Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy study

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
(Z)-3-Azido-3-methoxycarbonyl-2-chloro-acrylophenone (MACBP) has been synthesized, isolated in low temperature argon and xenon matrices and studied by FTIR spectroscopy, complemented by DFT(B3LYP)/6-311++G(d,p) calculations. The molecule was characterized both structurally and spectroscopically, and its photochemistry used to probe the mechanism of photo-induced conversion of 3-azido-acrylophenones into oxazoles. In situ UV irradiation (λ = 235 nm) of matrix-isolated MACBP yielded as primary photoproduct a 2H-azirine, which undergoes subsequent photoisomerization to methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate. In a competitive process, a ketenimine is also formed upon photolysis of MACBP. The reported results indicate that this ketenimine must be formed from the starting 3-azido-acrylophenone via a Curtius type concerted rearrangement.
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
3-Azido-acrylophenones
2H-Azirines
Oxazoles
Ketenimines
Matrix isolation
IR spectroscopy
DFT(B3LYP)/6-311þþG(d,p) calculations
Conformational analysis
Photochemistry
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:11336/109794
Acceder
id CONICETDig_b8b15d0496d11473b5224ec48ab12fa4
oai_identifier_str oai:ri.conicet.gov.ar:11336/109794
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy studyLopes, SusyNunes, Cláudio M.Gomez Zavaglia, AndreaPinho e Melo, Teresa M.V.D.Fausto, Rui3-Azido-acrylophenones2H-AzirinesOxazolesKeteniminesMatrix isolationIR spectroscopyDFT(B3LYP)/6-311þþG(d,p) calculationsConformational analysisPhotochemistryhttps://purl.org/becyt/ford/2.11https://purl.org/becyt/ford/2(Z)-3-Azido-3-methoxycarbonyl-2-chloro-acrylophenone (MACBP) has been synthesized, isolated in low temperature argon and xenon matrices and studied by FTIR spectroscopy, complemented by DFT(B3LYP)/6-311++G(d,p) calculations. The molecule was characterized both structurally and spectroscopically, and its photochemistry used to probe the mechanism of photo-induced conversion of 3-azido-acrylophenones into oxazoles. In situ UV irradiation (λ = 235 nm) of matrix-isolated MACBP yielded as primary photoproduct a 2H-azirine, which undergoes subsequent photoisomerization to methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate. In a competitive process, a ketenimine is also formed upon photolysis of MACBP. The reported results indicate that this ketenimine must be formed from the starting 3-azido-acrylophenone via a Curtius type concerted rearrangement.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; PortugalPergamon-Elsevier Science Ltd2011-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/109794Lopes, Susy; Nunes, Cláudio M.; Gomez Zavaglia, Andrea; Pinho e Melo, Teresa M.V.D.; Fausto, Rui; Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy study; Pergamon-Elsevier Science Ltd; Tetrahedron; 67; 40; 10-2011; 7794-78040040-40201464-5416CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0040402011011483info:eu-repo/semantics/altIdentifier/doi/10.1016/j.tet.2011.07.084info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-12-23T14:23:29Zoai:ri.conicet.gov.ar:11336/109794instacron: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:34982025-12-23 14:23:30.098CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy study
title Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy study
spellingShingle Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy study
Lopes, Susy
3-Azido-acrylophenones
2H-Azirines
Oxazoles
Ketenimines
Matrix isolation
IR spectroscopy
DFT(B3LYP)/6-311þþG(d,p) calculations
Conformational analysis
Photochemistry
title_short Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy study
title_full Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy study
title_fullStr Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy study
title_full_unstemmed Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy study
title_sort Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy study
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 3-Azido-acrylophenones
2H-Azirines
Oxazoles
Ketenimines
Matrix isolation
IR spectroscopy
DFT(B3LYP)/6-311þþG(d,p) calculations
Conformational analysis
Photochemistry
topic 3-Azido-acrylophenones
2H-Azirines
Oxazoles
Ketenimines
Matrix isolation
IR spectroscopy
DFT(B3LYP)/6-311þþG(d,p) calculations
Conformational analysis
Photochemistry
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.11
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv (Z)-3-Azido-3-methoxycarbonyl-2-chloro-acrylophenone (MACBP) has been synthesized, isolated in low temperature argon and xenon matrices and studied by FTIR spectroscopy, complemented by DFT(B3LYP)/6-311++G(d,p) calculations. The molecule was characterized both structurally and spectroscopically, and its photochemistry used to probe the mechanism of photo-induced conversion of 3-azido-acrylophenones into oxazoles. In situ UV irradiation (λ = 235 nm) of matrix-isolated MACBP yielded as primary photoproduct a 2H-azirine, which undergoes subsequent photoisomerization to methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate. In a competitive process, a ketenimine is also formed upon photolysis of MACBP. The reported results indicate that this ketenimine must be formed from the starting 3-azido-acrylophenone via a Curtius type concerted rearrangement.
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 (Z)-3-Azido-3-methoxycarbonyl-2-chloro-acrylophenone (MACBP) has been synthesized, isolated in low temperature argon and xenon matrices and studied by FTIR spectroscopy, complemented by DFT(B3LYP)/6-311++G(d,p) calculations. The molecule was characterized both structurally and spectroscopically, and its photochemistry used to probe the mechanism of photo-induced conversion of 3-azido-acrylophenones into oxazoles. In situ UV irradiation (λ = 235 nm) of matrix-isolated MACBP yielded as primary photoproduct a 2H-azirine, which undergoes subsequent photoisomerization to methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate. In a competitive process, a ketenimine is also formed upon photolysis of MACBP. The reported results indicate that this ketenimine must be formed from the starting 3-azido-acrylophenone via a Curtius type concerted rearrangement.
publishDate 2011
dc.date.none.fl_str_mv 2011-10
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/11336/109794
Lopes, Susy; Nunes, Cláudio M.; Gomez Zavaglia, Andrea; Pinho e Melo, Teresa M.V.D.; Fausto, Rui; Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy study; Pergamon-Elsevier Science Ltd; Tetrahedron; 67; 40; 10-2011; 7794-7804
0040-4020
1464-5416
CONICET Digital
CONICET
url http://hdl.handle.net/11336/109794
identifier_str_mv Lopes, Susy; Nunes, Cláudio M.; Gomez Zavaglia, Andrea; Pinho e Melo, Teresa M.V.D.; Fausto, Rui; Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy study; Pergamon-Elsevier Science Ltd; Tetrahedron; 67; 40; 10-2011; 7794-7804
0040-4020
1464-5416
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://www.sciencedirect.com/science/article/abs/pii/S0040402011011483
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.tet.2011.07.084
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 Pergamon-Elsevier Science Ltd
publisher.none.fl_str_mv Pergamon-Elsevier Science Ltd
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
_version_ 1852335656821325824
score 12.952241

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