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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/65056
Ver los metadatos del registro completo
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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 Técnicas2025-09-29T09:41:23Zoai: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:34982025-09-29 09:41:23.536CONICET 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 |
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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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13.070432 |