An economically meaningful hydroformylation of long-chain olefins requires an efficient combination of both a high-yield reaction step and efficient catalyst recycling. The application of thermomorphic multicomponent solvent (TMS) systems allows for optimal reaction as well as catalyst-recycling conditions. In this work, the TMS concept was applied to the homogeneously rhodium-catalyzed hydroformylation of 1-dodecene in the TMS system dimethylformamide (DMF)/decane using Rh(acac)(CO) 2 /Biphephos as the catalyst system. Thermodynamic investigations focused on the influence of the olefin (hydroformulation educt) and the aldehyde (hydroformylation product) on the phase behavior of the TMS system. Temperature dependent liquid−liquid equilibrium (LLE) data were measured for the binary systems DMF/decane and DMF/1-dodecene and for the ternary systems DMF/decane/1-dodecene and DMF/decane/dodecanal. Additionally, the corresponding LLE data were modeled applying the Perturbed Chain Polar Statistical Associating Fluid Theory (PCP-SAFT) using a heterosegmented approach for modeling the long-chain aldehyde. On the basis of the LLE data, adequate working points for hydroformylation experiments in the TMS system were selected. In these experiments, aldehyde yields of up to 87% with an n/iso ratio of up to 99:1 were achieved. Moreover, the TMS system was successfully applied to catalyst recycling in eight recycling runs with a catalyst leaching of 7 ppm rhodium at lowest.

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