Kinetic Modeling of Rhodium‐Catalyzed Reductive Amination of Undecanal in Different Solvent Systems

Abstract

This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made. Supporting Information available onlineThe homogenously rhodium-catalyzed reductive amination of 1-undecanal was performed in two different thermomorphic solvent systems with the ligand Xantphos. The influences of partial pressure, temperature, methanol and catalyst concentration on the reaction were investigated. Based on a network analysis a kinetic model was derived and successfully parametrized for all studied solvent systems. Simulation results were found to be in good agreement with the experiments and allow a further process development and optimization.

One-Pot Synthesis of Fatty Amines: Rh-Catalyzed Hydroaminomethylation of 1-Decene in an Aqueous Microemulsion System—Influence of Reaction Conditions on the Reaction Performance

“…Calculating the activation energies of both reactions of the tandem system increases the uncertainty of the two results. However, these observations are in agreement with the literature, for both hydroformylation (E A = 59 kJ/mol) and reductive amination (E A = 76.2 kJ/mol) by Schomäcker et al and others [22][23][24].…”

Rhodium‐Catalysed Reductive Amination for the Synthesis of Tertiary Amines

“…In particular, as catalyst system, a combination of Rh(acac)(cod) [acetylacetonato(1,5-cyclooctadiene)rhodium] as the precursor and Xantphos [4,5-bis (diphenylphosphino)-9,9-dimethylxanthene] as ligand has been chosen, since this system has already been reported to be active in RA. [22] This and similar catalyst…”

“…Due to stability issues using monodentate ligands as triphenylphosphine and related reproducibility challenges in reductive amination experiments, we decided to use a bidentate ligand for the reductive amination. In particular, as catalyst system, a combination of Rh(acac)(cod) [acetylacetonato(1,5‐cyclooctadiene)rhodium] as the precursor and Xantphos [4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene] as ligand has been chosen, since this system has already been reported to be active in RA [22] . This and similar catalyst systems with the solvent methanol have frequently been used in different reductive aminations and are also frequently reported in publications about hydroaminomethylation (hydroformylation with subsequent reductive amination) allowing high catalyst activities in these systems [12,13,19,20,22,23] .…”

“…In particular, as catalyst system, a combination of Rh(acac)(cod) [acetylacetonato(1,5‐cyclooctadiene)rhodium] as the precursor and Xantphos [4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene] as ligand has been chosen, since this system has already been reported to be active in RA [22] . This and similar catalyst systems with the solvent methanol have frequently been used in different reductive aminations and are also frequently reported in publications about hydroaminomethylation (hydroformylation with subsequent reductive amination) allowing high catalyst activities in these systems [12,13,19,20,22,23] . Moreover, Xantphos is a readily available bidentate ligand and offers the possibility of modification for more specialised applications such as catalyst recycling [23,24] .…”

“…asc.wiley-vch.de systems with the solvent methanol have frequently been used in different reductive aminations and are also frequently reported in publications about hydroaminomethylation (hydroformylation with subsequent reductive amination) allowing high catalyst activities in these systems. [12,13,19,20,22,23] Moreover, Xantphos is a readily available bidentate ligand and offers the possibility of modification for more specialised applications such as catalyst recycling. [23,24] According to a small optimisation, we chose methanol as solvent, a temperature of 100°C and H 2 pressure of 30 bar.…”