Catalytic and spectroscopic study of the allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones on acid-base catalysts

Autores
Braun, Fernando; Di Cosimo, Juana Isabel
Año de publicación
2006
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The hydrogen transfer reduction of an α,β-unsaturated ketone, mesityl oxide, was studied on several single oxides in the gas-phase using 2-propanol as a hydrogen source. Selectivity is essentially determined by oxide electronegativity because the reaction proceeds via surface intermediates formed by coordination of 2-propanol and also of C{double bond, long}O and C{double bond, long}C groups of the reactant ketone on the Lewis acid sites provided by the metal cations. Oxides that combine weak Lewis acid cations and strongly basic oxygens such as MgO or Y2O3 yield allylic alcohols as the main reduction products of the gas-phase reaction. Adsorption experiments on MgO monitored by FTIR spectroscopy show that competitive 2-propanol and mesityl oxide adsorption on Mg2+ cations favors the hydrogen transfer process by a concerted Meerwein-Ponndorf-Verley mechanism whereas strong mesityl oxide adsorption causes simultaneous reduction of C{double bond, long}O and C{double bond, long}C bonds with formation of the saturated alcohol. High reaction temperatures strongly affect the stability of the complex reaction intermediates postulated for saturated and allylic alcohol formation, thereby favoring the simpler double bond migration reaction over the reduction reactions. More electronegative oxides such as ZrO2 or Al2O3 tend to promote the C{double bond, long}C bond reduction giving the saturated ketone. On these oxides, 2-propanol decomposes into acetone and molecular hydrogen at high rates, which is detrimental to carbonyl reduction.
Fil: Braun, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Materia
Hydrogen Transfer
Reduction
Alpha,Beta-Unsaturated Ketone
Electronegativity
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:11336/65316
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/65316
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Catalytic and spectroscopic study of the allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones on acid-base catalystsBraun, FernandoDi Cosimo, Juana IsabelHydrogen TransferReductionAlpha,Beta-Unsaturated KetoneElectronegativityhttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2The hydrogen transfer reduction of an α,β-unsaturated ketone, mesityl oxide, was studied on several single oxides in the gas-phase using 2-propanol as a hydrogen source. Selectivity is essentially determined by oxide electronegativity because the reaction proceeds via surface intermediates formed by coordination of 2-propanol and also of C{double bond, long}O and C{double bond, long}C groups of the reactant ketone on the Lewis acid sites provided by the metal cations. Oxides that combine weak Lewis acid cations and strongly basic oxygens such as MgO or Y2O3 yield allylic alcohols as the main reduction products of the gas-phase reaction. Adsorption experiments on MgO monitored by FTIR spectroscopy show that competitive 2-propanol and mesityl oxide adsorption on Mg2+ cations favors the hydrogen transfer process by a concerted Meerwein-Ponndorf-Verley mechanism whereas strong mesityl oxide adsorption causes simultaneous reduction of C{double bond, long}O and C{double bond, long}C bonds with formation of the saturated alcohol. High reaction temperatures strongly affect the stability of the complex reaction intermediates postulated for saturated and allylic alcohol formation, thereby favoring the simpler double bond migration reaction over the reduction reactions. More electronegative oxides such as ZrO2 or Al2O3 tend to promote the C{double bond, long}C bond reduction giving the saturated ketone. On these oxides, 2-propanol decomposes into acetone and molecular hydrogen at high rates, which is detrimental to carbonyl reduction.Fil: Braun, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaElsevier Science2006-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/65316Braun, Fernando; Di Cosimo, Juana Isabel; Catalytic and spectroscopic study of the allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones on acid-base catalysts; Elsevier Science; Catalysis Today; 116; 2 SPEC. ISS.; 8-2006; 206-2150920-5861CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.cattod.2006.01.026info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:45:50Zoai:ri.conicet.gov.ar:11336/65316instacron: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 09:45:50.544CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Catalytic and spectroscopic study of the allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones on acid-base catalysts
title Catalytic and spectroscopic study of the allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones on acid-base catalysts
spellingShingle Catalytic and spectroscopic study of the allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones on acid-base catalysts
Braun, Fernando
Hydrogen Transfer
Reduction
Alpha,Beta-Unsaturated Ketone
Electronegativity
title_short Catalytic and spectroscopic study of the allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones on acid-base catalysts
