Improvement of Productivity for Aqueous Biphasic Hydroformylation of Methyl 10‐Undecenoate: A Detailed Phase Investigation

Abstract

The overall productivity of the aqueous biphasic hydroformylation of the castor oil-derived methyl 10-undecenoate is increased. To increase the reaction rate, the miscibility of water and the fatty compound is increased by addition of the green solvent 1-butanol as co-solvent. For the first time, the concentration of solvents, substrate, and product within the reaction process is experimentally examined in a biphasic system under 20 bar pressure of synthesis gas and 140°C. A reactor to get samples of both phases is developed to determine the quarternary mixture of the reaction system presented in a four-dimensional tetrahedron diagram. With the knowledge gained about the reaction and its drivers, it is possible to increase the efficiency of the reaction process reported so far. With simultaneously high reaction rates (turn over frequency = >5000 h −1), the space-time yield of the reaction reaches values of >120 g L −1 h −1 and can be improved significantly without negatively affecting catalyst leaching. Practical Applications: Most polymers are made of petrochemicals. Here, the development of a highly efficient process for the formation of bifunctional molecules starting from technical grade methyl 10-undecenoate made from castor oil in an aqueous biphasic reaction system is presented. By rhodium catalyzed hydroformylation, an aldehyde ester is formed which can be used to create alcohols, carboxylic acids, and amines. Subsequently, these molecules can be used as polymer precursors in polycondensation reactions.

Tandem Catalytic Amine Synthesis from Alkenes in Continuous Flow Enabled by Integrated Catalyst Recycling

“…First, as we have already shown in the section Recycling Limitations, water formation has a slightly negative influence on the reaction performance and selectivity. The water accumulation could cause the homogeneous mixture to decompose into a biphasic system, suffering from liquid–liquid phase limitations …”

“…The water accumulation could cause the homogeneous mixture to decompose into a biphasic system, suffering from liquid−liquid phase limitations. 47 Catalyst leaching, water formation, and accumulation in the polar catalyst phase could be a reason for the decreasing activity from run 4 onward. A third factor decreasing the reaction rate might be catalyst deactivation.…”

Productivity Leap in the Homogeneous Ruthenium-Catalyzed Alcohol Amination through Catalyst Recycling Avoiding Volatile Organic Solvents

“…In previous investigations, it was revealed that sulfonated ligands have a high affinity to dimcarb and can be used to effectively retain homogeneous catalysts in the polar dimcarb phase during the separation of the amine products. , Xantphos (Figure , right), having a comparable natural bite angle ( β n = 111°,) to DPEphos (Figure , left; β n = 102°,), has been used in the ruthenium-catalyzed alcohol amination to study the mechanism by our group and is, therefore, a well-established ligand for this reaction . Surprisingly, Sulfoxantphos (Figure , right; R = SO 3 Na), the sulfonated analogue of Xantphos, was never used for alcohol amination, although it was successfully applied in several other homogeneously catalyzed biphasic reactions. − Moreover, Sulfoxantphos shows similar selectivities in the rhodium-catalyzed hydroformylation as the nonsulfonated Xantphos, which indicates that it coordinates in the same way . After consideration of the absolute solubility of Xantphos (1.8 × 10 –3 mmol g –1 ) and Sulfoxantphos (324.6 × 10 –3 mmol g –1 ) in dimcarb at 25 °C, we decided to use Sulfoxantphos for further investigations.…”

Reusable Catalysts for Hydroformylation‐Based Reactions

“…However, after the first run, the conversion decreases to around 50 % and remained almost constant for nine additional runs. The same authors [106] extended this study for the valorization of methyl 10-undecenoate using a jet-loop reactor (JLR) for this biphasic system, in which intensive mixing was achieved to overcome the solubility limitations. [107] The low solubility of long-chain olefins in water often result in low olefin conversion in the biphasic hydroformylation reactions.…”