Gas-phase hydrogen transfer reduction of α,β-unsaturated ketones on Mg-based catalysts

Autores
Di Cosimo, Juana Isabel; Acosta, A.; Apesteguia, Carlos Rodolfo
Año de publicación
2004
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The gas-phase regioselective reduction of mesityl oxide to the allyl alcohol using 2-propanol as a hydrogen donor was studied at 523 K on basic MgO, MgAl0.33Ox and Cu0.05MgAl0.65Ox oxides. Catalysts were characterized using a variety of physical and spectroscopic techniques. The effect of contact time on the product distribution was determined in order to identify primary and secondary reaction pathways. Main reaction products from mesityl oxide conversion were the two allyl alcohol isomers (UOL, 4-methyl-3-penten-2-ol and 4-methyl-4-penten-2-ol), isomesityl oxide, methyl isobutyl ketone (MIBK), methyl isobutyl carbinol and C9 aldol condensation products. Bifunctional Cu0.05MgAl0.65Ox did not produce alcohols. Metallic Cu atoms readily decomposed 2-propanol forming acetone and mobile surface H atoms that selectively reduced the CC bond of mesityl oxide giving mainly MIBK. UOL formed on MgO at unusually high yields for a gas-phase reaction (40% at 523 K, 2-propanol/mesityl oxide = 5 and HLSV = 14 cm3/(h g)). UOL formation on MgO proceeds via a hydrogen transfer Meerwein–Ponndorf–Verley (MPV) mechanism without participation of surface H atoms from 2-propanol dissociation. Weak acid–strong base Mg2+O2− surface pairs efficiently promote formation of the six-atom cyclic intermediate required in the MPV mechanism for selectively reducing the CO bond of an unsaturated ketone to the corresponding allyl alcohol. In contrast, UOL yield on MgAl0.33Ox was always lower than 5%. UOL formation is hindered on MgAl0.33Ox because surface Al3+ sites decrease by dilution the density of Mg2+O2− pairs and concomitantly favor the adsorption of mesityl oxide via the CC bond, thereby promoting the selective formation of MIBK.
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 ; Argentina
Fil: Acosta, A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Fil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Materia
Regioselectivity
Hydrogen Transfer
Basic Catalysis
Α,Β-Unsaturated Ketones
Reduction
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:11336/55837
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/55837
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Gas-phase hydrogen transfer reduction of α,β-unsaturated ketones on Mg-based catalystsDi Cosimo, Juana IsabelAcosta, A.Apesteguia, Carlos RodolfoRegioselectivityHydrogen TransferBasic CatalysisΑ,Β-Unsaturated KetonesReductionhttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2The gas-phase regioselective reduction of mesityl oxide to the allyl alcohol using 2-propanol as a hydrogen donor was studied at 523 K on basic MgO, MgAl0.33Ox and Cu0.05MgAl0.65Ox oxides. Catalysts were characterized using a variety of physical and spectroscopic techniques. The effect of contact time on the product distribution was determined in order to identify primary and secondary reaction pathways. Main reaction products from mesityl oxide conversion were the two allyl alcohol isomers (UOL, 4-methyl-3-penten-2-ol and 4-methyl-4-penten-2-ol), isomesityl oxide, methyl isobutyl ketone (MIBK), methyl isobutyl carbinol and C9 aldol condensation products. Bifunctional Cu0.05MgAl0.65Ox did not produce alcohols. Metallic Cu atoms readily decomposed 2-propanol forming acetone and mobile surface H atoms that selectively reduced the CC bond of mesityl oxide giving mainly MIBK. UOL formed on MgO at unusually high yields for a gas-phase reaction (40% at 523 K, 2-propanol/mesityl oxide = 5 and HLSV = 14 cm3/(h g)). UOL formation on MgO proceeds via a hydrogen transfer Meerwein–Ponndorf–Verley (MPV) mechanism without participation of surface H atoms from 2-propanol dissociation. Weak acid–strong base Mg2+O2− surface pairs efficiently promote formation of the six-atom cyclic intermediate required in the MPV mechanism for selectively reducing the CO bond of an unsaturated ketone to the corresponding allyl alcohol. In contrast, UOL yield on MgAl0.33Ox was always lower than 5%. UOL formation is hindered on MgAl0.33Ox because surface Al3+ sites decrease by dilution the density of Mg2+O2− pairs and concomitantly favor the adsorption of mesityl oxide via the CC bond, thereby promoting the selective formation of MIBK.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 ; ArgentinaFil: Acosta, A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaElsevier Science2004-11info: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/11336/55837Di Cosimo, Juana Isabel; Acosta, A.; Apesteguia, Carlos Rodolfo; Gas-phase hydrogen transfer reduction of α,β-unsaturated ketones on Mg-based catalysts; Elsevier Science; Journal of Molecular Catalysis A: Chemical; 222; 1-2; 11-2004; 87-961381-1169CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.molcata.2004.07.020info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:07:38Zoai:ri.conicet.gov.ar:11336/55837instacron: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 10:07:38.682CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Gas-phase hydrogen transfer reduction of α,β-unsaturated ketones on Mg-based catalysts
title Gas-phase hydrogen transfer reduction of α,β-unsaturated ketones on Mg-based catalysts
spellingShingle Gas-phase hydrogen transfer reduction of α,β-unsaturated ketones on Mg-based catalysts
Di Cosimo, Juana Isabel
Regioselectivity
Hydrogen Transfer
Basic Catalysis
Α,Β-Unsaturated Ketones
Reduction
title_short Gas-phase hydrogen transfer reduction of α,β-unsaturated ketones on Mg-based catalysts
title_full Gas-phase hydrogen transfer reduction of α,β-unsaturated ketones on Mg-based catalysts
title_fullStr Gas-phase hydrogen transfer reduction of α,β-unsaturated ketones on Mg-based catalysts
title_full_unstemmed Gas-phase hydrogen transfer reduction of α,β-unsaturated ketones on Mg-based catalysts
title_sort Gas-phase hydrogen transfer reduction of α,β-unsaturated ketones on Mg-based catalysts
dc.creator.none.fl_str_mv Di Cosimo, Juana Isabel
Acosta, A.
