A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanes

Autores
Cafferata, Lazaro; Jeandupeax, Rene; Romanelli, Gustavo Pablo; Mateo, Carmen Margarita; Jefford, Charles W.
Año de publicación
2003
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The kinetics of the thermal decomposition reactions of artemisinine (1), a cis-fused 1,2,4-trioxane, and trans-3,3dimethyl-1,2,4-trioxane (6) in solutions of benzene, toluene, and methanol in sealed tubes were compared at temperatures between 100.1° and 171.4 °C. Pseudo first-order rate constant values were determined for conversions of both cyclic peroxides up to ca. 60%. The activation parameters and the composition of the reaction products were indicative of homolytic cleavage of their O-O bonds as the rate-determining steps followed by stepwise fragmentation. The free energies of activation (ΔG#) for 1 and 6 reactions in the aromatic solvents were calculated at the middle of each temperature range, giving values of 30.7 and 35.1 kcal/mol, respectively, which are evaluated considering their different molecular configurations. Furthermore, the rates of the thermal decomposition reactions of those trioxanes were sensitive to solvent effects.
Fil: Cafferata, Lazaro. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina
Fil: Jeandupeax, Rene. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina
Fil: Romanelli, Gustavo Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina
Fil: Mateo, Carmen Margarita. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingenieria de Olavarria; Argentina
Fil: Jefford, Charles W.. Università degli Studi di Genova; Italia
Materia
cis- and trans- fused 1,2,4-trioxanes
artemisinine
thermolysis
reactions kinetics
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:11336/65056
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/65056
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanesCafferata, LazaroJeandupeax, ReneRomanelli, Gustavo PabloMateo, Carmen MargaritaJefford, Charles W.cis- and trans- fused 1,2,4-trioxanesartemisininethermolysisreactions kineticshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The kinetics of the thermal decomposition reactions of artemisinine (1), a cis-fused 1,2,4-trioxane, and trans-3,3dimethyl-1,2,4-trioxane (6) in solutions of benzene, toluene, and methanol in sealed tubes were compared at temperatures between 100.1° and 171.4 °C. Pseudo first-order rate constant values were determined for conversions of both cyclic peroxides up to ca. 60%. The activation parameters and the composition of the reaction products were indicative of homolytic cleavage of their O-O bonds as the rate-determining steps followed by stepwise fragmentation. The free energies of activation (ΔG#) for 1 and 6 reactions in the aromatic solvents were calculated at the middle of each temperature range, giving values of 30.7 and 35.1 kcal/mol, respectively, which are evaluated considering their different molecular configurations. Furthermore, the rates of the thermal decomposition reactions of those trioxanes were sensitive to solvent effects.Fil: Cafferata, Lazaro. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; ArgentinaFil: Jeandupeax, Rene. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; ArgentinaFil: Romanelli, Gustavo Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; ArgentinaFil: Mateo, Carmen Margarita. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingenieria de Olavarria; ArgentinaFil: Jefford, Charles W.. Università degli Studi di Genova; ItaliaAsociación de Químicos e Ingenieros2003-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/65056Cafferata, Lazaro; Jeandupeax, Rene; Romanelli, Gustavo Pablo; Mateo, Carmen Margarita; Jefford, Charles W.; A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanes; Asociación de Químicos e Ingenieros; Afinidad; 60; 504; 9-2003; 206-2110001-9704CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.raco.cat/index.php/afinidad/indexinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-12T09:37:33Zoai:ri.conicet.gov.ar:11336/65056instacron: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 09:37:34.25CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanes
title A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanes
spellingShingle A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanes
Cafferata, Lazaro
cis- and trans- fused 1,2,4-trioxanes
artemisinine
thermolysis
reactions kinetics
title_short A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanes
title_full A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanes
title_fullStr A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanes
title_full_unstemmed A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanes
title_sort A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanes
dc.creator.none.fl_str_mv Cafferata, Lazaro
Jeandupeax, Rene
Romanelli, Gustavo Pablo
Mateo, Carmen Margarita
Jefford, Charles W.
