Activity and stability of mesoporous molecular sieves modified with vanadium in the oxyfunctionalization of alpha-pinene

Autores
Cánepa, Analía; Vaschetto, Eliana; Herrero, Eduardo; Eimer, Griselda; Casuscelli, Sandra
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Selective oxyfunctionalization of terpenes is an interesting route to utilize these inexpensive natural products for numerous industrial applications. Thus, the oxygenated derivates obtained from the α-pinene oxidation in liquid phase (campholenic aldehyde, verbenol, verbenone) are important as flavor chemicals and precursors of fine chemicals, including sandalwood fragrance, taxol and vitamins A and E [1]. Traditionally, the high aggregated value chemicals are frequently produced by classic organic chemistry, focusing only on the desired product instead of considering the synthesis route, which leads to generate significant amounts of contaminated effluents that cause a great environmental impact. Thus green chemistry appears as a practical approach to achieve clean technologies and sustainable developments, providing the catalysis as a fundamental tool to minimize the process steps and allow the use of mild reaction conditions. In addition, a catalytic process to be economically and environmentally viable, it is essential that the catalyst can be recovered and regenerated. However a particular problem associated with the use of solid catalysts in the liquid phase, as opposed to the gas phase, is the leaching of the metal ion into solution. Mesoporous molecular materials with V contents varying from 0.035 wt% to 1.21 %wt were prepared by hydrothermal synthesis [2] to be used as potential catalysts in the reaction of α-pinene oxidation with H2O2. The major products observed were: verbenone, verbenol and campholenic aldehyde which are used in the pharmaceutical, perfume and cosmetics industry. The material with lower V content (0.035% w/w) was selected for a further study due to its high activity, TON and selectivity to allylic oxidation products. In this way, the effect of the nature of protic solvent: ethanol (EtOH), isoamyl alcohol (iAOH), and nonprotic solvent: acetonitrile (AcN), methyl ethyl ketone (MEK), on the α-pinene activity and products distribution were studied. The best results were obtained with AcN. Finally, the stability of the catalyst to the leaching of the active species and the possibility of recycling were checked. The experiments confirm that the V active species are not leached during the reaction. Thus the heterogeneous catalyst can be recovered and reused many times without loss in catalytic activity and selectivity.
Fil: Cánepa, Analía. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.
Fil: Vaschetto, Eliana. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.
Fil: Herrero, Eduardo. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.
Fil: Eimer, Griselda. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.
Fil: Casuscelli, Sandra. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.
Materia
alpha-pinene
oxyfunctionalization
mesoporous molecular
vanadium
Nivel de accesibilidad
acceso abierto
Condiciones de uso
Attribution-NonCommercial-NoDerivatives 4.0 International
Repositorio
Repositorio Institucional Abierto (UTN)
Institución
Universidad Tecnológica Nacional
OAI Identificador
oai:ria.utn.edu.ar:20.500.12272/13567
Acceder
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oai_identifier_str oai:ria.utn.edu.ar:20.500.12272/13567
network_acronym_str RIAUTN
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network_name_str Repositorio Institucional Abierto (UTN)
spelling Activity and stability of mesoporous molecular sieves modified with vanadium in the oxyfunctionalization of alpha-pineneCánepa, AnalíaVaschetto, ElianaHerrero, EduardoEimer, GriseldaCasuscelli, Sandraalpha-pineneoxyfunctionalizationmesoporous molecularvanadiumSelective oxyfunctionalization of terpenes is an interesting route to utilize these inexpensive natural products for numerous industrial applications. Thus, the oxygenated derivates obtained from the α-pinene oxidation in liquid phase (campholenic aldehyde, verbenol, verbenone) are important as flavor chemicals and precursors of fine chemicals, including sandalwood fragrance, taxol and vitamins A and E [1]. Traditionally, the high aggregated value chemicals are frequently produced by classic organic chemistry, focusing only on the desired product instead of considering the synthesis route, which leads to generate significant amounts of contaminated effluents that cause a great environmental impact. Thus green chemistry appears as a practical approach to achieve clean technologies and sustainable developments, providing the catalysis as a fundamental tool to minimize the process steps and allow the use of mild reaction conditions. In addition, a catalytic process to be economically and environmentally viable, it is essential that the catalyst can be recovered and regenerated. However a particular problem associated with the use of solid catalysts in the liquid phase, as opposed to the gas phase, is the leaching of the metal ion into solution. Mesoporous molecular materials with V contents varying from 0.035 wt% to 1.21 %wt were prepared by hydrothermal synthesis [2] to be used as potential catalysts in the reaction of α-pinene oxidation with H2O2. The major products observed were: verbenone, verbenol and campholenic aldehyde which are used in the pharmaceutical, perfume and cosmetics industry. The material with lower V content (0.035% w/w) was selected for a further study due to its high activity, TON and selectivity to allylic oxidation products. In this way, the effect of the nature of protic solvent: ethanol (EtOH), isoamyl alcohol (iAOH), and nonprotic solvent: acetonitrile (AcN), methyl ethyl ketone (MEK), on the α-pinene activity and products distribution were studied. The best results were obtained with AcN. Finally, the stability of the catalyst to the leaching of the active species and the possibility of recycling were checked. The experiments confirm that the V active species are not leached during the reaction. Thus the heterogeneous catalyst can be recovered and reused many times without loss in catalytic activity and selectivity.Fil: Cánepa, Analía. