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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.
The experimental and model‐based investigation of the palladium‐catalyzed methoxycarbonylation of 1‐decene using methanol and carbon monoxide is presented. The reaction was studied in a thermomorphic solvent system using the industrially applied ligand DTBPMB in order to describe the kinetics of the main and the most relevant side reactions. Based on a reaction analysis, kinetic models including main influencing variables were derived and successfully parametrized. Thus, inhibition effects of the substrate 1‐decene as well as carbon monoxide on the isomerization and methoxycarbonylation rate could be identified.
The homogenously rhodium-catalyzed tandem reaction of the hydroaminomethylation of 1-decene is investigated in a thermomorphic solvent system consisting of methanol and n-dodecane with the ligand sulfoxantphos. The influence of temperature, pressure and catalyst concentration is studied experimentally as the basis for kinetic modeling and parameter estimation. A kinetic model for the hydroaminomethylation is developed by connecting and reparametrizing a mechanistic approach for the hydroformylation with a reductive amination model. Simulations and experimental data are in good agreement indicating the transferability of mechanistic kinetic models.
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