Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylate

Autores
Lopes, Susy; Nunes, Cláudio M.; Gomez Zavaglia, Andrea; Pinho e Melo, Teresa M. V. D.; Fausto, Rui
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Methyl 4-chloro-5-phenylisoxazole-3-carboxylate (MCPIC) has been synthesized, isolated in low temperature argon and xenon matrices, and studied by FTIR spectroscopy. The characterization of the low energy conformers of MCPIC was made by undertaking a systematic investigation of the DFT(B3LYP)/6-311þþG(d,p) potential energy surface of the molecule. The theoretical calculations predicted the existence of three low energy conformers. Two of them (I and II) were observed experimentally in the cryogenic matrices. The third one (III) was found to be converted into conformer II during deposition of the matrices, a result that is in agreement with the predicted low III f II energy barrier (<0.3 kJ mol-1). In situ UV irradiation (λ > 235 nm) of matrix-isolated MCPIC yielded as final photoproduct the corresponding oxazole (methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate). Identification of the azirine and nitrile-ylide intermediates in the spectra of the irradiated matrices confirmed their mechanistic relevance in the isoxazolefoxazole photoisomerization.
Fil: Lopes, Susy. Universidad de Coimbra; Portugal
Fil: Nunes, Cláudio M.. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina
Fil: Pinho e Melo, Teresa M. V. D.. Universidad de Coimbra; Portugal
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
Materia
Deposition
Infrared Light
Energy
Molecular structure
Potential energy
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:11336/109703
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/109703
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylateLopes, SusyNunes, Cláudio M.Gomez Zavaglia, AndreaPinho e Melo, Teresa M. V. D.Fausto, RuiDepositionInfrared LightEnergyMolecular structurePotential energyhttps://purl.org/becyt/ford/2.11https://purl.org/becyt/ford/2Methyl 4-chloro-5-phenylisoxazole-3-carboxylate (MCPIC) has been synthesized, isolated in low temperature argon and xenon matrices, and studied by FTIR spectroscopy. The characterization of the low energy conformers of MCPIC was made by undertaking a systematic investigation of the DFT(B3LYP)/6-311þþG(d,p) potential energy surface of the molecule. The theoretical calculations predicted the existence of three low energy conformers. Two of them (I and II) were observed experimentally in the cryogenic matrices. The third one (III) was found to be converted into conformer II during deposition of the matrices, a result that is in agreement with the predicted low III f II energy barrier (<0.3 kJ mol-1). In situ UV irradiation (λ > 235 nm) of matrix-isolated MCPIC yielded as final photoproduct the corresponding oxazole (methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate). Identification of the azirine and nitrile-ylide intermediates in the spectra of the irradiated matrices confirmed their mechanistic relevance in the isoxazolefoxazole photoisomerization.Fil: Lopes, Susy. Universidad de Coimbra; PortugalFil: Nunes, Cláudio M.. Universidad de Coimbra; PortugalFil: Gomez Zavaglia, Andrea. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; ArgentinaFil: Pinho e Melo, Teresa M. V. D.. Universidad de Coimbra; PortugalFil: Fausto, Rui. Universidad de Coimbra; PortugalAmerican Chemical Society2011-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/109703Lopes, Susy; Nunes, Cláudio M.; Gomez Zavaglia, Andrea; Pinho e Melo, Teresa M. V. D.; Fausto, Rui; Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylate; American Chemical Society; Journal of Physical Chemistry A; 115; 7; 2-2011; 1199-12091089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/pdf/10.1021/jp110705c#info:eu-repo/semantics/altIdentifier/doi/10.1021/jp110705cinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:05:46Zoai:ri.conicet.gov.ar:11336/109703instacron: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 10:05:46.483CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylate
title Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylate
spellingShingle Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylate
Lopes, Susy
Deposition
Infrared Light
Energy
Molecular structure
Potential energy
title_short Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylate
title_full Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylate
title_fullStr Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylate
title_full_unstemmed Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylate
title_sort Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylate
dc.creator.none.fl_str_mv Lopes, Susy
Nunes, Cláudio M.
