A New Look at the Halogenation of Porphyrins

Autores
Gazzano, Emiliano R. A.; Lazaro Martinez, Juan Manuel; Buldain, Graciela Yolanda
Año de publicación
2016
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The present study describes the selective halogenation at the β - or meso-position of the porphyrin macrocycle. The reactions of deuteroporphyrin IX dimethyl ester, mesoporphyrin III dimethyl ester and their Cu(II) and Ni(II) complexes with N-bromosuccinimide or phenylselenyl chloride were investigated. It could be observed that when the bromination of deuteroporphyn IX dimethyl ester using NBS took place, the isolated products were the result of an electrophilic substitution in β-free porphyrin ring positions. Employing the same reagent for halogenating mesoporphyrin III dimethyl ester, which does not possess β-free position, different derivatives were obtained from the allylic bromination of the ethyl side chain. When phenylselenyl chloride was used as halogenating agent with deuteroporphyn IX dimethyl ester or its Cu(II) complex, in both cases the replacement of β-free hydrogen atoms by phenylselenyl group was afforded. When the Ni(II) mesoporphyrin III dimethyl ester was used the desired and selective replacement of meso hydrogen atoms of aromatic ring by chlorine atoms was obtained. The structural assignment of the porphyrin derivatives thus obtained was performed by high-resolution mass spectrometry and detailed analysis of the NMR spectra.
Fil: Gazzano, Emiliano R. A.. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina
Fil: Lazaro Martinez, Juan Manuel. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Buldain, Graciela Yolanda. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Materia
Halogenacion
Deuteroporfirina Ix Dimetil Ester
Mesoporfirina Iii Dimetil Ester
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:11336/47235
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/47235
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling A New Look at the Halogenation of PorphyrinsGazzano, Emiliano R. A.Lazaro Martinez, Juan ManuelBuldain, Graciela YolandaHalogenacionDeuteroporfirina Ix Dimetil EsterMesoporfirina Iii Dimetil Esterhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The present study describes the selective halogenation at the β - or meso-position of the porphyrin macrocycle. The reactions of deuteroporphyrin IX dimethyl ester, mesoporphyrin III dimethyl ester and their Cu(II) and Ni(II) complexes with N-bromosuccinimide or phenylselenyl chloride were investigated. It could be observed that when the bromination of deuteroporphyn IX dimethyl ester using NBS took place, the isolated products were the result of an electrophilic substitution in β-free porphyrin ring positions. Employing the same reagent for halogenating mesoporphyrin III dimethyl ester, which does not possess β-free position, different derivatives were obtained from the allylic bromination of the ethyl side chain. When phenylselenyl chloride was used as halogenating agent with deuteroporphyn IX dimethyl ester or its Cu(II) complex, in both cases the replacement of β-free hydrogen atoms by phenylselenyl group was afforded. When the Ni(II) mesoporphyrin III dimethyl ester was used the desired and selective replacement of meso hydrogen atoms of aromatic ring by chlorine atoms was obtained. The structural assignment of the porphyrin derivatives thus obtained was performed by high-resolution mass spectrometry and detailed analysis of the NMR spectra.Fil: Gazzano, Emiliano R. A.. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; ArgentinaFil: Lazaro Martinez, Juan Manuel. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Buldain, Graciela Yolanda. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaBentham Science Publishers2016-12info: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/11336/47235Gazzano, Emiliano R. A.; Lazaro Martinez, Juan Manuel; Buldain, Graciela Yolanda; A New Look at the Halogenation of Porphyrins; Bentham Science Publishers; Current Organic Chemistry; 21; 2; 12-2016; 177-1821385-2728CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://www.eurekaselect.com/145720info:eu-repo/semantics/altIdentifier/doi/10.2174/1385272820666160922154159info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:39:44Zoai:ri.conicet.gov.ar:11336/47235instacron: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:34982025-09-29 09:39:45.209CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A New Look at the Halogenation of Porphyrins
title A New Look at the Halogenation of Porphyrins
spellingShingle A New Look at the Halogenation of Porphyrins
Gazzano, Emiliano R. A.
Halogenacion
Deuteroporfirina Ix Dimetil Ester
Mesoporfirina Iii Dimetil Ester
title_short A New Look at the Halogenation of Porphyrins
title_full A New Look at the Halogenation of Porphyrins
title_fullStr A New Look at the Halogenation of Porphyrins
title_full_unstemmed A New Look at the Halogenation of Porphyrins
title_sort A New Look at the Halogenation of Porphyrins
dc.creator.none.fl_str_mv Gazzano, Emiliano R. A.
