Rhodium‐Catalysed Reductive Amination for the Synthesis of Tertiary Amines

Bianga, Jonas; Kopplin, Niklas; Hülsmann, Jonas; Vogt, Dieter; Seidensticker, Thomas

doi:10.1002/adsc.202000746

Cited by 15 publications

(18 citation statements)

References 39 publications

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“…Referring to the 12 principles of Green Chemistry, chemical reactions should be performed as selective as possible, which can be accomplished by the application of homogeneous catalysts. For the homogeneously catalyzed reductive amination of aldehydes with amines, transition metals like Rh, Ir or Ru are frequently used for the hydrogenation of the imine/enamine intermediate [6,7]. Undeniably, the separation of the dissolved catalyst from the products is the biggest challenge for homogeneous catalysis.…”

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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“…Tyramine was bought from Alfa Aesar with a purity ≥98%, and dimethylsulfoxid (DMSO) was purchased from Merck. Undecyldiethylamine was synthesized by Bianga et al with purity ≥98%. All chemicals were used as received and are listed in Table .…”

Section: Methodsmentioning

confidence: 99%

“…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%

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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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“…The purity of H 2 is given in volume%, whereas all other purities are mass purities as provided by the supplier. N,N-Diethylundecan-1-amine was synthesized according to the procedure reported by Bianga et al 25 All chemicals were used as received. Water was purified using a Milli-Q device by Merck.…”

Section: ■ Materialsmentioning

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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Rhodium‐Catalysed Reductive Amination for the Synthesis of Tertiary Amines

Cited by 15 publications

References 39 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

Thermodynamic Properties of Biogenic Amines and Their Solutions

Phase Equilibria for the Hydroaminomethylation of 1-Decene

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