Reactivity of the insecticide chlorpyrifos-methyl toward hydroxy! and perhydroxyl ion. Effect of cyclodextrins

Autores
Vico, Raquel Viviana; Hoyos, Maria Rita Micaela; Bujan, Elba Ines
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The reactivity of Chlorpyrifos-Methyl (1) toward hydroxyl ion and the α-nucleophile, perhydroxyl ion was investigated in aqueous basic media. The hydrolysis of 1 was studied at 25° C in water containing 10% ACN or 7% 1,4-dioxane at NaOH concentrations between 0.01 and 0.6m; the second-order rate constant is 1.88 × 10-2m-1 s-1 in 10% ACN and 1.70 × 10-2m-1 s-1 in 7% 1,4-dioxane. The reaction with H2O2 was studied in a pH range from 9.14 to 12.40 in 7% 1,4-dioxane/H2O; the second-order rate constant for the reaction of HOO ion is 7.9 m-1 s-1 whereas neutral H2O2 does not compete as nucleophile. In all cases quantitative formation of 3,5,6-trichloro-2-pyridinol (3) was observed indicating an SN2(P) pathway. The hydrolysis reaction is inhibited by α-, β-, and γ-cyclodextrin showing saturation kinetics; the greater inhibition is produced by γ-cyclodextrin. The reaction with hydrogen peroxide is weakly inhibited by α- and β-cyclodextrin (β-CD), whereas g-cyclodextrin produces a greater inhibition and saturation kinetics. The kinetic data obtained in the presence of β-or γ-cyclodextrin for the reaction with hydroxyl or perhydroxyl ion indicate that the main reaction pathway for the cyclodextrin-mediated reaction is the reaction of HO- or HOO- ion with the substrate complexed with the anion of the cyclodextrin. The inhibition is attributed to the inclusion of the substrate with the reaction center far from the ionized secondary OH groups of the cyclodextrin and protected from external attack of the nucleophile. Sucrose also inhibits the hydrolysis reaction but the effect is independent of its concentration.
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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; 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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; 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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina
Materia
Cyclodextrins
Hostguest Systems
Hydrogen Peroxide
Hydrolysis
Inclusion Complexes
Organophosphorus Insecticides
Reaction Mechanisms
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:11336/73964
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/73964
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Reactivity of the insecticide chlorpyrifos-methyl toward hydroxy! and perhydroxyl ion. Effect of cyclodextrinsVico, Raquel VivianaHoyos, Maria Rita MicaelaBujan, Elba InesCyclodextrinsHostguest SystemsHydrogen PeroxideHydrolysisInclusion ComplexesOrganophosphorus InsecticidesReaction Mechanismshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The reactivity of Chlorpyrifos-Methyl (1) toward hydroxyl ion and the α-nucleophile, perhydroxyl ion was investigated in aqueous basic media. The hydrolysis of 1 was studied at 25° C in water containing 10% ACN or 7% 1,4-dioxane at NaOH concentrations between 0.01 and 0.6m; the second-order rate constant is 1.88 × 10-2m-1 s-1 in 10% ACN and 1.70 × 10-2m-1 s-1 in 7% 1,4-dioxane. The reaction with H2O2 was studied in a pH range from 9.14 to 12.40 in 7% 1,4-dioxane/H2O; the second-order rate constant for the reaction of HOO ion is 7.9 m-1 s-1 whereas neutral H2O2 does not compete as nucleophile. In all cases quantitative formation of 3,5,6-trichloro-2-pyridinol (3) was observed indicating an SN2(P) pathway. The hydrolysis reaction is inhibited by α-, β-, and γ-cyclodextrin showing saturation kinetics; the greater inhibition is produced by γ-cyclodextrin. The reaction with hydrogen peroxide is weakly inhibited by α- and β-cyclodextrin (β-CD), whereas g-cyclodextrin produces a greater inhibition and saturation kinetics. The kinetic data obtained in the presence of β-or γ-cyclodextrin for the reaction with hydroxyl or perhydroxyl ion indicate that the main reaction pathway for the cyclodextrin-mediated reaction is the reaction of HO- or HOO- ion with the substrate complexed with the anion of the cyclodextrin. The inhibition is attributed to the inclusion of the substrate with the reaction center far from the ionized secondary OH groups of the cyclodextrin and protected from external attack of the nucleophile. Sucrose also inhibits the hydrolysis reaction but the effect is independent of its concentration.