Apesteguia, Carlos Rodolfo
author Di Cosimo, Juana Isabel
author_facet Di Cosimo, Juana Isabel
Acosta, A.
Apesteguia, Carlos Rodolfo
author_role author
author2 Acosta, A.
Apesteguia, Carlos Rodolfo
author2_role author
author
dc.subject.none.fl_str_mv Regioselectivity
Hydrogen Transfer
Basic Catalysis
Α,Β-Unsaturated Ketones
Reduction
topic Regioselectivity
Hydrogen Transfer
Basic Catalysis
Α,Β-Unsaturated Ketones
Reduction
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 gas-phase regioselective reduction of mesityl oxide to the allyl alcohol using 2-propanol as a hydrogen donor was studied at 523 K on basic MgO, MgAl0.33Ox and Cu0.05MgAl0.65Ox oxides. Catalysts were characterized using a variety of physical and spectroscopic techniques. The effect of contact time on the product distribution was determined in order to identify primary and secondary reaction pathways. Main reaction products from mesityl oxide conversion were the two allyl alcohol isomers (UOL, 4-methyl-3-penten-2-ol and 4-methyl-4-penten-2-ol), isomesityl oxide, methyl isobutyl ketone (MIBK), methyl isobutyl carbinol and C9 aldol condensation products. Bifunctional Cu0.05MgAl0.65Ox did not produce alcohols. Metallic Cu atoms readily decomposed 2-propanol forming acetone and mobile surface H atoms that selectively reduced the CC bond of mesityl oxide giving mainly MIBK. UOL formed on MgO at unusually high yields for a gas-phase reaction (40% at 523 K, 2-propanol/mesityl oxide = 5 and HLSV = 14 cm3/(h g)). UOL formation on MgO proceeds via a hydrogen transfer Meerwein–Ponndorf–Verley (MPV) mechanism without participation of surface H atoms from 2-propanol dissociation. Weak acid–strong base Mg2+O2− surface pairs efficiently promote formation of the six-atom cyclic intermediate required in the MPV mechanism for selectively reducing the CO bond of an unsaturated ketone to the corresponding allyl alcohol. In contrast, UOL yield on MgAl0.33Ox was always lower than 5%. UOL formation is hindered on MgAl0.33Ox because surface Al3+ sites decrease by dilution the density of Mg2+O2− pairs and concomitantly favor the adsorption of mesityl oxide via the CC bond, thereby promoting the selective formation of MIBK.
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 ; Argentina
Fil: Acosta, A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Fil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
description The gas-phase regioselective reduction of mesityl oxide to the allyl alcohol using 2-propanol as a hydrogen donor was studied at 523 K on basic MgO, MgAl0.33Ox and Cu0.05MgAl0.65Ox oxides. Catalysts were characterized using a variety of physical and spectroscopic techniques. The effect of contact time on the product distribution was determined in order to identify primary and secondary reaction pathways. Main reaction products from mesityl oxide conversion were the two allyl alcohol isomers (UOL, 4-methyl-3-penten-2-ol and 4-methyl-4-penten-2-ol), isomesityl oxide, methyl isobutyl ketone (MIBK), methyl isobutyl carbinol and C9 aldol condensation products. Bifunctional Cu0.05MgAl0.65Ox did not produce alcohols. Metallic Cu atoms readily decomposed 2-propanol forming acetone and mobile surface H atoms that selectively reduced the CC bond of mesityl oxide giving mainly MIBK. UOL formed on MgO at unusually high yields for a gas-phase reaction (40% at 523 K, 2-propanol/mesityl oxide = 5 and HLSV = 14 cm3/(h g)). UOL formation on MgO proceeds via a hydrogen transfer Meerwein–Ponndorf–Verley (MPV) mechanism without participation of surface H atoms from 2-propanol dissociation. Weak acid–strong base Mg2+O2− surface pairs efficiently promote formation of the six-atom cyclic intermediate required in the MPV mechanism for selectively reducing the CO bond of an unsaturated ketone to the corresponding allyl alcohol. In contrast, UOL yield on MgAl0.33Ox was always lower than 5%. UOL formation is hindered on MgAl0.33Ox because surface Al3+ sites decrease by dilution the density of Mg2+O2− pairs and concomitantly favor the adsorption of mesityl oxide via the CC bond, thereby promoting the selective formation of MIBK.
publishDate 2004
dc.date.none.fl_str_mv 2004-11
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/11336/55837
Di Cosimo, Juana Isabel; Acosta, A.; Apesteguia, Carlos Rodolfo; Gas-phase hydrogen transfer reduction of α,β-unsaturated ketones on Mg-based catalysts; Elsevier Science; Journal of Molecular Catalysis A: Chemical; 222; 1-2; 11-2004; 87-96
1381-1169
CONICET Digital
CONICET
url http://hdl.handle.net/11336/55837
identifier_str_mv Di Cosimo, Juana Isabel; Acosta, A.; Apesteguia, Carlos Rodolfo; Gas-phase hydrogen transfer reduction of α,β-unsaturated ketones on Mg-based catalysts; Elsevier Science; Journal of Molecular Catalysis A: Chemical; 222; 1-2; 11-2004; 87-96
1381-1169
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.molcata.2004.07.020
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
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score 13.13397

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