Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2H-azirines

Autores
Gomez Zavaglia, Andrea; Kaczor, Agnieszka; Cardoso, Ana Lucía; Pinho e Melo, Teresa M.V.D.; Fausto, Rui
Año de publicación
2007
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this study, the UV induced photochemical reactions of two 2H-azirines – methyl 2-chloro-3-methyl-2H-azirine-2-carboxylate (MCMAC) and methyl 3-methyl-2H-azirine-2-carboxylate (MMAC) – isolated in argon matrices are compared. For both compounds, irradiation with λ > 235 nm led to observation of two primary photoprocesses: (a) CC bond cleavage, with production of nitrile ylides (P1-type products), and (b) CN bond cleavage, with production of methylated ketene imines (P2-type products). However, subsequent photoprocesses were found to be different in the two cases. In MCMAC, both primary photoproducts were shown to undergo further reactions: P1-type products decarboxylate, giving [(1-chloroethylidene)imino]ethanide, which bears a CN+C− group (P3-type product); P2-type products decarbonylate, yielding a substituted ylidene methanamine (P4-type product). In MMAC, only P2-type primary photoproducts appeared to react, undergoing decarbonylation or decarboxylation (both reactions leading to P4-type products), whereas P1-type products were found to be non-reactive. The non-observation of any secondary photoproduct resulting from photolysis of P1-MMAC revealed the higher photostability of this species when compared with the corresponding photoproduct obtained from MCMAC.
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. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Universidad de Coimbra; Portugal
Fil: Kaczor, Agnieszka. Universidad de Coimbra; Portugal
Fil: Cardoso, Ana Lucía. Universidad de Coimbra; Portugal
Fil: Pinho e Melo, Teresa M.V.D.. Universidad de Coimbra; Portugal
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
Materia
2H-azirines
Photolysis
Matrix isolation FTIR spectroscopy
Substituent effects
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:11336/113288
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/113288
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2H-azirinesGomez Zavaglia, AndreaKaczor, AgnieszkaCardoso, Ana LucíaPinho e Melo, Teresa M.V.D.Fausto, Rui2H-azirinesPhotolysisMatrix isolation FTIR spectroscopySubstituent effectshttps://purl.org/becyt/ford/2.11https://purl.org/becyt/ford/2In this study, the UV induced photochemical reactions of two 2H-azirines – methyl 2-chloro-3-methyl-2H-azirine-2-carboxylate (MCMAC) and methyl 3-methyl-2H-azirine-2-carboxylate (MMAC) – isolated in argon matrices are compared. For both compounds, irradiation with λ > 235 nm led to observation of two primary photoprocesses: (a) CC bond cleavage, with production of nitrile ylides (P1-type products), and (b) CN bond cleavage, with production of methylated ketene imines (P2-type products). However, subsequent photoprocesses were found to be different in the two cases. In MCMAC, both primary photoproducts were shown to undergo further reactions: P1-type products decarboxylate, giving [(1-chloroethylidene)imino]ethanide, which bears a CN+C− group (P3-type product); P2-type products decarbonylate, yielding a substituted ylidene methanamine (P4-type product). In MMAC, only P2-type primary photoproducts appeared to react, undergoing decarbonylation or decarboxylation (both reactions leading to P4-type products), whereas P1-type products were found to be non-reactive. The non-observation of any secondary photoproduct resulting from photolysis of P1-MMAC revealed the higher photostability of this species when compared with the corresponding photoproduct obtained from MCMAC.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. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Universidad de Coimbra; PortugalFil: Kaczor, Agnieszka. Universidad de Coimbra; PortugalFil: Cardoso, Ana Lucía. Universidad de Coimbra; PortugalFil: Pinho e Melo, Teresa M.V.D.. Universidad de Coimbra; PortugalFil: Fausto, Rui. Universidad de Coimbra; PortugalElsevier Science2007-05info: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/11336/113288Gomez Zavaglia, Andrea; Kaczor, Agnieszka; Cardoso, Ana Lucía; Pinho e Melo, Teresa M.V.D.; Fausto, Rui; Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2H-azirines; Elsevier Science; Journal of Molecular Structure; 834-836; 5-2007; 262-2690022-28601872-8014CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0022286006009884info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2006.12.027info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:03:32Zoai:ri.conicet.gov.ar:11336/113288instacron: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 10:03:32.867CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2H-azirines
title Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2H-azirines
spellingShingle Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2H-azirines
Gomez Zavaglia, Andrea
2H-azirines
Photolysis
Matrix isolation FTIR spectroscopy
Substituent effects
title_short Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2H-azirines
title_full Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2H-azirines
title_fullStr Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2H-azirines
title_full_unstemmed Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2H-azirines
title_sort Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2H-azirines
dc.creator.none.fl_str_mv Gomez Zavaglia, Andrea
Kaczor, Agnieszka
Cardoso, Ana Lucía
Pinho e Melo, Teresa M.V.D.
