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Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids

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Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids

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dc.contributor.author Oliver-Tomás, Borja es_ES
dc.contributor.author Renz, Michael es_ES
dc.contributor.author Corma Canós, Avelino es_ES
dc.date.accessioned 2020-07-17T03:32:04Z
dc.date.available 2020-07-17T03:32:04Z
dc.date.issued 2017-09-18 es_ES
dc.identifier.issn 0947-6539 es_ES
dc.identifier.uri http://hdl.handle.net/10251/148183
dc.description "This is the peer reviewed version of the following article: Oliver-Tomas, Borja, Michael Renz, and Avelino Corma. 2017. Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids. Chemistry - A European Journal 23 (52). Wiley: 12900 908. doi:10.1002/chem.201702680, which has been published in final form at https://doi.org/10.1002/chem.201702680. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving." es_ES
dc.description.abstract [EN] For the reaction mechanism of the ketonic decarboxylation of two carboxylic acids, a -keto acid is favored as key intermediate in many experimental and theoretical studies. Hydrogen atoms in the -position are an indispensable requirement for the substrates to react by following this mechanism. However, isolated observations with tertiary carboxylic acids are not consistent with it and these are revisited and discussed herein. The experimental results obtained with pivalic acid indicate that the ketonic decarboxylation does not occur with this substrate. Instead, it is consumed in alternative reactions such as disintegration into isobutene, carbon monoxide, and water (retro-Koch reaction). In addition, the carboxylic acid is isomerized or loses carbon atoms, which converts the tertiary carboxylic acid into carboxylic acids bearing -proton atoms. Hence, the latter are suitable to react through the -keto acid pathway. A second substrate, 2,2,5,5-tetramethyladipic acid, reacted by following the same retro-Koch pathway. The primary product was the monocarboxylic acid 2,2,5-trimethyl-4-hexenoic acid (and its double bond isomer), which might be further transformed into a cyclic enone or a lactone. The ketonic decarboxylation product, 2,2,5,5-tetramethylcyclopentanone was observed in traces (<0.2% yield). Therefore, it can be concluded that the observed experimental results further support the proposed mechanism for the ketonic decarboxylation via the -keto acid intermediate. es_ES
dc.description.sponsorship The authors thank MINECO (CTQ2015-67591-P and Severo Ochoa program, SEV-2016-0683) and Generalitat Valenciana (PROMETEO II/2013/011 Project) for funding this work. B.O.-T. is grateful to the CSIC (JAE program) for his PhD fellowship. es_ES
dc.language Inglés es_ES
dc.publisher John Wiley & Sons es_ES
dc.relation MINECO/CTQ2015-67591-P es_ES
dc.relation.ispartof Chemistry - A European Journal es_ES
dc.rights Reserva de todos los derechos es_ES
dc.subject Biomass es_ES
dc.subject Cyclization es_ES
dc.subject Green chemistry es_ES
dc.subject Surface chemistry es_ES
dc.subject Lactones es_ES
dc.subject Reaction mechanisms es_ES
dc.subject.classification QUIMICA INORGANICA es_ES
dc.subject.classification QUIMICA ORGANICA es_ES
dc.subject.classification QUIMICA ANALITICA es_ES
dc.title Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1002/chem.201702680 es_ES
dc.relation.projectID info:eu-repo/grantAgreement/GVA//PROMETEOII%2F2013%2F011/ES/Catalizadores moleculares y supramoleculares altamente selectivos, estables y energéticamente eficientes en reacciones químicas (PROMETEO)/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/MINECO//SEV-2016-0683/ es_ES
dc.rights.accessRights Abierto es_ES
dc.contributor.affiliation Universitat Politècnica de València. Departamento de Química - Departament de Química es_ES
dc.contributor.affiliation Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química es_ES
dc.description.bibliographicCitation Oliver-Tomás, B.; Renz, M.; Corma Canós, A. (2017). Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids. Chemistry - A European Journal. 23(52):12900-12908. https://doi.org/10.1002/chem.201702680 es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion https://doi.org/10.1002/chem.201702680 es_ES
dc.description.upvformatpinicio 12900 es_ES
dc.description.upvformatpfin 12908 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 23 es_ES
dc.description.issue 52 es_ES
dc.identifier.pmid 28677251 es_ES
dc.relation.pasarela S\351152 es_ES
dc.contributor.funder Generalitat Valenciana es_ES
dc.contributor.funder Ministerio de Economía y Competitividad es_ES
dc.contributor.funder Consejo Superior de Investigaciones Científicas es_ES
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