4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution

Autores
Nesprias, Rosa Karina; Iglesias, Mariángeles; Rivas, Sonia; Alvarez, Elida; Barreto, Gastón Pablo; Eyler, Gladys Nora; Cañizo, Adriana Ines
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Cyclic organic peroxides have interesting pharmacological properties and are used at industrial level as polyfunctional initiators of polymerization, and so their preparation through novel methods has attracted the attention of numerous researchers. White crystals of 4-heptanone cyclic diperoxide (HDP) can be obtained in acidic media at −1°C by a reaction between 4-heptanone and hydrogen peroxide. Its thermal decomposition was studied in acetone, cyclohexane, acetonitrile, ethyl acetate, ethanol, 2-propanol, 2-butanol, and 1,4-dioxane at temperatures higher than 120°C, showing a behavior accordingly with a pseudo-first-order kinetic law up to at least 80% HDP conversion. It was demonstrated that an increase in solvent polarity is accompanied by an increase in reaction rates. The effect of solvent polarity on the thermal decomposition rate constant values can be associated with a reaction mechanism involving a more dipolar-activated complex than the diperoxide initial molecule. The activation parameters varied widely from 31.2 to 46.6 kcal mol−1 and −1.33 to 31.7 cal mol−1 K−1 when going from ethanol to cyclohexane as reaction solvents, respectively. An enthalpy–entropy compensation effect was observed in all solvents. Specific interactions between the oxygen atoms from the peroxidic bond and the hydrogen atom bonded to C2 and/or from the OH group can be taken into account to explain that the existence of the compensation effect does not mean that an isokinetic relationship consequently can be established. The kinetic results showed that an isokinetic relationship is observed only for a group of solvents.
Fil: Nesprias, Rosa Karina. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
Fil: Iglesias, Mariángeles. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
Fil: Rivas, Sonia. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
Fil: Alvarez, Elida. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
Fil: Barreto, Gastón Pablo. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Eyler, Gladys Nora. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
Fil: Cañizo, Adriana Ines. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Materia
CYCLIC PEROXIDE
KINETICS IN SOLUTION
SOLVENT EFFECT
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:11336/179747
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling 4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solutionNesprias, Rosa KarinaIglesias, MariángelesRivas, SoniaAlvarez, ElidaBarreto, Gastón PabloEyler, Gladys NoraCañizo, Adriana InesCYCLIC PEROXIDEKINETICS IN SOLUTIONSOLVENT EFFECThttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Cyclic organic peroxides have interesting pharmacological properties and are used at industrial level as polyfunctional initiators of polymerization, and so their preparation through novel methods has attracted the attention of numerous researchers. White crystals of 4-heptanone cyclic diperoxide (HDP) can be obtained in acidic media at −1°C by a reaction between 4-heptanone and hydrogen peroxide. Its thermal decomposition was studied in acetone, cyclohexane, acetonitrile, ethyl acetate, ethanol, 2-propanol, 2-butanol, and 1,4-dioxane at temperatures higher than 120°C, showing a behavior accordingly with a pseudo-first-order kinetic law up to at least 80% HDP conversion. It was demonstrated that an increase in solvent polarity is accompanied by an increase in reaction rates. The effect of solvent polarity on the thermal decomposition rate constant values can be associated with a reaction mechanism involving a more dipolar-activated complex than the diperoxide initial molecule. The activation parameters varied widely from 31.2 to 46.6 kcal mol−1 and −1.33 to 31.7 cal mol−1 K−1 when going from ethanol to cyclohexane as reaction solvents, respectively. An enthalpy–entropy compensation effect was observed in all solvents. Specific interactions between the oxygen atoms from the peroxidic bond and the hydrogen atom bonded to C2 and/or from the OH group can be taken into account to explain that the existence of the compensation effect does not mean that an isokinetic relationship consequently can be established. The kinetic results showed that an isokinetic relationship is observed only for a group of solvents.Fil: Nesprias, Rosa Karina. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; ArgentinaFil: Iglesias, Mariángeles. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; ArgentinaFil: Rivas, Sonia. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; ArgentinaFil: Alvarez, Elida. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; ArgentinaFil: Barreto, Gastón Pablo. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Eyler, Gladys Nora. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; ArgentinaFil: Cañizo, Adriana Ines. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaJohn Wiley & Sons Inc.2011-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/179747Nesprias, Rosa Karina; Iglesias, Mariángeles; Rivas, Sonia; Alvarez, Elida; Barreto, Gastón Pablo; et al.; 4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution; John Wiley & Sons Inc.; International Journal of Chemical Kinetics; 43; 11; 7-2011; 657-6660538-8066CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/full/10.1002/kin.20600info:eu-repo/semantics/altIdentifier/doi/10.1002/kin.20600info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:19:32Zoai:ri.conicet.gov.ar:11336/179747instacron: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 10:19:32.502CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv 4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution
title 4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution
spellingShingle 4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution
Nesprias, Rosa Karina
