Understanding the Role of Nonionic Surfactants during Catalysis in Microemulsion Systems on the Example of Rhodium-Catalyzed Hydroformylation

Pogrzeba, Tobias; Schmidt, Marcel; Milojević, Nataša; Urban, Carolina; Illner, Markus; Repke, Jens‐Uwe; Schomäcker, Reinhard

doi:10.1021/acs.iecr.7b02242

Cited by 30 publications

(33 citation statements)

References 28 publications

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“…Undeniably, the separation of the dissolved catalyst from the products is the biggest challenge for homogeneous catalysis. There are several approaches available for the separation and reuse of the homogeneous catalyst, e.g., a simple biphasic system [8] or so-called switchable solvent systems, like switchable-hydrophilicity solvents (SHS [9,10]), thermomorphic systems (TMS [11,12]), and microemulsion systems (MES [13,14]). The homogeneously catalyzed reductive amination of aldehydes using aqueous media has also been described in the literature [15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Rh-Catalyzed Reductive Amination of Undecanal in an Aqueous Microemulsion System Using a Non-Ionic Surfactant

2021

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The homogeneously catalyzed reductive amination of the long-chain aldehyde undecanal with diethylamine was performed in an aqueous microemulsion system using the non-ionic surfactant Marlophen NP8. The experiments showed that the used water-soluble rhodium/SulfoXantphos catalyst system is suitable for this reaction. The Rh-catalyzed formation of the alcohol by-product can be completely suppressed by the use of carbon monoxide with its stabilizing effect of the catalyst system. In addition to pressure and temperature, the most important parameters for the reaction performance of the reductive amination are the concentrations of reactants. Especially, the initial concentration of the aldehyde has a strong impact on the chemoselectivity, and the formation of aldol by-product due to the fact that both, the enamine condensation and the aldol condensation are equilibrium reactions.

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Section: Introductionmentioning

confidence: 99%

Rh-Catalyzed Reductive Amination of Undecanal in an Aqueous Microemulsion System Using a Non-Ionic Surfactant

2021

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“…A further increase in surfactant concentration leads to yields of up to 55 %. It is well known that the ligand SulfoXantPhos is surface‐active itself 10, 17. This indicates that the catalyst complex is located at the water‐oil interface.…”

Section: Resultsmentioning

confidence: 99%

“…Numerous examples of multiphasic recyclable carbonylation reactions are given in the literature. The hydroformylation of 1-dodecene can be promoted using the ionic surfactant cetyltrimethylammonium bromide (CTAB) [9] whereas nonionic surfactants (e.g., alkyl polyethylene glycol ethers) are successfully used for the hydroformylation and hydrocarboxylation of 1-dodecene [10,11]. Porada et al described the amphiphilic character of ionic liquids like alkylmethylimidazolium salts and their ability to form the described microemulsions [12].…”

Section: Introductionmentioning

confidence: 99%

Ionic Liquids as Surfactants in Aqueous Multiphase Systems for the Pd‐Catalyzed Hydrocarboxylation

Weber

Isbrücker

Schmidt

et al. 2020

Chemie Ingenieur Technik

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This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. Dedicated to Prof. Dr.-Ing. Matthias Kraume on the occasion of his 65th birthday The suitability of ionic liquids (alkylmethylimidazolium bromides) as surfactants in an aqueous multiphase system for the Pd-catalyzed hydrocarboxylation of 1-dodecene is discussed. Attention is paid to the influence of these ionic liquids on the reaction performance and the phase separation. All tested ionic liquids are suitable as surfactants, but their concentration has a strong impact on the reaction performance. The resulting product concentrations are crucial for the phase behavior and so for the phase separation. In recycling experiments, the Pd-catalyst is successfully separated and reused.

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“…Interestingly, the phase behavior of the microemulsion system has no strong impact on the reaction performance of hydroxycarbonylation, which is in good agreement to the findings for hydroformylation of 1-dodecene in the same systems. 21 The initially prepared microemulsion system changes from an oil-in-water microemulsion system at a surfactant concentration of γ = 7% to a macroscopically three-phase system and finally to a water-in-oil microemulsion system at γ = 11%. No significant change in the conversion and yield of the reaction is observed at the shift of the phase states, which would indicate a change in mass transfer conditions.…”

Section: Resultsmentioning

confidence: 99%

Palladium-Catalyzed Hydroxycarbonylation of 1-Dodecene in Microemulsion Systems: Does Reaction Performance Care about Phase Behavior?

et al. 2018

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Catalysis, particularly metal-catalyzed reactions in microemulsion systems, offers a sustainable approach for organic reactions in water. However, it is still a challenging task because of the complex role of the nonionic surfactant in such a system and the interaction of the phase behavior and reaction performance. To get a profound knowledge of this role and interaction, a systematic study of the palladium-catalyzed hydroxycarbonylation of 1-dodecene in a microemulsion system is reported. The influence of the temperature, additives such as cosolvents, the catalyst concentration, and the hydrophilicity of the surfactant and its concentration has been investigated with regard to both the phase behavior and reaction performance. Interestingly, the investigations reveal that not the phase behavior of the microemulsion system but mainly the dimension of the oil–water interface and the local concentrations of the substrates at this interface, which is provided by the amount and hydrophilicity of the surfactant, control the reaction performance of hydroxycarbonylation in these systems. Moreover, it was found that the local concentration of the active catalyst complex at the interface is essential for the reaction performance. Dependent on the surface active properties of the catalyst complex, its bulk concentration, and the nature and amount of additives, the local concentration of the active catalyst complex at the interface is strongly influenced, which has a huge impact on the reaction performance.

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Understanding the Role of Nonionic Surfactants during Catalysis in Microemulsion Systems on the Example of Rhodium-Catalyzed Hydroformylation

Cited by 30 publications

References 28 publications

Rh-Catalyzed Reductive Amination of Undecanal in an Aqueous Microemulsion System Using a Non-Ionic Surfactant

Rh-Catalyzed Reductive Amination of Undecanal in an Aqueous Microemulsion System Using a Non-Ionic Surfactant

Ionic Liquids as Surfactants in Aqueous Multiphase Systems for the Pd‐Catalyzed Hydrocarboxylation

Palladium-Catalyzed Hydroxycarbonylation of 1-Dodecene in Microemulsion Systems: Does Reaction Performance Care about Phase Behavior?

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