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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/179747
Ver los metadatos del registro completo
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CONICET Digital (CONICET) |
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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 Técnicas2025-09-03T10:03:03Zoai: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:34982025-09-03 10:03:04.253CONICET 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 |
_version_ |
1842269781220130816 |
score |
13.13397 |