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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; 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; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; 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; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; ArgentinaJohn Wiley & Sons Ltd2009-07info: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/11336/73964Vico, Raquel Viviana; Hoyos, Maria Rita Micaela; Bujan, Elba Ines; Reactivity of the insecticide chlorpyrifos-methyl toward hydroxy! and perhydroxyl ion. Effect of cyclodextrins; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 22; 7; 7-2009; 691-7020894-3230CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/poc.1502info:eu-repo/semantics/altIdentifier/doi/10.1002/poc.1502info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-12-17T15:44:35Zoai:ri.conicet.gov.ar:11336/73964instacron: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:34982025-12-17 15:44:36.273CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Reactivity of the insecticide chlorpyrifos-methyl toward hydroxy! and perhydroxyl ion. Effect of cyclodextrins
title Reactivity of the insecticide chlorpyrifos-methyl toward hydroxy! and perhydroxyl ion. Effect of cyclodextrins
spellingShingle Reactivity of the insecticide chlorpyrifos-methyl toward hydroxy! and perhydroxyl ion. Effect of cyclodextrins
Vico, Raquel Viviana
Cyclodextrins
Hostguest Systems
Hydrogen Peroxide
Hydrolysis
Inclusion Complexes
Organophosphorus Insecticides
Reaction Mechanisms
title_short Reactivity of the insecticide chlorpyrifos-methyl toward hydroxy! and perhydroxyl ion. Effect of cyclodextrins
title_full Reactivity of the insecticide chlorpyrifos-methyl toward hydroxy! and perhydroxyl ion. Effect of cyclodextrins
title_fullStr Reactivity of the insecticide chlorpyrifos-methyl toward hydroxy! and perhydroxyl ion. Effect of cyclodextrins
title_full_unstemmed Reactivity of the insecticide chlorpyrifos-methyl toward hydroxy! and perhydroxyl ion. Effect of cyclodextrins
title_sort Reactivity of the insecticide chlorpyrifos-methyl toward hydroxy! and perhydroxyl ion. Effect of cyclodextrins
dc.creator.none.fl_str_mv Vico, Raquel Viviana
Hoyos, Maria Rita Micaela
Bujan, Elba Ines
author Vico, Raquel Viviana
author_facet Vico, Raquel Viviana
Hoyos, Maria Rita Micaela
Bujan, Elba Ines
author_role author
author2 Hoyos, Maria Rita Micaela
Bujan, Elba Ines
author2_role author
author
dc.subject.none.fl_str_mv Cyclodextrins
Hostguest Systems
Hydrogen Peroxide
Hydrolysis
Inclusion Complexes
Organophosphorus Insecticides
Reaction Mechanisms
topic Cyclodextrins
Hostguest Systems
Hydrogen Peroxide
Hydrolysis
Inclusion Complexes
Organophosphorus Insecticides
Reaction Mechanisms
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 reactivity of Chlorpyrifos-Methyl (1) toward hydroxyl ion and the α-nucleophile, perhydroxyl ion was investigated in aqueous basic media. The hydrolysis of 1 was studied at 25° C in water containing 10% ACN or 7% 1,4-dioxane at NaOH concentrations between 0.01 and 0.6m; the second-order rate constant is 1.88 × 10-2m-1 s-1 in 10% ACN and 1.70 × 10-2m-1 s-1 in 7% 1,4-dioxane. The reaction with H2O2 was studied in a pH range from 9.14 to 12.40 in 7% 1,4-dioxane/H2O; the second-order rate constant for the reaction of HOO ion is 7.9 m-1 s-1 whereas neutral H2O2 does not compete as nucleophile. In all cases quantitative formation of 3,5,6-trichloro-2-pyridinol (3) was observed indicating an SN2(P) pathway. The hydrolysis reaction is inhibited by α-, β-, and γ-cyclodextrin showing saturation kinetics; the greater inhibition is produced by γ-cyclodextrin. The reaction with hydrogen peroxide is weakly inhibited by α- and β-cyclodextrin (β-CD), whereas g-cyclodextrin produces a greater inhibition and saturation kinetics. The kinetic data obtained in the presence of β-or γ-cyclodextrin for the reaction with hydroxyl or perhydroxyl ion indicate that the main reaction pathway for the cyclodextrin-mediated reaction is the reaction of HO- or HOO- ion with the substrate complexed with the anion of the cyclodextrin. The inhibition is attributed to the inclusion of the substrate with the reaction center far from the ionized secondary OH groups of the cyclodextrin and protected from external attack of the nucleophile. Sucrose also inhibits the hydrolysis reaction but the effect is independent of its concentration.