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.Fil: Vaschetto, Eliana. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.Fil: Herrero, Eduardo. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.Fil: Eimer, Griselda. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.Fil: Casuscelli, Sandra. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.5th Czech-Italian-Spanish Conference on Molecular Sieves and Catalysis2025-07-30T19:40:47Z2013info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articulopdfapplication/pdfhttps://hdl.handle.net/20.500.12272/13567enginfo:eu-repo/semantics/openAccessAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/Griselda Eimerreponame:Repositorio Institucional Abierto (UTN)instname:Universidad Tecnológica Nacional2026-09-24T12:47:23Zoai:ria.utn.edu.ar:20.500.12272/13567instacron:UTNInstitucionalhttp://ria.utn.edu.ar/Universidad públicaNo correspondehttp://ria.utn.edu.ar/oaigestionria@rec.utn.edu.ar; fsuarez@rec.utn.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:a2026-09-24 12:47:24.173Repositorio Institucional Abierto (UTN) - Universidad Tecnológica Nacionalfalse
dc.title.none.fl_str_mv Activity and stability of mesoporous molecular sieves modified with vanadium in the oxyfunctionalization of alpha-pinene
title Activity and stability of mesoporous molecular sieves modified with vanadium in the oxyfunctionalization of alpha-pinene
spellingShingle Activity and stability of mesoporous molecular sieves modified with vanadium in the oxyfunctionalization of alpha-pinene
Cánepa, Analía
alpha-pinene
oxyfunctionalization
mesoporous molecular
vanadium
title_short Activity and stability of mesoporous molecular sieves modified with vanadium in the oxyfunctionalization of alpha-pinene
title_full Activity and stability of mesoporous molecular sieves modified with vanadium in the oxyfunctionalization of alpha-pinene
title_fullStr Activity and stability of mesoporous molecular sieves modified with vanadium in the oxyfunctionalization of alpha-pinene
title_full_unstemmed Activity and stability of mesoporous molecular sieves modified with vanadium in the oxyfunctionalization of alpha-pinene
title_sort Activity and stability of mesoporous molecular sieves modified with vanadium in the oxyfunctionalization of alpha-pinene
dc.creator.none.fl_str_mv Cánepa, Analía
Vaschetto, Eliana
Herrero, Eduardo
Eimer, Griselda
Casuscelli, Sandra
author Cánepa, Analía
author_facet Cánepa, Analía
Vaschetto, Eliana
Herrero, Eduardo
Eimer, Griselda
Casuscelli, Sandra
author_role author
author2 Vaschetto, Eliana
Herrero, Eduardo
Eimer, Griselda
Casuscelli, Sandra
author2_role author
author
author
author
dc.subject.none.fl_str_mv alpha-pinene
oxyfunctionalization
mesoporous molecular
vanadium
topic alpha-pinene
oxyfunctionalization
mesoporous molecular
vanadium
dc.description.none.fl_txt_mv Selective oxyfunctionalization of terpenes is an interesting route to utilize these inexpensive natural products for numerous industrial applications. Thus, the oxygenated derivates obtained from the α-pinene oxidation in liquid phase (campholenic aldehyde, verbenol, verbenone) are important as flavor chemicals and precursors of fine chemicals, including sandalwood fragrance, taxol and vitamins A and E [1]. Traditionally, the high aggregated value chemicals are frequently produced by classic organic chemistry, focusing only on the desired product instead of considering the synthesis route, which leads to generate significant amounts of contaminated effluents that cause a great environmental impact. Thus green chemistry appears as a practical approach to achieve clean technologies and sustainable developments, providing the catalysis as a fundamental tool to minimize the process steps and allow the use of mild reaction conditions. In addition, a catalytic process to be economically and environmentally viable, it is essential that the catalyst can be recovered and regenerated. However a particular problem associated with the use of solid catalysts in the liquid phase, as opposed to the gas phase, is the leaching of the metal ion into solution. Mesoporous molecular materials with V contents varying from 0.035 wt% to 1.21 %wt were prepared by hydrothermal synthesis [2] to be used as potential catalysts in the reaction of α-pinene oxidation with H2O2. The major products observed were: verbenone, verbenol and campholenic aldehyde which are used in the pharmaceutical, perfume and cosmetics industry. The material with lower V content (0.035% w/w) was selected for a further study due to its high activity, TON and selectivity to allylic oxidation products. In this way, the effect of the nature of protic solvent: ethanol (EtOH), isoamyl alcohol (iAOH), and nonprotic solvent: acetonitrile (AcN), methyl ethyl ketone (MEK), on the α-pinene activity and products distribution were studied. The best results were obtained with AcN. Finally, the stability of the catalyst to the leaching of the active species and the possibility of recycling were checked. The experiments confirm that the V active species are not leached during the reaction. Thus the heterogeneous catalyst can be recovered and reused many times without loss in catalytic activity and selectivity.
