordprocessingml.document
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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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