CYCLIC PEROXIDE
KINETICS IN SOLUTION
SOLVENT EFFECT
title_short 4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution
title_full 4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution
title_fullStr 4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution
title_full_unstemmed 4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution
title_sort 4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution
dc.creator.none.fl_str_mv Nesprias, Rosa Karina
Iglesias, Mariángeles
Rivas, Sonia
Alvarez, Elida
Barreto, Gastón Pablo
Eyler, Gladys Nora
Cañizo, Adriana Ines
author Nesprias, Rosa Karina
author_facet Nesprias, Rosa Karina
Iglesias, Mariángeles
Rivas, Sonia
Alvarez, Elida
Barreto, Gastón Pablo
Eyler, Gladys Nora
Cañizo, Adriana Ines
author_role author
author2 Iglesias, Mariángeles
Rivas, Sonia
Alvarez, Elida
Barreto, Gastón Pablo
Eyler, Gladys Nora
Cañizo, Adriana Ines
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv CYCLIC PEROXIDE
KINETICS IN SOLUTION
SOLVENT EFFECT
topic CYCLIC PEROXIDE
KINETICS IN SOLUTION
SOLVENT EFFECT
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Cyclic organic peroxides have interesting pharmacological properties and are used at industrial level as polyfunctional initiators of polymerization, and so their preparation through novel methods has attracted the attention of numerous researchers. White crystals of 4-heptanone cyclic diperoxide (HDP) can be obtained in acidic media at −1°C by a reaction between 4-heptanone and hydrogen peroxide. Its thermal decomposition was studied in acetone, cyclohexane, acetonitrile, ethyl acetate, ethanol, 2-propanol, 2-butanol, and 1,4-dioxane at temperatures higher than 120°C, showing a behavior accordingly with a pseudo-first-order kinetic law up to at least 80% HDP conversion. It was demonstrated that an increase in solvent polarity is accompanied by an increase in reaction rates. The effect of solvent polarity on the thermal decomposition rate constant values can be associated with a reaction mechanism involving a more dipolar-activated complex than the diperoxide initial molecule. The activation parameters varied widely from 31.2 to 46.6 kcal mol−1 and −1.33 to 31.7 cal mol−1 K−1 when going from ethanol to cyclohexane as reaction solvents, respectively. An enthalpy–entropy compensation effect was observed in all solvents. Specific interactions between the oxygen atoms from the peroxidic bond and the hydrogen atom bonded to C2 and/or from the OH group can be taken into account to explain that the existence of the compensation effect does not mean that an isokinetic relationship consequently can be established. The kinetic results showed that an isokinetic relationship is observed only for a group of solvents.
Fil: Nesprias, Rosa Karina. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
Fil: Iglesias, Mariángeles. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
Fil: Rivas, Sonia. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
Fil: Alvarez, Elida. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
Fil: Barreto, Gastón Pablo. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Eyler, Gladys Nora. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
Fil: Cañizo, Adriana Ines. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
description Cyclic organic peroxides have interesting pharmacological properties and are used at industrial level as polyfunctional initiators of polymerization, and so their preparation through novel methods has attracted the attention of numerous researchers. White crystals of 4-heptanone cyclic diperoxide (HDP) can be obtained in acidic media at −1°C by a reaction between 4-heptanone and hydrogen peroxide. Its thermal decomposition was studied in acetone, cyclohexane, acetonitrile, ethyl acetate, ethanol, 2-propanol, 2-butanol, and 1,4-dioxane at temperatures higher than 120°C, showing a behavior accordingly with a pseudo-first-order kinetic law up to at least 80% HDP conversion. It was demonstrated that an increase in solvent polarity is accompanied by an increase in reaction rates. The effect of solvent polarity on the thermal decomposition rate constant values can be associated with a reaction mechanism involving a more dipolar-activated complex than the diperoxide initial molecule. The activation parameters varied widely from 31.2 to 46.6 kcal mol−1 and −1.33 to 31.7 cal mol−1 K−1 when going from ethanol to cyclohexane as reaction solvents, respectively. An enthalpy–entropy compensation effect was observed in all solvents. Specific interactions between the oxygen atoms from the peroxidic bond and the hydrogen atom bonded to C2 and/or from the OH group can be taken into account to explain that the existence of the compensation effect does not mean that an isokinetic relationship consequently can be established. The kinetic results showed that an isokinetic relationship is observed only for a group of solvents.
publishDate 2011
dc.date.none.fl_str_mv 2011-07
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/11336/179747
Nesprias, Rosa Karina; Iglesias, Mariángeles; Rivas, Sonia; Alvarez, Elida; Barreto, Gastón Pablo; et al.; 4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution; John Wiley & Sons Inc.; International Journal of Chemical Kinetics; 43; 11; 7-2011; 657-666
0538-8066
CONICET Digital
CONICET
url http://hdl.handle.net/11336/179747
identifier_str_mv Nesprias, Rosa Karina; Iglesias, Mariángeles; Rivas, Sonia; Alvarez, Elida; Barreto, Gastón Pablo; et al.; 4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution; John Wiley & Sons Inc.; International Journal of Chemical Kinetics; 43; 11; 7-2011; 657-666
0538-8066
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/full/10.1002/kin.20600
info:eu-repo/semantics/altIdentifier/doi/10.1002/kin.20600
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
dc.publisher.none.fl_str_mv John Wiley & Sons Inc.
publisher.none.fl_str_mv John Wiley & Sons Inc.
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 13.070432

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