Überwindung von Phasentransportlimitierungen in der Umsetzung lipophiler Oleoverbindungen in wässrigen Medien – ein temperaturgesteuerter Ansatz

Gaide, Tom; Dreimann, Jens M.; Behr, Arno; Vorholt, Andreas J.

doi:10.1002/ange.201510738

Cited by 10 publications

(2 citation statements)

References 44 publications

(16 reference statements)

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“…Tandem catalyses are a hot topic in catalytic carbonylation reactions [3][4][5][6][7][8][9][10] when it comes to increasing the efficiency of chemical processes, because it makes merging different reaction steps into a single preparative step possible, reducing waste while saving time and energy [11][12][13]. Transition metal catalyzed tandem catalyses often involve hydroformylation as the initial reaction step to form reactive aldehydes [14], which constitutes a well investigated reaction that is also the subject ongoing research [15][16][17]. Hydroformylation is an important part of the hydroaminomethylation, which is a three step autotandem catalysis catalyzed by a single catalyst [16,[18][19][20][21][22][23][24].…”

Section: Introductionmentioning

confidence: 99%

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

Vorholt

Immohr

Ostrowski

et al. 2016

Euro J Lipid Sci & Tech

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This article describes the development of an effective thermomorphic multicomponent solvent (TMS) system for the production of branched polyamide monomers. In this system, methyl oleate, a renewable from fats and oils, and a functionalized amine are used as starting materials in a tandem catalytic reaction, which merges different reaction steps into a single preparative step. This particular TMS system consisted of a heptane/acetonitrile solvent mixture and made reusing the precious rhodium catalyst possible in three recycle runs. A constant yield of 61–65% was obtained for each run due to low‐catalyst leaching. Fortunately, the catalyst system does not require any additional phosphorous ligands and allows high yields. A scale‐up for the production of 10–11 g of the desired product in each run was realized. Subsequent hydrogenation of the product directly provided an amine ester, which is a valuable polyamide monomer. Practical applications: A method was developed to enable access to primary amines via hydroaminomethylation and hydrogenation. The product, a nitrile ester, is a valuable intermediate for polyamide monomers. This nitrile ester was successfully hydrogenated to an amine ester, which features a potential polyamide monomer directly. A catalyst recycle of the homogeneous rhodium complex within the hydroaminomethylation of methyl oleate and an amino nitrile was successfully carried out, enabling constant homogeneous catalyst activity over the course of three recycle runs. A scale‐up to obtain 10–11 g of the hydroaminomethylation product was realized. A general method is described for the conversion of methyl oleate within a hydroaminomethylation reaction. The catalyst can be recovered and reused. Valuable polyamide intermediates were obtained.

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Section: Introductionmentioning

confidence: 99%

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

Vorholt

Immohr

Ostrowski

et al. 2016

Euro J Lipid Sci & Tech

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“…Recently, our group reported on the use of co-solvents in the aqueous biphasic hydroformylation of unsaturated oleochemicals. Short-chain alcohols, namely 1-butanol and ispropanol, have been used as green [14] and very effective mediators in the hydroformylation of methyl 10-undecenoate (M10U) [36,37] and methyl oleate (MO), [38] respectively. It was shown that by adjusting the solvent ratios accordingly, on the one hand, the selectivity and activity of the chosen catalytic system is maintained, and on the other hand, efficient separation of the organic product phase from the catalyst containing aqueous phase by simple decantation is ensured.…”

Section: Introductionmentioning

confidence: 99%

Improving Aqueous Biphasic Hydroformylation of Unsaturated Oleochemicals Using a Jet‐Loop‐Reactor

Herrmann

Bianga

Palten

et al. 2019

Euro J Lipid Sci & Tech

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In two case studies, the reaction performance of the aqueous biphasic hydroformylation of two industrially relevant oleochemicals, namely methyl 10-undecenoate (case 1) and methyl oleate (case 2), is significantly improved by the use of a Jet-Loop Reactor concept. Based on previously reported studies, only the two green and benign co-solvents, 1-butanol and isopropanol are applied, respectively, in the absence of any additional auxiliary. Both reactions benefit highly from using this special piece of equipment, specifically designed for improving gas-liquid-liquid mixing to create large interfacial areas with no moving internals. In case 1, the loading of the co-solvent 1-butanol is successfully reduced. For the first time significant yields (>40% after 1 h) are obtained in the absence of any co-solvent, which is very beneficial, since aldehyde products and substrate form a pure product phase enabling straightforward separation. In case 2, the loading of the substrate methyl oleate is successfully increased from 6 to 30 wt% still showing satisfying productivity. At 15 wt%, the yield of the desired internal aldehydes in the jet-loop reactor is increased by a factor of five compared to a stirred tank reactor after 3 h. Practical Applications: The production of aldehydes from hydroformylation of olefins is highly relevant for the chemical industry, since these can undergo numerous subsequent reactions, to form for instance alcohols, amines, and carboxylic acids. Generally, aldehydes from oleochemicals can serve as platform chemicals for gaining access to bifunctional molecules, which are interesting as polymer precursors. Performing hydroformylation with a water-based solvent system enables efficient product separation from the aqueous catalyst phase for the realzation of more sustainable processes. By using the Jet-Loop Reactor, the performance of the reaction system can be greatly improved addressing its practical relevance.

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Fettsäuren und Fettsäurederivate als nachwachsende Plattformmoleküle für die chemische Industrie

et al. 2021

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Überwindung von Phasentransportlimitierungen in der Umsetzung lipophiler Oleoverbindungen in wässrigen Medien – ein temperaturgesteuerter Ansatz

Cited by 10 publications

References 44 publications

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

Improving Aqueous Biphasic Hydroformylation of Unsaturated Oleochemicals Using a Jet‐Loop‐Reactor

Fettsäuren und Fettsäurederivate als nachwachsende Plattformmoleküle für die chemische Industrie

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