Evolution des especes carboxylates dans le cadre des syntheses CO-H2. Reduction de l'acide acetique sur systeme Co, Cu, Fe

Cressely, J.; Farkhani, D.; Deluzarche, A.; Kiennemann, A.

doi:10.1016/0254-0584(84)90065-8

Cited by 20 publications

(15 citation statements)

References 24 publications

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“…The addition of Dowtherm A (a eutectic mixture of diphenyl ether and biphenyl) proved to be particularly beneficial, leading to full conversion of 2a (entry 12). Under these conditions, the iron(II) carboxylates can also be generated from basic iron(II) precursors and the arenecarboxylic acids, or from sodium carboxylates and iron salts (entries [13][14][15]. With ironA C H T U N G T R E N N U N G (III) precursors, lower yields were obtained (entry 16).…”

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confidence: 99%

“…In such a decarboxylative cross-ketonisation, the carboxylate groups would predefine the position of bond formation, potentially allowing a selective synthesis of any desired regioisomer. If mediated by catalytic amounts of an inexpensive metal with high selectivity for hetero-over homocoupling, the overall process would be advantageous both from economical and ecological standpoints.The decarboxylative homoketonisation of aliphatic carboxylic acids is an established strategy for the preparation of symmetrical dialkyl ketones or cyclic alkanones.[9] State-of-the-art protocols involve gasphase transformations at temperatures above 350 8C at solid catalysts, for example, CaO, ZnO, MgO, [10] TiO 2 , [11] ZrO 2 , [12] MnO, [13] Fe 2 O 3 , [14] or rare earth metal oxides [15] on SiO 2 -, Al 2 O 3 -, or pumice-based supports. However, if equimolar mixtures of aromatic and aliphatic carboxylic acids are subjected to the above catalysts, dialkyl and aryl alkyl ketones are obtained at best in a 1:1 ratio, using elaborate reaction technology such as gas-phase reactions above 400 8C, [16] or continuous-flow reactors.…”

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confidence: 99%

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Catalytic Decarboxylative Cross‐Ketonisation of Aryl‐ and Alkylcarboxylic Acids using Magnetite Nanoparticles

2010

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In the presence of catalytic amounts of magnetite nanopowder, mixtures of aromatic and aliphatic carboxylic acids are converted selectively into the corresponding aryl alkyl ketones. As byproducts, only carbon dioxide and water are released. This catalytic cross-ketonisation allows the regioselective acylation of aromatic systems and, thus, represents a sustainable alternative to FriedelCrafts acylations.Keywords: aryl alkyl ketones; catalysis; cross-ketonisation; decarboxylation; iron Aryl alkyl ketones are among the most important synthons in the industrial manufacture of commodities, [1] fine chemicals, and pharmaceuticals.[2] Simple derivatives, at early stages of the chemical value creation chain, are synthesised almost exclusively via FriedelCrafts acylation of arenes, because the low cost of this reaction is unrivalled to date.[3] However, two main issues are associated with this approach. Its low regioselectivity leads to the co-manufacture of large amounts of isomeric by-products, and the use of acyl chlorides as starting materials activated with superstoichiometric amounts of salt mediators (e.g., AlCl 3 ) is responsible for the formation of enormous quantities of salt waste.Regioselective and less waste-intensive acylations, e.g., cross-couplings [4] of sensitive arylmetal reagents with either preformed [5] or in situ-generated [6] carboxylic acid derivatives are widely used to access highervalue synthetic intermediates. However, their high cost precludes their application in the manufacture of base chemicals. This is also the case for alternative approaches, such as Heck-type reactions, [7] or the Pdcatalysed decarboxylative cross-coupling of a-oxocarboxylate salts with aryl halides.[8] Thus, a clear need remained for a broadly applicable, regioselective and waste-minimised aryl alkyl ketone synthesis starting from simple, inexpensive, and widely available chemicals.As a solution to this long-standing problem, we envisioned a catalytic process in which an aromatic and an aliphatic carboxylic acid are cross-coupled under release of CO 2 and water, to selectively give the aryl alkyl ketone (Scheme 1). In such a decarboxylative cross-ketonisation, the carboxylate groups would predefine the position of bond formation, potentially allowing a selective synthesis of any desired regioisomer. If mediated by catalytic amounts of an inexpensive metal with high selectivity for hetero-over homocoupling, the overall process would be advantageous both from economical and ecological standpoints.The decarboxylative homoketonisation of aliphatic carboxylic acids is an established strategy for the preparation of symmetrical dialkyl ketones or cyclic alkanones.[9] State-of-the-art protocols involve gasphase transformations at temperatures above 350 8C at solid catalysts, for example, CaO, ZnO, MgO, [10] TiO 2 , [11] ZrO 2 , [12] MnO, [13] Fe 2 O 3 , [14] or rare earth metal oxides [15] on SiO 2 -, Al 2 O 3 -, or pumice-based supports. However, if equimolar mixtures of aromatic and aliphatic carboxylic acids ar...

