Hydrodeoxygenation of Acetophenone over Supported Precious Metal Catalysts at Mild Conditions: Process Optimization and Reaction Kinetics

González, Cristina Rodríguez; Marín, Pablo; Dı́ez, Fernando V.; Ordóñez, Salvador

doi:10.1021/acs.energyfuels.5b02112

Cited by 23 publications

(33 citation statements)

References 48 publications

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“…The enantioselective synthesis of PE from acetophenone has been chosen as a model system because it is an interesting compound in bio-oil in which ketones are present in a large portion (27 wt%) 51 . Acetophenone is a very simple aromatic ketone, and therefore well-suited for first proof-of-principle studies, which then might be extended to other, more complex, ketones 52 , 53 . In addition, the conversion of this compound into a pure enantiomer of 1-PE as an important chiral building block in pharmaceutical industries can be considered as a representative example for the production of high-added-value products.…”

Section: Resultsmentioning

confidence: 99%

Pulsed electroconversion for highly selective enantiomer synthesis

et al. 2017

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Asymmetric synthesis of molecules is of crucial importance to obtain pure chiral compounds, which are of primary interest in many areas including medicine, biotechnology, and chemistry. Various methods have been used very successfully to increase the enantiomeric yield of reaction pathways, but there is still room for the development of alternative highly enantioselective reaction concepts, either as a scientific challenge of tremendous fundamental significance, or owing to the increasing demand for enantiopure products, e.g., in the pharmaceutical industry. In this context, we report here a strategy for the synthesis of chiral compounds, based on pulsed electrochemical conversion. We illustrate the approach with the stereospecific electroreduction of a prochiral model molecule at chiral mesoporous metal structures, resulting in an enantiomeric excess of over 90%. This change of paradigm opens up promising reaction schemes for the straightforward synthesis of high-added-value molecules.

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Section: Resultsmentioning

confidence: 99%

Pulsed electroconversion for highly selective enantiomer synthesis

et al. 2017

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“…This pretreatment can easily be done through transalkylation by feeding the mixture over zeolite to convert the alkoxy (−OR) to hydroxyl (−OH) and alkyl (−R) functional groups . Therefore, although acetic acid is not a good acylating agent, it can undergo esterification with these phenolic compounds (Ar−OH) to produce aromatic esters, which further create the desired acetophenones, versatile molecules that can be directly hydrotreated to drop‐in fuels or further upgraded to longer‐chain molecules by using different chemistries, such as aldol condensation, due to the ketone functionality …”

Section: Discussionmentioning

confidence: 99%

“…This pretreatment can easily be done through transalkylation by feeding the mixture over zeolite to convert the alkoxy (ÀOR) to hydroxyl (ÀOH) and alkyl (ÀR) functional groups. [23] Therefore, althougha cetic acid is not ag ood acylating agent, it can undergo esterification with thesep henolic compounds (ArÀOH) to produce aromatic esters, which further create the desired acetophenones, versatile molecules that can be directly hydrotreated [24] to drop-in fuels or further upgraded to longer-chain moleculesb yu sing different chemistries, such as aldol condensation, due to the ketone functionality. [1a, 25] Furthermore, in this reaction, once the acylium ions are generated, the aromatic compounds with oxygen-containing functionalities, such as hydroxyl and alkoxy,a re all able to interact with them.T he activity of this CÀCc oupling step decreased in the order m-cresol > phenol > anisole.…”

Section: Discussionmentioning

confidence: 99%

Enhancing the Acylation Activity of Acetic Acid by Formation of an Intermediate Aromatic Ester

et al. 2017

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Acylation is an effective C-C bond-forming reaction to condense acetic acid and lignin-derived aromatic compounds into acetophenones, valuable precursors to fuels and chemicals. However, acetic acid is intrinsically an ineffective acylating agent. Here, we report that its acylation activity can be greatly enhanced by forming intermediate aromatic esters directly derived from acetic acid and phenolic compounds. Additionally, the acylation reaction was studied in the liquid phase over acid zeolites and was found to happen in two steps: 1) formation of an acylium ion and 2) C-C bond formation between the acylium ion and the aromatic substrate. Each of these steps may be rate-limiting, depending on the type of acylating agent and the aromatic substrate. Oxygen-containing substituents, such as -OH and -OCH , can activate aromatic substrates for step 2, with -OH> -OCH , whereas alkyl substituent -R cannot. At the same time, aromatic esters can rearrange to acetophenones by both an intramolecular pathway and, preferentially, an intermolecular one.

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“…designed a heterogeneous catalyst composed of bimetallic Fe‐Ru NPs that can selectively hydrodeoxygenate aromatic substrates without reducing the aromatic rings, even at H 2 pressures of 50 bar . In this context, a first model reaction would be the hydrodeoxygenation of acetophenone catalyzed by Ru NPs even though Ru NPs are good catalysts for the hydrogenation of aromatic rings at room temperature, an undesired side reaction in the hydrodeoxygenation of aromatic ketones …”

Section: Figurementioning

confidence: 99%

Hydrodeoxygenation Using Magnetic Induction: High‐Temperature Heterogeneous Catalysis in Solution

et al. 2019

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Magnetic heating has recently been demonstrated as an efficient way to perform catalytic reactions after deposition of the heating agent and the catalyst on a support. Here we show that in solution, and under mild conditions of mean temperature and pressure, it is possible to use magnetic heating to carry out transformations that are otherwise performed heterogeneously at high pressure and/or high temperature. As a proof of concept, we chose the hydrodeoxygenation of acetophenone derivatives and of biomass‐derived molecules, namely furfural and hydroxymethylfurfural. These reactions are difficult, require heterogeneous catalysts and high pressures, and, to the best of our knowledge, have no precedent in standard solution. Here, hydrodeoxygenations are fully selective under mild conditions (3 bar H2, moderate mean temperature of the solvent). The reason for this reactivity is the fast heating of the particles well above the boiling temperature of the solvent and the local creation of hot spots surrounded by a vapor layer, in which high temperature and pressure may be present. This technology may be practicable for many organic transformations.

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Hydrodeoxygenation of Acetophenone over Supported Precious Metal Catalysts at Mild Conditions: Process Optimization and Reaction Kinetics

Cited by 23 publications

References 48 publications

Pulsed electroconversion for highly selective enantiomer synthesis

Pulsed electroconversion for highly selective enantiomer synthesis

Enhancing the Acylation Activity of Acetic Acid by Formation of an Intermediate Aromatic Ester

Hydrodeoxygenation Using Magnetic Induction: High‐Temperature Heterogeneous Catalysis in Solution

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