Vom Laborkuriosum zum kontinuierlichen Prozess: Die Entwicklung thermomorpher Lösungsmittelsysteme

Dreimann, Jens M.; Faßbach, Thiemo A.; Fuchs, Sarah; Furst, Marc R. L.; Gaide, Tom; Kuhlmann, René; Ostrowski, Karoline A.; Stadler, Andreas; Seidensticker, Thomas; Vogelsang, Dennis; Warmeling, H.; Vorholt, Andreas J.

doi:10.1002/cite.201600119

Cited by 16 publications

(14 citation statements)

References 57 publications

(24 reference statements)

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“…The selectivity to one or more of the possible skeletal structures can be adjusted to some extent by using additives. Due to the highly non‐polar products, the catalyst can be separated from the products using a so‐called thermomorphic solvent system (TMS) …”

Section: 3‐dienesmentioning

confidence: 99%

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The Telomerization of 1,3‐Dienes – A Reaction Grows Up

2019

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Telomerization is a versatile tool for synthesizing unsaturated ethers, amines and other molecules starting from 1,3‐dienes and respective nucleophiles. The homogeneously catalyzed reaction has been the subject of academic and industrial research for over 50 years, offering a broad variety of substrates, catalysts and process concepts. This Minireview presents the advances and developments in this field over the last decade. The focus was on the conversion of renewable resources, the synthesis of promising new products and the development of efficient process concepts to combine these.

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Section: 3‐dienesmentioning

confidence: 99%

“…This can be achieved, for example, by extracting the product from the reaction mixture or by immobilizing the catalyst on a solid support or in a separate phase. The latter can be combined with the use of thermomorphic solvent systems (TMS) ,. This separation has to be carried out without any catalyst deactivation.…”

Section: Catalystsmentioning

confidence: 99%

The Telomerization of 1,3‐Dienes – A Reaction Grows Up

2019

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“…[39] The advantages of TMSs compared with other recycling strategies for homogeneous transition-metal catalysts are the general applicabilityo fs tandard solvents and readily available catalyst systems(precursors and ligands). [45] Certainly,v ariousr eviews on the recovery of homogeneous catalysts exist that enumerate the large number of different recovery strategies. However,t he focus herein is on the description of TMSs, giving ah olistic and detailed descriptiono fT MSs by considering the physical background, as well as challenges (e.g.,p roduct purification and cross-dissolubility of the product) and opportunities for the application of those systems.…”

Section: Introductionmentioning

confidence: 99%

“…However, these strategies usually require sophisticated solvents or specific catalysts . The advantages of TMSs compared with other recycling strategies for homogeneous transition‐metal catalysts are the general applicability of standard solvents and readily available catalyst systems (precursors and ligands) …”

Section: Introductionmentioning

confidence: 99%

Thermomorphic Multiphase Systems: Switchable Solvent Mixtures for the Recovery of Homogeneous Catalysts in Batch and Flow Processes

Bianga

Künnemann

Gaide

et al. 2019

Chemistry A European J

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Over the past 20 years, thermomorphic multiphase systems (TMS) have been used as a versatile and elegant strategy for the recovery and recycling of homogeneous transition‐metal catalysts, in both batch‐scale experiments and continuously operated processes. TMS ensure a homogeneous reaction in a monophasic reaction mixture at reaction temperature and the recovery of the homogeneous transition‐metal catalyst through liquid–liquid separation at a lower separation temperature. This is achieved by using at least two solvents, which have a highly temperature‐sensitive miscibility gap. The suitability of commercially available solvents makes this approach highly interesting from an industrial point of view. For the first time, herein, all studies in the area of TMS are reviewed, with the aim of providing a concise and integral representation of this approach for homogeneous catalyst recovery. In addition to the discussion of examples from the literature, the thermodynamic fundamentals of the temperature‐dependent miscibility of solvents are also presented. This review also gives key indicators to compare different TMS approaches, for instance. In this way, new solvent combinations and in‐depth research, as well as improvements to existing approaches, can be addressed and promoted.

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“…In this context, Gaide et al , successfully demonstrated the Pd/DTBPMB‐catalyzed methoxycarbonylation of UME with high yields of the desired diester using a thermomorphic solvent system (TMS) to recycle the homogeneous catalyst. Thus, a temperature‐dependent miscibility gap enables phase separation at low temperature and an efficient reaction without mass transport limitations at elevated temperature .…”

Section: Introductionmentioning

confidence: 99%

Kinetic Modeling of the Palladium‐Catalyzed Isomerizing Methoxycarbonylation of 1‐Decene

Gerlach

Kirschtowski

Seidel‐Morgenstern

et al. 2018

Chemie Ingenieur Technik

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The experimental and model‐based investigation of the palladium‐catalyzed methoxycarbonylation of 1‐decene using methanol and carbon monoxide is presented. The reaction was studied in a thermomorphic solvent system using the industrially applied ligand DTBPMB in order to describe the kinetics of the main and the most relevant side reactions. Based on a reaction analysis, kinetic models including main influencing variables were derived and successfully parametrized. Thus, inhibition effects of the substrate 1‐decene as well as carbon monoxide on the isomerization and methoxycarbonylation rate could be identified.

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Vom Laborkuriosum zum kontinuierlichen Prozess: Die Entwicklung thermomorpher Lösungsmittelsysteme

Cited by 16 publications

References 57 publications

The Telomerization of 1,3‐Dienes – A Reaction Grows Up

The Telomerization of 1,3‐Dienes – A Reaction Grows Up

Thermomorphic Multiphase Systems: Switchable Solvent Mixtures for the Recovery of Homogeneous Catalysts in Batch and Flow Processes

Kinetic Modeling of the Palladium‐Catalyzed Isomerizing Methoxycarbonylation of 1‐Decene

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