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confidence: 99%

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confidence: 99%

Catalytic Decarboxylative Cross‐Ketonisation of Aryl‐ and Alkylcarboxylic Acids using Magnetite Nanoparticles

2010

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“…Although some previous old literatures reported that Co‐based catalysts have some potential for the hydrogenation of carboxylic acids, Co‐based catalysts were not taken notice because of the low activity. Recently, non‐noble metal‐based catalysts have attracted much attention as the alternatives for noble metals because of the high demand for extrication of use of noble metals.…”

Section: Heterogeneous Monometallic Catalystsmentioning

confidence: 99%

Recent Developments of Heterogeneous Catalysts for Hydrogenation of Carboxylic Acids to their Corresponding Alcohols

2020

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Hydrogenation of carboxylic acids is an important organic reaction for the synthesis of alcohols, aldehydes, alkanes, and so on. Selective hydrogenation of carboxylic acids to alcohols is particularly important because alcohols are useful and valuable chemicals. However, the hydrogenation of carboxylic acids is difficult due to the low reactivity of the carboxy group and the acidic property, which require rational design of catalysts. Up to now, various effective homogeneous and heterogeneous catalysts have been intensively developed, and remarkable advances have been made in heterogeneous catalysts. In this minireview, recent progress (2010 and after) on the development of heterogeneous catalysts for hydrogenation of carboxylic acids to alcohols, particularly for monocarboxylic acids to mono primary alcohols, is reviewed. The reported literatures were categorized in terms of catalyst systems, such as monometallic catalysts and bimetallic catalysts. The characteristics, particularly the structure of active sites, reaction mechanism and stability, were introduced.

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“…Among cheaper, non-precious metal hydrogenating agents (Cu and Ni studied recently profoundly) cobalt is also highly efficient in some important dispersed on an inert silica support, and Co loaded on various supports or using bimetallic combinations of the mentioned metals. 11,12 Their results showed that Cu/SiO 2 was active and quite selective for the production of ethanol, acetaldehyde and ethyl-acetate through consecutive reduction of acetic acid, whereas Fe/SiO 2 resulted in the production of acetone and CO 2 following the ketonization reaction route. However over Co/SiO 2 , dominantly decomposition products (CH 4 and CO 2 ) were obtained.…”

Section: Introductionmentioning

confidence: 99%

Bioacid Hydroconversion over Co, Ni, Cu Mono- and Indium-doped Bimetallic Catalysts

Onyestyák

Harnos

Kalló

2015

ACSi

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Caprylic acid (CA) as model reactant was selectively reduced in a flow-through reactor in hydrogen stream at 21 bar total pressure and 240-360°C over alumina loaded with the adjacent Co, Ni, Cu host and In guest metals. The main target of this research is the recognition of efficient cobalt catalysts for carboxylic group hydroconversion compared to more familiar nickel and copper composites. The catalysts were activated in H 2 flow at 21 bar and 450°C. By variation of main metal or modification with indium, mono-or bimetallic catalysts can be obtained with low hydrodecarbonylation activity and high alcohol selectivity. These composites have higher hydrodeoxygenation (HDO) activity and alcohol selectivity than the conventional commercial catalysts applied for fatty alcohol production. Great variety of catalytic behavior indicates complexity of the surface reactions determined by several interacting factors.

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Evolution des especes carboxylates dans le cadre des syntheses CO-H2. Reduction de l'acide acetique sur systeme Co, Cu, Fe

Cited by 20 publications

References 24 publications

Catalytic Decarboxylative Cross‐Ketonisation of Aryl‐ and Alkylcarboxylic Acids using Magnetite Nanoparticles

Catalytic Decarboxylative Cross‐Ketonisation of Aryl‐ and Alkylcarboxylic Acids using Magnetite Nanoparticles

Recent Developments of Heterogeneous Catalysts for Hydrogenation of Carboxylic Acids to their Corresponding Alcohols

Bioacid Hydroconversion over Co, Ni, Cu Mono- and Indium-doped Bimetallic Catalysts

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