Reactivity of the Insecticide Fenitrothion toward O and N Nucleophiles

Autores
Rougier, Natalia Mercedes; Vico, Raquel Viviana; Hoyos, Maria Rita Micaela; Bujan, Elba Ines
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The reactivity of Fenitrothion (1) toward several O- and N-based nucleophiles, including ambident and alfa-nucleophiles, was investigated in basic media at 25ºC in water containing 2% 1,4-dioxane. In the reactions with HO- and HOO- quantitative formation of 3-methyl-4-nitrophenoxide (2) was observed indicating a SN2(P) pathway. In the reactions with NH2OH, NH2O-, and BuNH2, demethylfenitrothion (4) was formed along with 2, indicating competition between the SN2(P) and SN2(C) pathways; no evidence of a SNAr pathway was observed in any case. The observed rate constants were dissected into the values corresponding to the SN2(P) and SN2(C) pathways. The yield of 4 depends on the nucleophile and on the pH of the reaction, being the main product in the case of BuNH2. With HOO-, NH2OH, and NH2O- a significant alfa-effect was observed, confirming the participation of the nucleophile in the rate-limiting step of the reaction.
Fil: Rougier, Natalia Mercedes. 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: Vico, Raquel Viviana. 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
Fil: Bujan, Elba Ines. 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
FENITROTHION
ORGANOPHOSPHORUS INSECTICIDES
NUCLEOPHILIC REACTIVITY
REGIOCHEMISTRY
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:11336/277688
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/277688
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Reactivity of the Insecticide Fenitrothion toward O and N NucleophilesRougier, Natalia MercedesVico, Raquel VivianaHoyos, Maria Rita MicaelaBujan, Elba InesFENITROTHIONORGANOPHOSPHORUS INSECTICIDESNUCLEOPHILIC REACTIVITYREGIOCHEMISTRYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The reactivity of Fenitrothion (1) toward several O- and N-based nucleophiles, including ambident and alfa-nucleophiles, was investigated in basic media at 25ºC in water containing 2% 1,4-dioxane. In the reactions with HO- and HOO- quantitative formation of 3-methyl-4-nitrophenoxide (2) was observed indicating a SN2(P) pathway. In the reactions with NH2OH, NH2O-, and BuNH2, demethylfenitrothion (4) was formed along with 2, indicating competition between the SN2(P) and SN2(C) pathways; no evidence of a SNAr pathway was observed in any case. The observed rate constants were dissected into the values corresponding to the SN2(P) and SN2(C) pathways. The yield of 4 depends on the nucleophile and on the pH of the reaction, being the main product in the case of BuNH2. With HOO-, NH2OH, and NH2O- a significant alfa-effect was observed, confirming the participation of the nucleophile in the rate-limiting step of the reaction.Fil: Rougier, Natalia Mercedes. 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: Vico, Raquel Viviana. 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; ArgentinaFil: Bujan, Elba Ines. 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 Society2010-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/277688Rougier, Natalia Mercedes; Vico, Raquel Viviana; Hoyos, Maria Rita Micaela; Bujan, Elba Ines; Reactivity of the Insecticide Fenitrothion toward O and N Nucleophiles; American Chemical Society; Journal of Organic Chemistry; 75; 4-2010; 3427-34360022-3263CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jo100541yinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jo100541yinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-01-08T12:51:43Zoai:ri.conicet.gov.ar:11336/277688instacron: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:34982026-01-08 12:51:43.694CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Reactivity of the Insecticide Fenitrothion toward O and N Nucleophiles
title Reactivity of the Insecticide Fenitrothion toward O and N Nucleophiles
spellingShingle Reactivity of the Insecticide Fenitrothion toward O and N Nucleophiles
Rougier, Natalia Mercedes
FENITROTHION
ORGANOPHOSPHORUS INSECTICIDES
NUCLEOPHILIC REACTIVITY