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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; 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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; 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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina
description The reactivity of Chlorpyrifos-Methyl (1) toward hydroxyl ion and the α-nucleophile, perhydroxyl ion was investigated in aqueous basic media. The hydrolysis of 1 was studied at 25° C in water containing 10% ACN or 7% 1,4-dioxane at NaOH concentrations between 0.01 and 0.6m; the second-order rate constant is 1.88 × 10-2m-1 s-1 in 10% ACN and 1.70 × 10-2m-1 s-1 in 7% 1,4-dioxane. The reaction with H2O2 was studied in a pH range from 9.14 to 12.40 in 7% 1,4-dioxane/H2O; the second-order rate constant for the reaction of HOO ion is 7.9 m-1 s-1 whereas neutral H2O2 does not compete as nucleophile. In all cases quantitative formation of 3,5,6-trichloro-2-pyridinol (3) was observed indicating an SN2(P) pathway. The hydrolysis reaction is inhibited by α-, β-, and γ-cyclodextrin showing saturation kinetics; the greater inhibition is produced by γ-cyclodextrin. The reaction with hydrogen peroxide is weakly inhibited by α- and β-cyclodextrin (β-CD), whereas g-cyclodextrin produces a greater inhibition and saturation kinetics. The kinetic data obtained in the presence of β-or γ-cyclodextrin for the reaction with hydroxyl or perhydroxyl ion indicate that the main reaction pathway for the cyclodextrin-mediated reaction is the reaction of HO- or HOO- ion with the substrate complexed with the anion of the cyclodextrin. The inhibition is attributed to the inclusion of the substrate with the reaction center far from the ionized secondary OH groups of the cyclodextrin and protected from external attack of the nucleophile. Sucrose also inhibits the hydrolysis reaction but the effect is independent of its concentration.
publishDate 2009
dc.date.none.fl_str_mv 2009-07
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/11336/73964
Vico, Raquel Viviana; Hoyos, Maria Rita Micaela; Bujan, Elba Ines; Reactivity of the insecticide chlorpyrifos-methyl toward hydroxy! and perhydroxyl ion. Effect of cyclodextrins; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 22; 7; 7-2009; 691-702
0894-3230
CONICET Digital
CONICET
url http://hdl.handle.net/11336/73964
identifier_str_mv Vico, Raquel Viviana; Hoyos, Maria Rita Micaela; Bujan, Elba Ines; Reactivity of the insecticide chlorpyrifos-methyl toward hydroxy! and perhydroxyl ion. Effect of cyclodextrins; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 22; 7; 7-2009; 691-702
0894-3230
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://onlinelibrary.wiley.com/doi/abs/10.1002/poc.1502
info:eu-repo/semantics/altIdentifier/doi/10.1002/poc.1502
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 John Wiley & Sons Ltd
publisher.none.fl_str_mv John Wiley & Sons 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
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score 13.176297

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