Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3

Autores
Kinen, Claudio Omar; Rossi, Laura Isabel; Hoyos, Maria Rita Micaela
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The oxidation of aryl methyl sulfides containing electron withdrawing and electron donating groups (p-NO2, p-CHO, p-NCS, p-Br, H, p-CH3, p-OCH3) was carried out in homogeneous solution in acetonitrile in the presence of catalytic amounts of HNO3 and FeBr3. The FeBr3 is required for the reaction to proceed for compounds with strongly electron withdrawing groups (p-NO2 and p-CHO) but is not necessary in the case of all the other compounds, although in the latter cases the yield decreases considerably. The rate of the reaction was measured as a function of substrate, FeBr3 and HNO3 concentration. From the experimental data a mechanism is suggested where there are two reaction pathways, one involving the formation of a ternary complex between the substrate, FeBr3 and NO 3- and one involving a complex formed between the sulfide and the HNO3. From these complexes HNO2 is generated, which then combines with HNO3 to yield N2O4, initiating a catalytic cycle where the sulfide is oxidized and O2 from the air is stoichiometrically consumed.
Fil: Kinen, Claudio Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Rossi, Laura Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Hoyos, Maria Rita Micaela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
Oxidation
Mechanism
Catalyst
Febr3
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:11336/113766
Acceder
id CONICETDig_4865bc1617fcaf100b3141cc8c59f38e
oai_identifier_str oai:ri.conicet.gov.ar:11336/113766
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3Kinen, Claudio OmarRossi, Laura IsabelHoyos, Maria Rita MicaelaOxidationMechanismCatalystFebr3https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The oxidation of aryl methyl sulfides containing electron withdrawing and electron donating groups (p-NO2, p-CHO, p-NCS, p-Br, H, p-CH3, p-OCH3) was carried out in homogeneous solution in acetonitrile in the presence of catalytic amounts of HNO3 and FeBr3. The FeBr3 is required for the reaction to proceed for compounds with strongly electron withdrawing groups (p-NO2 and p-CHO) but is not necessary in the case of all the other compounds, although in the latter cases the yield decreases considerably. The rate of the reaction was measured as a function of substrate, FeBr3 and HNO3 concentration. From the experimental data a mechanism is suggested where there are two reaction pathways, one involving the formation of a ternary complex between the substrate, FeBr3 and NO 3- and one involving a complex formed between the sulfide and the HNO3. From these complexes HNO2 is generated, which then combines with HNO3 to yield N2O4, initiating a catalytic cycle where the sulfide is oxidized and O2 from the air is stoichiometrically consumed.Fil: Kinen, Claudio Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Rossi, Laura Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Hoyos, Maria Rita Micaela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaAmerican Chemical Society2009-09info: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/11336/113766Kinen, Claudio Omar; Rossi, Laura Isabel; Hoyos, Maria Rita Micaela; Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3; American Chemical Society; Journal of Organic Chemistry; 74; 18; 9-2009; 7132-71390022-32631520-6904CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jo9015248info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jo9015248info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-12T09:33:55Zoai:ri.conicet.gov.ar:11336/113766instacron: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:34982025-11-12 09:33:55.676CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3
title Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3
spellingShingle Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3
Kinen, Claudio Omar
Oxidation
Mechanism
Catalyst
Febr3
title_short Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3
title_full Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3
title_fullStr Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3
title_full_unstemmed Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3
title_sort Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3
dc.creator.none.fl_str_mv Kinen, Claudio Omar
Rossi, Laura Isabel
Hoyos, Maria Rita Micaela
author Kinen, Claudio Omar
author_facet Kinen, Claudio Omar
Rossi, Laura Isabel
Hoyos, Maria Rita Micaela
author_role author
author2 Rossi, Laura Isabel
Hoyos, Maria Rita Micaela
author2_role author
author
dc.subject.none.fl_str_mv Oxidation
Mechanism
Catalyst
Febr3
topic Oxidation
Mechanism
Catalyst
Febr3
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 oxidation of aryl methyl sulfides containing electron withdrawing and electron donating groups (p-NO2, p-CHO, p-NCS, p-Br, H, p-CH3, p-OCH3) was carried out in homogeneous solution in acetonitrile in the presence of catalytic amounts of HNO3 and FeBr3. The FeBr3 is required for the reaction to proceed for compounds with strongly electron withdrawing groups (p-NO2 and p-CHO) but is not necessary in the case of all the other compounds, although in the latter cases the yield decreases considerably. The rate of the reaction was measured as a function of substrate, FeBr3 and HNO3 concentration. From the experimental data a mechanism is suggested where there are two reaction pathways, one involving the formation of a ternary complex between the substrate, FeBr3 and NO 3- and one involving a complex formed between the sulfide and the HNO3. From these complexes HNO2 is generated, which then combines with HNO3 to yield N2O4, initiating a catalytic cycle where the sulfide is oxidized and O2 from the air is stoichiometrically consumed.
Fil: Kinen, Claudio Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Rossi, Laura Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Hoyos, Maria Rita Micaela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description The oxidation of aryl methyl sulfides containing electron withdrawing and electron donating groups (p-NO2, p-CHO, p-NCS, p-Br, H, p-CH3, p-OCH3) was carried out in homogeneous solution in acetonitrile in the presence of catalytic amounts of HNO3 and FeBr3. The FeBr3 is required for the reaction to proceed for compounds with strongly electron withdrawing groups (p-NO2 and p-CHO) but is not necessary in the case of all the other compounds, although in the latter cases the yield decreases considerably. The rate of the reaction was measured as a function of substrate, FeBr3 and HNO3 concentration. From the experimental data a mechanism is suggested where there are two reaction pathways, one involving the formation of a ternary complex between the substrate, FeBr3 and NO 3- and one involving a complex formed between the sulfide and the HNO3. From these complexes HNO2 is generated, which then combines with HNO3 to yield N2O4, initiating a catalytic cycle where the sulfide is oxidized and O2 from the air is stoichiometrically consumed.
publishDate 2009
dc.date.none.fl_str_mv 2009-09
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/11336/113766
Kinen, Claudio Omar; Rossi, Laura Isabel; Hoyos, Maria Rita Micaela; Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3; American Chemical Society; Journal of Organic Chemistry; 74; 18; 9-2009; 7132-7139
0022-3263
1520-6904
CONICET Digital
CONICET
url http://hdl.handle.net/11336/113766
identifier_str_mv Kinen, Claudio Omar; Rossi, Laura Isabel; Hoyos, Maria Rita Micaela; Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3; American Chemical Society; Journal of Organic Chemistry; 74; 18; 9-2009; 7132-7139
0022-3263
1520-6904
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jo9015248
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jo9015248
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 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
_version_ 1848597088461389824
score 12.976206

Publicaciones similares