REGIOCHEMISTRY
title_short Reactivity of the Insecticide Fenitrothion toward O and N Nucleophiles
title_full Reactivity of the Insecticide Fenitrothion toward O and N Nucleophiles
title_fullStr Reactivity of the Insecticide Fenitrothion toward O and N Nucleophiles
title_full_unstemmed Reactivity of the Insecticide Fenitrothion toward O and N Nucleophiles
title_sort Reactivity of the Insecticide Fenitrothion toward O and N Nucleophiles
dc.creator.none.fl_str_mv Rougier, Natalia Mercedes
Vico, Raquel Viviana
Hoyos, Maria Rita Micaela
Bujan, Elba Ines
author Rougier, Natalia Mercedes
author_facet Rougier, Natalia Mercedes
Vico, Raquel Viviana
Hoyos, Maria Rita Micaela
Bujan, Elba Ines
author_role author
author2 Vico, Raquel Viviana
Hoyos, Maria Rita Micaela
Bujan, Elba Ines
author2_role author
author
author
dc.subject.none.fl_str_mv FENITROTHION
ORGANOPHOSPHORUS INSECTICIDES
NUCLEOPHILIC REACTIVITY
REGIOCHEMISTRY
topic FENITROTHION
ORGANOPHOSPHORUS INSECTICIDES
NUCLEOPHILIC REACTIVITY
REGIOCHEMISTRY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The reactivity of Fenitrothion (1) toward several O- and N-based nucleophiles, including ambident and alfa-nucleophiles, was investigated in basic media at 25ºC in water containing 2% 1,4-dioxane. In the reactions with HO- and HOO- quantitative formation of 3-methyl-4-nitrophenoxide (2) was observed indicating a SN2(P) pathway. In the reactions with NH2OH, NH2O-, and BuNH2, demethylfenitrothion (4) was formed along with 2, indicating competition between the SN2(P) and SN2(C) pathways; no evidence of a SNAr pathway was observed in any case. The observed rate constants were dissected into the values corresponding to the SN2(P) and SN2(C) pathways. The yield of 4 depends on the nucleophile and on the pH of the reaction, being the main product in the case of BuNH2. With HOO-, NH2OH, and NH2O- a significant alfa-effect was observed, confirming the participation of the nucleophile in the rate-limiting step of the reaction.
Fil: Rougier, Natalia Mercedes. 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: Vico, Raquel Viviana. 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
Fil: Bujan, Elba Ines. 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 reactivity of Fenitrothion (1) toward several O- and N-based nucleophiles, including ambident and alfa-nucleophiles, was investigated in basic media at 25ºC in water containing 2% 1,4-dioxane. In the reactions with HO- and HOO- quantitative formation of 3-methyl-4-nitrophenoxide (2) was observed indicating a SN2(P) pathway. In the reactions with NH2OH, NH2O-, and BuNH2, demethylfenitrothion (4) was formed along with 2, indicating competition between the SN2(P) and SN2(C) pathways; no evidence of a SNAr pathway was observed in any case. The observed rate constants were dissected into the values corresponding to the SN2(P) and SN2(C) pathways. The yield of 4 depends on the nucleophile and on the pH of the reaction, being the main product in the case of BuNH2. With HOO-, NH2OH, and NH2O- a significant alfa-effect was observed, confirming the participation of the nucleophile in the rate-limiting step of the reaction.
publishDate 2010
dc.date.none.fl_str_mv 2010-04
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/11336/277688
Rougier, Natalia Mercedes; Vico, Raquel Viviana; Hoyos, Maria Rita Micaela; Bujan, Elba Ines; Reactivity of the Insecticide Fenitrothion toward O and N Nucleophiles; American Chemical Society; Journal of Organic Chemistry; 75; 4-2010; 3427-3436
0022-3263
CONICET Digital
CONICET
url http://hdl.handle.net/11336/277688
identifier_str_mv Rougier, Natalia Mercedes; Vico, Raquel Viviana; Hoyos, Maria Rita Micaela; Bujan, Elba Ines; Reactivity of the Insecticide Fenitrothion toward O and N Nucleophiles; American Chemical Society; Journal of Organic Chemistry; 75; 4-2010; 3427-3436
0022-3263
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/10.1021/jo100541y
info:eu-repo/semantics/altIdentifier/doi/10.1021/jo100541y
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
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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