Fausto, Rui
author Gomez Zavaglia, Andrea
author_facet Gomez Zavaglia, Andrea
Kaczor, Agnieszka
Cardoso, Ana Lucía
Pinho e Melo, Teresa M.V.D.
Fausto, Rui
author_role author
author2 Kaczor, Agnieszka
Cardoso, Ana Lucía
Pinho e Melo, Teresa M.V.D.
Fausto, Rui
author2_role author
author
author
author
dc.subject.none.fl_str_mv 2H-azirines
Photolysis
Matrix isolation FTIR spectroscopy
Substituent effects
topic 2H-azirines
Photolysis
Matrix isolation FTIR spectroscopy
Substituent effects
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.11
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv In this study, the UV induced photochemical reactions of two 2H-azirines – methyl 2-chloro-3-methyl-2H-azirine-2-carboxylate (MCMAC) and methyl 3-methyl-2H-azirine-2-carboxylate (MMAC) – isolated in argon matrices are compared. For both compounds, irradiation with λ > 235 nm led to observation of two primary photoprocesses: (a) CC bond cleavage, with production of nitrile ylides (P1-type products), and (b) CN bond cleavage, with production of methylated ketene imines (P2-type products). However, subsequent photoprocesses were found to be different in the two cases. In MCMAC, both primary photoproducts were shown to undergo further reactions: P1-type products decarboxylate, giving [(1-chloroethylidene)imino]ethanide, which bears a CN+C− group (P3-type product); P2-type products decarbonylate, yielding a substituted ylidene methanamine (P4-type product). In MMAC, only P2-type primary photoproducts appeared to react, undergoing decarbonylation or decarboxylation (both reactions leading to P4-type products), whereas P1-type products were found to be non-reactive. The non-observation of any secondary photoproduct resulting from photolysis of P1-MMAC revealed the higher photostability of this species when compared with the corresponding photoproduct obtained from MCMAC.
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. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Universidad de Coimbra; Portugal
Fil: Kaczor, Agnieszka. Universidad de Coimbra; Portugal
Fil: Cardoso, Ana Lucía. Universidad de Coimbra; Portugal
Fil: Pinho e Melo, Teresa M.V.D.. Universidad de Coimbra; Portugal
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
description In this study, the UV induced photochemical reactions of two 2H-azirines – methyl 2-chloro-3-methyl-2H-azirine-2-carboxylate (MCMAC) and methyl 3-methyl-2H-azirine-2-carboxylate (MMAC) – isolated in argon matrices are compared. For both compounds, irradiation with λ > 235 nm led to observation of two primary photoprocesses: (a) CC bond cleavage, with production of nitrile ylides (P1-type products), and (b) CN bond cleavage, with production of methylated ketene imines (P2-type products). However, subsequent photoprocesses were found to be different in the two cases. In MCMAC, both primary photoproducts were shown to undergo further reactions: P1-type products decarboxylate, giving [(1-chloroethylidene)imino]ethanide, which bears a CN+C− group (P3-type product); P2-type products decarbonylate, yielding a substituted ylidene methanamine (P4-type product). In MMAC, only P2-type primary photoproducts appeared to react, undergoing decarbonylation or decarboxylation (both reactions leading to P4-type products), whereas P1-type products were found to be non-reactive. The non-observation of any secondary photoproduct resulting from photolysis of P1-MMAC revealed the higher photostability of this species when compared with the corresponding photoproduct obtained from MCMAC.
publishDate 2007
dc.date.none.fl_str_mv 2007-05
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/11336/113288
Gomez Zavaglia, Andrea; Kaczor, Agnieszka; Cardoso, Ana Lucía; Pinho e Melo, Teresa M.V.D.; Fausto, Rui; Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2H-azirines; Elsevier Science; Journal of Molecular Structure; 834-836; 5-2007; 262-269
0022-2860
1872-8014
CONICET Digital
CONICET
url http://hdl.handle.net/11336/113288
identifier_str_mv Gomez Zavaglia, Andrea; Kaczor, Agnieszka; Cardoso, Ana Lucía; Pinho e Melo, Teresa M.V.D.; Fausto, Rui; Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2H-azirines; Elsevier Science; Journal of Molecular Structure; 834-836; 5-2007; 262-269
0022-2860
1872-8014
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/S0022286006009884
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2006.12.027
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 Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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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