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

Autores
Cafferata, Lázaro F. R.; 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.
Laboratorio de Estudio de Compuestos Orgánicos
Centro de Investigación y Desarrollo en Ciencias Aplicadas
Materia
Química
Cis- and trans- fused 1,2,4-trioxanes
Artemisinine
Thermolysis
Reactions kinetics
Artemisinina
Termófisis
Cinética de reacción
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/98261
Acceder
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oai_identifier_str oai:sedici.unlp.edu.ar:10915/98261
network_acronym_str SEDICI
repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling A kinetic and mechanistic study on the thermal decomposition reactions of cis- and trans- fused 1,2,4-trioxanesCafferata, Lázaro F. R.Jeandupeax, ReneRomanelli, Gustavo PabloMateo, Carmen MargaritaJefford, Charles W.QuímicaCis- and trans- fused 1,2,4-trioxanesArtemisinineThermolysisReactions kineticsArtemisininaTermófisisCinética de reacciónThe 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.Laboratorio de Estudio de Compuestos OrgánicosCentro de Investigación y Desarrollo en Ciencias Aplicadas2003-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf206-211http://sedici.unlp.edu.ar/handle/10915/98261enginfo:eu-repo/semantics/altIdentifier/url/https://ri.conicet.gov.ar/11336/65056info:eu-repo/semantics/altIdentifier/url/https://dialnet.unirioja.es/servlet/articulo?codigo=2642748info:eu-repo/semantics/altIdentifier/issn/0001-9704info:eu-repo/semantics/altIdentifier/hdl/11336/65056info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-29T11:20:16Zoai:sedici.unlp.edu.ar:10915/98261Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:20:17.236SEDICI (UNLP) - Universidad Nacional de La Platafalse
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, Lázaro F. R.
Química
Cis- and trans- fused 1,2,4-trioxanes
Artemisinine
Thermolysis
Reactions kinetics
Artemisinina
Termófisis
Cinética de reacción
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, Lázaro F. R.
Jeandupeax, Rene
Romanelli, Gustavo Pablo
Mateo, Carmen Margarita
Jefford, Charles W.
author Cafferata, Lázaro F. R.
author_facet Cafferata, Lázaro F. R.
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 Química
Cis- and trans- fused 1,2,4-trioxanes
Artemisinine
Thermolysis
Reactions kinetics
Artemisinina
Termófisis
Cinética de reacción
topic Química
Cis- and trans- fused 1,2,4-trioxanes
Artemisinine
Thermolysis
Reactions kinetics
Artemisinina
Termófisis
Cinética de reacción
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.
Laboratorio de Estudio de Compuestos Orgánicos
Centro de Investigación y Desarrollo en Ciencias Aplicadas
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
Articulo
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://sedici.unlp.edu.ar/handle/10915/98261
url http://sedici.unlp.edu.ar/handle/10915/98261
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://ri.conicet.gov.ar/11336/65056
info:eu-repo/semantics/altIdentifier/url/https://dialnet.unirioja.es/servlet/articulo?codigo=2642748
info:eu-repo/semantics/altIdentifier/issn/0001-9704
info:eu-repo/semantics/altIdentifier/hdl/11336/65056
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
dc.format.none.fl_str_mv application/pdf
206-211
dc.source.none.fl_str_mv reponame:SEDICI (UNLP)
instname:Universidad Nacional de La Plata
instacron:UNLP
reponame_str SEDICI (UNLP)
collection SEDICI (UNLP)
instname_str Universidad Nacional de La Plata
instacron_str UNLP
institution UNLP
repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
repository.mail.fl_str_mv alira@sedici.unlp.edu.ar
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score 13.070432

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