Selection process of new solvents in temperature-dependent multi-component solvent systems and its application in isomerising hydroformylation

Behr, Arno; Henze, Guido; Obst, Dietmar; Turkowski, Barbara

doi:10.1039/b508032k

Cited by 64 publications

(40 citation statements)

References 8 publications

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“…[57] 6.2 Different Types of Temperature-Dependent Multicomponent Solvent Systems Classical TMS systems (type I) show a closed miscibility gap both at reaction temperature and at separation temperature ( Figure 15, pathway 1, type I). That means that the catalyst layer as well as the product layer consists of all three solvents even though in different compositions.…”

Section: Solvent Selection For Temperature-dependent Multicomponent Smentioning

confidence: 99%

“…So far the successful concept of type II TMS systems was used in hydroaminomethylation (HAM, Figure 16) of 1-octene with morpholine [62] and in isomerising hydroformylation of 4-octene ( Figure 17). [57,63] For both reactions a TMS system consisting of propylene carbonate, N-methylpyrrolidone and n-dodecane is suitable to suppress catalyst leaching to below 2 ppm. Total conversion with excellent yields over 80 % could be achieved after 2 h for HAM and 4 h for isomerising hydroformylation with turnover numbers (TON) of about 200 to 1000.…”

Section: Examples Of Usementioning

confidence: 99%

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Thermoregulated Liquid/Liquid Catalyst Separation and Recycling

2006

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Considerable effort has been done to overcome the loss of catalyst in homogeneously catalysed processes. In this contribution we describe five recycling concepts for thermoregulated catalyst separation and recycling: fluorous biphasic systems (FBS), thermoregulated phase transfer catalysis (TRPTC), soluble polymer-based catalysis, thermoregulated microemulsions and temperature-dependent multicomponent solvent systems (TMS). Each of these concepts has its own special advantages like low catalyst leaching or simple process engineering but also drawbacks like usage of expensive special solvents or complex and expensive catalysts. In this context, TMS systems exhibit most advantages of the other concepts combined with the possibility to use common and cheap solvents as well as numerous classical molecular catalysts. Therefore, TMS systems are expected to be one of the most promising thermomorphic recycling concepts for industrial scale.

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Section: Solvent Selection For Temperature-dependent Multicomponent Smentioning

confidence: 99%

Section: Examples Of Usementioning

confidence: 99%

Thermoregulated Liquid/Liquid Catalyst Separation and Recycling

2006

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“…Das Katalysatorrecycling vieler homogenkatalysierter Reaktionen konnte so bereits realisiert werden. Beispiele sind die Hydroformylierung [67], die Hydroaminomethylierung [68], Cooligomerisierungen [69,70] und die Telomerisation [71]. Auch für das Recycling von Biokatalysatoren konnte das Konzept der TML-Systeme erfolgreich angewendet werden [72].…”

Section: Grüne Lösungsmittelunclassified

Construction Kit for the Solvent Selection in Homogeneous Catalyzed Reactions

Behr

Wintzer

2011

Chemie Ingenieur Technik

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Construction Kit for the Solvent Selection in Homogeneous Catalyzed ReactionsChoosing the right solvent for chemical syntheses is often the base for a successful large-scale implementation. Especially in homogeneous transition metal catalyzed reactions, the solvent can be the limiting factor in issues of catalyst recycling and product separation. This review presents possible solvent types for chemical synthesis and which tools can be used to select a suitable one. A view at new solvents will be taken, possible concepts of catalyst recycling will be explained and the concept of the green solvents will be discussed.

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“…Cooling down under the critical solution temperature leads to a biphasic system, from which the catalyst phase can be simply separated from the extract phase and used again. With this concept, the catalyst recycling of many homogeneous catalysed reactions have been realised, for example, hydroformylation, [27,28] hydroaminomethylation, [29] cooligomerisation, [30,31] codimerisation [32] and telomerisation. [33] In this contribution, we report on the performance of a palladium-based catalyst system for the hydroamination of myrcene with morpholine.…”

Section: Introductionmentioning

confidence: 99%

Novel Palladium‐Catalysed Hydroamination of Myrcene and Catalyst Separation by Thermomorphic Solvent Systems

2010

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Hydroamination is an elegant and atom economical reaction to convert alkenes into amines. One of the few technical realisations of this reaction is the hydroamination of myrcene to diethylgeranyl-A C H T U N G T R E N N U N G amine, an important precursor of (À)-menthol. However, this so-called "Takasago process" is catalysed by high amounts of alkali metals, especially lithium, which makes it a relatively expensive approach. In the present work, the hydroamination of myrcene with morpholine is catalysed by palladium complexes with bidentate ligands such as bis(diphenylphosphino)butane (DPPB) or bis(2-diphenylphosphinophenyl) ether (DPEphos). The systematic optimisation of the reaction parameters under single-phase conditions led to yields of the 1,4-adducts of higher than 90%. The only side products proved to be the telomers of myrcene, whose formation could be decreased by using appropriate reaction conditions. The method of temperature-dependent solvent systems was successfully applied to separate the palladium catalyst from the amines with a palladium leaching lower than 1.0%.

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Selection process of new solvents in temperature-dependent multi-component solvent systems and its application in isomerising hydroformylation

Cited by 64 publications

References 8 publications

Thermoregulated Liquid/Liquid Catalyst Separation and Recycling

Thermoregulated Liquid/Liquid Catalyst Separation and Recycling

Construction Kit for the Solvent Selection in Homogeneous Catalyzed Reactions

Novel Palladium‐Catalysed Hydroamination of Myrcene and Catalyst Separation by Thermomorphic Solvent Systems

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