Fil: Cánepa, Analía. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.
Fil: Vaschetto, Eliana. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.
Fil: Herrero, Eduardo. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.
Fil: Eimer, Griselda. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.
Fil: Casuscelli, Sandra. Universidad tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina.
description Selective oxyfunctionalization of terpenes is an interesting route to utilize these inexpensive natural products for numerous industrial applications. Thus, the oxygenated derivates obtained from the α-pinene oxidation in liquid phase (campholenic aldehyde, verbenol, verbenone) are important as flavor chemicals and precursors of fine chemicals, including sandalwood fragrance, taxol and vitamins A and E [1]. Traditionally, the high aggregated value chemicals are frequently produced by classic organic chemistry, focusing only on the desired product instead of considering the synthesis route, which leads to generate significant amounts of contaminated effluents that cause a great environmental impact. Thus green chemistry appears as a practical approach to achieve clean technologies and sustainable developments, providing the catalysis as a fundamental tool to minimize the process steps and allow the use of mild reaction conditions. In addition, a catalytic process to be economically and environmentally viable, it is essential that the catalyst can be recovered and regenerated. However a particular problem associated with the use of solid catalysts in the liquid phase, as opposed to the gas phase, is the leaching of the metal ion into solution. Mesoporous molecular materials with V contents varying from 0.035 wt% to 1.21 %wt were prepared by hydrothermal synthesis [2] to be used as potential catalysts in the reaction of α-pinene oxidation with H2O2. The major products observed were: verbenone, verbenol and campholenic aldehyde which are used in the pharmaceutical, perfume and cosmetics industry. The material with lower V content (0.035% w/w) was selected for a further study due to its high activity, TON and selectivity to allylic oxidation products. In this way, the effect of the nature of protic solvent: ethanol (EtOH), isoamyl alcohol (iAOH), and nonprotic solvent: acetonitrile (AcN), methyl ethyl ketone (MEK), on the α-pinene activity and products distribution were studied. The best results were obtained with AcN. Finally, the stability of the catalyst to the leaching of the active species and the possibility of recycling were checked. The experiments confirm that the V active species are not leached during the reaction. Thus the heterogeneous catalyst can be recovered and reused many times without loss in catalytic activity and selectivity.
publishDate 2013
dc.date.none.fl_str_mv 2013
2025-07-30T19:40:47Z
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 https://hdl.handle.net/20.500.12272/13567
url https://hdl.handle.net/20.500.12272/13567
dc.language.none.fl_str_mv eng
language eng
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
Griselda Eimer
eu_rights_str_mv openAccess
rights_invalid_str_mv Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
Griselda Eimer
dc.format.none.fl_str_mv pdf
application/pdf
dc.publisher.none.fl_str_mv 5th Czech-Italian-Spanish Conference on Molecular Sieves and Catalysis
publisher.none.fl_str_mv 5th Czech-Italian-Spanish Conference on Molecular Sieves and Catalysis
dc.source.none.fl_str_mv reponame:Repositorio Institucional Abierto (UTN)
instname:Universidad Tecnológica Nacional
reponame_str Repositorio Institucional Abierto (UTN)
collection Repositorio Institucional Abierto (UTN)
instname_str Universidad Tecnológica Nacional
repository.name.fl_str_mv Repositorio Institucional Abierto (UTN) - Universidad Tecnológica Nacional
repository.mail.fl_str_mv gestionria@rec.utn.edu.ar; fsuarez@rec.utn.edu.ar
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score 13.265058

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