title_full Catalytic and spectroscopic study of the allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones on acid-base catalysts
title_fullStr Catalytic and spectroscopic study of the allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones on acid-base catalysts
title_full_unstemmed Catalytic and spectroscopic study of the allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones on acid-base catalysts
title_sort Catalytic and spectroscopic study of the allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones on acid-base catalysts
dc.creator.none.fl_str_mv Braun, Fernando
Di Cosimo, Juana Isabel
author Braun, Fernando
author_facet Braun, Fernando
Di Cosimo, Juana Isabel
author_role author
author2 Di Cosimo, Juana Isabel
author2_role author
dc.subject.none.fl_str_mv Hydrogen Transfer
Reduction
Alpha,Beta-Unsaturated Ketone
Electronegativity
topic Hydrogen Transfer
Reduction
Alpha,Beta-Unsaturated Ketone
Electronegativity
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv The hydrogen transfer reduction of an α,β-unsaturated ketone, mesityl oxide, was studied on several single oxides in the gas-phase using 2-propanol as a hydrogen source. Selectivity is essentially determined by oxide electronegativity because the reaction proceeds via surface intermediates formed by coordination of 2-propanol and also of C{double bond, long}O and C{double bond, long}C groups of the reactant ketone on the Lewis acid sites provided by the metal cations. Oxides that combine weak Lewis acid cations and strongly basic oxygens such as MgO or Y2O3 yield allylic alcohols as the main reduction products of the gas-phase reaction. Adsorption experiments on MgO monitored by FTIR spectroscopy show that competitive 2-propanol and mesityl oxide adsorption on Mg2+ cations favors the hydrogen transfer process by a concerted Meerwein-Ponndorf-Verley mechanism whereas strong mesityl oxide adsorption causes simultaneous reduction of C{double bond, long}O and C{double bond, long}C bonds with formation of the saturated alcohol. High reaction temperatures strongly affect the stability of the complex reaction intermediates postulated for saturated and allylic alcohol formation, thereby favoring the simpler double bond migration reaction over the reduction reactions. More electronegative oxides such as ZrO2 or Al2O3 tend to promote the C{double bond, long}C bond reduction giving the saturated ketone. On these oxides, 2-propanol decomposes into acetone and molecular hydrogen at high rates, which is detrimental to carbonyl reduction.
Fil: Braun, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
description The hydrogen transfer reduction of an α,β-unsaturated ketone, mesityl oxide, was studied on several single oxides in the gas-phase using 2-propanol as a hydrogen source. Selectivity is essentially determined by oxide electronegativity because the reaction proceeds via surface intermediates formed by coordination of 2-propanol and also of C{double bond, long}O and C{double bond, long}C groups of the reactant ketone on the Lewis acid sites provided by the metal cations. Oxides that combine weak Lewis acid cations and strongly basic oxygens such as MgO or Y2O3 yield allylic alcohols as the main reduction products of the gas-phase reaction. Adsorption experiments on MgO monitored by FTIR spectroscopy show that competitive 2-propanol and mesityl oxide adsorption on Mg2+ cations favors the hydrogen transfer process by a concerted Meerwein-Ponndorf-Verley mechanism whereas strong mesityl oxide adsorption causes simultaneous reduction of C{double bond, long}O and C{double bond, long}C bonds with formation of the saturated alcohol. High reaction temperatures strongly affect the stability of the complex reaction intermediates postulated for saturated and allylic alcohol formation, thereby favoring the simpler double bond migration reaction over the reduction reactions. More electronegative oxides such as ZrO2 or Al2O3 tend to promote the C{double bond, long}C bond reduction giving the saturated ketone. On these oxides, 2-propanol decomposes into acetone and molecular hydrogen at high rates, which is detrimental to carbonyl reduction.
publishDate 2006
dc.date.none.fl_str_mv 2006-08
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/11336/65316
Braun, Fernando; Di Cosimo, Juana Isabel; Catalytic and spectroscopic study of the allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones on acid-base catalysts; Elsevier Science; Catalysis Today; 116; 2 SPEC. ISS.; 8-2006; 206-215
0920-5861
CONICET Digital
CONICET
url http://hdl.handle.net/11336/65316
identifier_str_mv Braun, Fernando; Di Cosimo, Juana Isabel; Catalytic and spectroscopic study of the allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones on acid-base catalysts; Elsevier Science; Catalysis Today; 116; 2 SPEC. ISS.; 8-2006; 206-215
0920-5861
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.cattod.2006.01.026
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
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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_ 1844613433145688064
score 13.070432

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