author Cafferata, Lazaro
author_facet Cafferata, Lazaro
Jeandupeax, Rene
Romanelli, Gustavo Pablo
Mateo, Carmen Margarita
Jefford, Charles W.
author_role author
author2 Jeandupeax, Rene
Romanelli, Gustavo Pablo
Mateo, Carmen Margarita
Jefford, Charles W.
author2_role author
author
author
author
dc.subject.none.fl_str_mv cis- and trans- fused 1,2,4-trioxanes
artemisinine
thermolysis
reactions kinetics
topic cis- and trans- fused 1,2,4-trioxanes
artemisinine
thermolysis
reactions kinetics
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 kinetics of the thermal decomposition reactions of artemisinine (1), a cis-fused 1,2,4-trioxane, and trans-3,3dimethyl-1,2,4-trioxane (6) in solutions of benzene, toluene, and methanol in sealed tubes were compared at temperatures between 100.1° and 171.4 °C. Pseudo first-order rate constant values were determined for conversions of both cyclic peroxides up to ca. 60%. The activation parameters and the composition of the reaction products were indicative of homolytic cleavage of their O-O bonds as the rate-determining steps followed by stepwise fragmentation. The free energies of activation (ΔG#) for 1 and 6 reactions in the aromatic solvents were calculated at the middle of each temperature range, giving values of 30.7 and 35.1 kcal/mol, respectively, which are evaluated considering their different molecular configurations. Furthermore, the rates of the thermal decomposition reactions of those trioxanes were sensitive to solvent effects.
Fil: Cafferata, Lazaro. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina
Fil: Jeandupeax, Rene. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina
Fil: Romanelli, Gustavo Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina
Fil: Mateo, Carmen Margarita. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingenieria de Olavarria; Argentina
Fil: Jefford, Charles W.. Università degli Studi di Genova; Italia
description The kinetics of the thermal decomposition reactions of artemisinine (1), a cis-fused 1,2,4-trioxane, and trans-3,3dimethyl-1,2,4-trioxane (6) in solutions of benzene, toluene, and methanol in sealed tubes were compared at temperatures between 100.1° and 171.4 °C. Pseudo first-order rate constant values were determined for conversions of both cyclic peroxides up to ca. 60%. The activation parameters and the composition of the reaction products were indicative of homolytic cleavage of their O-O bonds as the rate-determining steps followed by stepwise fragmentation. The free energies of activation (ΔG#) for 1 and 6 reactions in the aromatic solvents were calculated at the middle of each temperature range, giving values of 30.7 and 35.1 kcal/mol, respectively, which are evaluated considering their different molecular configurations. Furthermore, the rates of the thermal decomposition reactions of those trioxanes were sensitive to solvent effects.
publishDate 2003
dc.date.none.fl_str_mv 2003-09
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/11336/65056
Cafferata, Lazaro; Jeandupeax, Rene; Romanelli, Gustavo Pablo; Mateo, Carmen Margarita; Jefford, Charles W.; A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanes; Asociación de Químicos e Ingenieros; Afinidad; 60; 504; 9-2003; 206-211
0001-9704
CONICET Digital
CONICET
url http://hdl.handle.net/11336/65056
identifier_str_mv Cafferata, Lazaro; Jeandupeax, Rene; Romanelli, Gustavo Pablo; Mateo, Carmen Margarita; Jefford, Charles W.; A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanes; Asociación de Químicos e Ingenieros; Afinidad; 60; 504; 9-2003; 206-211
0001-9704
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.raco.cat/index.php/afinidad/index
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
dc.publisher.none.fl_str_mv Asociación de Químicos e Ingenieros
publisher.none.fl_str_mv Asociación de Químicos e Ingenieros
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 12.976206

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