Gomez Zavaglia, Andrea
Pinho e Melo, Teresa M. V. D.
Fausto, Rui
author Lopes, Susy
author_facet Lopes, Susy
Nunes, Cláudio M.
Gomez Zavaglia, Andrea
Pinho e Melo, Teresa M. V. D.
Fausto, Rui
author_role author
author2 Nunes, Cláudio M.
Gomez Zavaglia, Andrea
Pinho e Melo, Teresa M. V. D.
Fausto, Rui
author2_role author
author
author
author
dc.subject.none.fl_str_mv Deposition
Infrared Light
Energy
Molecular structure
Potential energy
topic Deposition
Infrared Light
Energy
Molecular structure
Potential energy
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.11
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv Methyl 4-chloro-5-phenylisoxazole-3-carboxylate (MCPIC) has been synthesized, isolated in low temperature argon and xenon matrices, and studied by FTIR spectroscopy. The characterization of the low energy conformers of MCPIC was made by undertaking a systematic investigation of the DFT(B3LYP)/6-311þþG(d,p) potential energy surface of the molecule. The theoretical calculations predicted the existence of three low energy conformers. Two of them (I and II) were observed experimentally in the cryogenic matrices. The third one (III) was found to be converted into conformer II during deposition of the matrices, a result that is in agreement with the predicted low III f II energy barrier (<0.3 kJ mol-1). In situ UV irradiation (λ > 235 nm) of matrix-isolated MCPIC yielded as final photoproduct the corresponding oxazole (methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate). Identification of the azirine and nitrile-ylide intermediates in the spectra of the irradiated matrices confirmed their mechanistic relevance in the isoxazolefoxazole photoisomerization.
Fil: Lopes, Susy. Universidad de Coimbra; Portugal
Fil: Nunes, Cláudio M.. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina
Fil: Pinho e Melo, Teresa M. V. D.. Universidad de Coimbra; Portugal
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
description Methyl 4-chloro-5-phenylisoxazole-3-carboxylate (MCPIC) has been synthesized, isolated in low temperature argon and xenon matrices, and studied by FTIR spectroscopy. The characterization of the low energy conformers of MCPIC was made by undertaking a systematic investigation of the DFT(B3LYP)/6-311þþG(d,p) potential energy surface of the molecule. The theoretical calculations predicted the existence of three low energy conformers. Two of them (I and II) were observed experimentally in the cryogenic matrices. The third one (III) was found to be converted into conformer II during deposition of the matrices, a result that is in agreement with the predicted low III f II energy barrier (<0.3 kJ mol-1). In situ UV irradiation (λ > 235 nm) of matrix-isolated MCPIC yielded as final photoproduct the corresponding oxazole (methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate). Identification of the azirine and nitrile-ylide intermediates in the spectra of the irradiated matrices confirmed their mechanistic relevance in the isoxazolefoxazole photoisomerization.
publishDate 2011
dc.date.none.fl_str_mv 2011-02
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/11336/109703
Lopes, Susy; Nunes, Cláudio M.; Gomez Zavaglia, Andrea; Pinho e Melo, Teresa M. V. D.; Fausto, Rui; Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylate; American Chemical Society; Journal of Physical Chemistry A; 115; 7; 2-2011; 1199-1209
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/109703
identifier_str_mv Lopes, Susy; Nunes, Cláudio M.; Gomez Zavaglia, Andrea; Pinho e Melo, Teresa M. V. D.; Fausto, Rui; Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylate; American Chemical Society; Journal of Physical Chemistry A; 115; 7; 2-2011; 1199-1209
1089-5639
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://pubs.acs.org/doi/pdf/10.1021/jp110705c#
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp110705c
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 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 12.885934

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