Lazaro Martinez, Juan Manuel
Buldain, Graciela Yolanda
author Gazzano, Emiliano R. A.
author_facet Gazzano, Emiliano R. A.
Lazaro Martinez, Juan Manuel
Buldain, Graciela Yolanda
author_role author
author2 Lazaro Martinez, Juan Manuel
Buldain, Graciela Yolanda
author2_role author
author
dc.subject.none.fl_str_mv Halogenacion
Deuteroporfirina Ix Dimetil Ester
Mesoporfirina Iii Dimetil Ester
topic Halogenacion
Deuteroporfirina Ix Dimetil Ester
Mesoporfirina Iii Dimetil Ester
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 present study describes the selective halogenation at the β - or meso-position of the porphyrin macrocycle. The reactions of deuteroporphyrin IX dimethyl ester, mesoporphyrin III dimethyl ester and their Cu(II) and Ni(II) complexes with N-bromosuccinimide or phenylselenyl chloride were investigated. It could be observed that when the bromination of deuteroporphyn IX dimethyl ester using NBS took place, the isolated products were the result of an electrophilic substitution in β-free porphyrin ring positions. Employing the same reagent for halogenating mesoporphyrin III dimethyl ester, which does not possess β-free position, different derivatives were obtained from the allylic bromination of the ethyl side chain. When phenylselenyl chloride was used as halogenating agent with deuteroporphyn IX dimethyl ester or its Cu(II) complex, in both cases the replacement of β-free hydrogen atoms by phenylselenyl group was afforded. When the Ni(II) mesoporphyrin III dimethyl ester was used the desired and selective replacement of meso hydrogen atoms of aromatic ring by chlorine atoms was obtained. The structural assignment of the porphyrin derivatives thus obtained was performed by high-resolution mass spectrometry and detailed analysis of the NMR spectra.
Fil: Gazzano, Emiliano R. A.. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina
Fil: Lazaro Martinez, Juan Manuel. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Buldain, Graciela Yolanda. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
description The present study describes the selective halogenation at the β - or meso-position of the porphyrin macrocycle. The reactions of deuteroporphyrin IX dimethyl ester, mesoporphyrin III dimethyl ester and their Cu(II) and Ni(II) complexes with N-bromosuccinimide or phenylselenyl chloride were investigated. It could be observed that when the bromination of deuteroporphyn IX dimethyl ester using NBS took place, the isolated products were the result of an electrophilic substitution in β-free porphyrin ring positions. Employing the same reagent for halogenating mesoporphyrin III dimethyl ester, which does not possess β-free position, different derivatives were obtained from the allylic bromination of the ethyl side chain. When phenylselenyl chloride was used as halogenating agent with deuteroporphyn IX dimethyl ester or its Cu(II) complex, in both cases the replacement of β-free hydrogen atoms by phenylselenyl group was afforded. When the Ni(II) mesoporphyrin III dimethyl ester was used the desired and selective replacement of meso hydrogen atoms of aromatic ring by chlorine atoms was obtained. The structural assignment of the porphyrin derivatives thus obtained was performed by high-resolution mass spectrometry and detailed analysis of the NMR spectra.
publishDate 2016
dc.date.none.fl_str_mv 2016-12
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/11336/47235
Gazzano, Emiliano R. A.; Lazaro Martinez, Juan Manuel; Buldain, Graciela Yolanda; A New Look at the Halogenation of Porphyrins; Bentham Science Publishers; Current Organic Chemistry; 21; 2; 12-2016; 177-182
1385-2728
CONICET Digital
CONICET
url http://hdl.handle.net/11336/47235
identifier_str_mv Gazzano, Emiliano R. A.; Lazaro Martinez, Juan Manuel; Buldain, Graciela Yolanda; A New Look at the Halogenation of Porphyrins; Bentham Science Publishers; Current Organic Chemistry; 21; 2; 12-2016; 177-182
1385-2728
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.eurekaselect.com/145720
info:eu-repo/semantics/altIdentifier/doi/10.2174/1385272820666160922154159
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 Bentham Science Publishers
publisher.none.fl_str_mv Bentham Science Publishers
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 13.070432

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