Kinetics of the reductive amination of 1-undecanal in thermomorphic multicomponent system

Kirschtowski, Sabine; Jameel, Froze; Stein, Matthias; Seidel‐Morgenstern, Andreas; Hamel, Christof

doi:10.1016/j.ces.2020.116187

Cited by 13 publications

(15 citation statements)

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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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“…The PCP-SAFT pure-component parameters (Table ) and k ij values (Table ) were further used to model the Henry constants ( K H ) of H 2 and CO in the different components of the reaction system (Table ) at temperatures (373.15 and 393.15 K) at which the HAM reaction is usually performed in TMS. , As the modeled gas solubilities of all investigated systems increase with increasing temperature, the Henry constants decrease when the temperature increases. Except for water, the obtained Henry constants of H 2 in the investigated liquids are greater than those of CO, for example, by a factor of 1.3–2.3 at 373 K. Consequently, CO is more soluble in these components than H 2 .…”

Section: Resultsmentioning

confidence: 99%

“…Since the HAM reaction is homogeneously catalyzed by a transition-metal complex to enable mild reaction conditions (373.15–398.15 K and 3 MPa) , as well as high selectivities and efficiencies, catalyst recycling is required for both economic and environmental reasons. For that purpose, Behr et al developed the approach of a so-called thermomorphic multiphase system (TMS) to achieve an efficient product separation and catalyst recycling by combining a polar and a nonpolar solvent, which exhibits a strongly temperature-dependent miscibility gap in the binary solvent system .…”

Section: Introductionmentioning

confidence: 99%

Phase Equilibria for the Hydroaminomethylation of 1-Decene

et al. 2021

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This work focuses on the measuring and modeling of phase equilibria of interest for the hydroaminomethylation of 1-decene with syngas (CO/H2) and diethylamine to N,N-diethylundecan-1-amine and water in a solvent system of methanol and n-dodecane. H2 solubilities were measured in undecanal and N,N-dimethyldodecan-1-amine at 343 and 363 K between 2 and 4 MPa via the isochoric saturation method. Vapor–Liquid equilibrium data were measured for the binary systems methanol/N,N-diethylundecan-1-amine, 1-decene/diethylamine, and 1-decene/N,N-diethylundecan-1-amine at temperatures between 299 and 372 K and at pressures of 0.005, 0.018, 0.025, or 0.030 MPa. Liquid–Liquid equilibria were measured in the ternary systems methanol/n-dodecane/diethylamine, methanol/n-dodecane/undecanal, and methanol/n-dodecane/N,N-diethylundecan-1-amine at 0.1 MPa and at temperatures ranging from 278.15 to 308.15 K. Measured and available phase-equilibrium data from literature were modeled using perturbed-chain polar statistical associating fluid theory. This then allowed for modeling the Henry’s law constant for H2 and CO in the liquid components (methanol, n-dodecane, 1-decene, diethylamine, undecanal, N,N-diethylundecan-1-amine, and water) at 373.15 and 393.15 K.

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“…In this work, the biogenic amines 2-phenylethan-1-amine (phenethylamine), 2-amino-1-phenylethanol (phenylethanolamine), α-(methylaminomethyl)benzyl alcohol (halostachine), and 4-(2-aminoethyl)phenol (tyramine) were investigated next to the non-naturally occurring and industry-relevant amines 1-phenylmethanamine (benzylamine) and N , N -diethylundecan-1-amine (undecyldiethylamine) (Figure ). Benzylamine is a potential solvent for use in CO 2 capturing, whereas undecyldiethylamine is a model compound for long-chain tertiary amines, produced from aldehydes derived from sustainable sources. , …”

Section: Introductionmentioning

confidence: 99%

“…Benzylamine is a potential solvent for use in CO 2 capturing, 9 whereas undecyldiethylamine is a model compound for long-chain tertiary amines, produced from aldehydes derived from sustainable sources. 10,11 Liquid densities and vapor pressures of these amines were measured and compared to partly available literature data. PC-SAFT pure-component parameters were fitted to the experimentally determined pure-component vapor pressures and liquid densities.…”

Section: ■ Introductionmentioning

confidence: 99%

Thermodynamic Properties of Biogenic Amines and Their Solutions

et al. 2021

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Vapor pressures of the biologically and industrially relevant amines 2-phenylethan-1-amine, 2-amino-1-phenylethanol, α-(methylaminomethyl)benzyl alcohol, 1-phenylmethanamine, and N,N-diethylundecan-1-amine were measured via the transpiration method. Pure-component parameters for the thermodynamic model PC-SAFT were fitted to these vapor pressures and to liquid densities. The pure-component parameters were validated with measured liquid densities of binary mixtures dimethylsulfoxid + 4-(2-aminoethyl)phenol, dimethylsulfoxid + 2-amino-1-phenylethanol, dimethylsulfoxid + α-(methylaminomethyl)benzyl alcohol, and dimethylsulfoxid + 1-phenylmethanamine at 0.102 MPa and temperatures from 298.15 to 343.15 K at different amine mass fractions. Solid−liquid equilibria at 0.1 MPa were measured in binary mixtures of α-(methylaminomethyl)benzyl alcohol + water and 4-(2-aminoethyl)phenol + water at 298.15 and 308.15 K. Finally, the presence of liquid−liquid phase separation for these systems was qualitatively predicted using PC-SAFT based on the solid−liquid equilibria only and validated for the system α-(methylaminomethyl)benzyl alcohol + water by experiments at 293.15 and 323 K at 0.1 MPa.

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Kinetics of the reductive amination of 1-undecanal in thermomorphic multicomponent system

Cited by 13 publications

References 50 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

Phase Equilibria for the Hydroaminomethylation of 1-Decene

Thermodynamic Properties of Biogenic Amines and Their Solutions

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