Continuous Production of Bifunctional Platform Chemicals From Plant Oils in Water by Cyclodextrin-Mediated Hydroformylation.

Abstract

Platform chemicals from renewable resources with broad applications are highly desirable, particularly for replacing fossil-based monomers. Bifunctional aliphatic ester-aldehydes, accessible via regioselective hydroformylation of unsaturated oleochemicals, can be converted into linear ω-amino/ω-hydroxy esters and dicarboxylic acids-key building blocks for biobased aliphatic polycondensates. However, their success hinges on efficient, economically viable production, with catalyst recycling being critical. We present the Rh-catalyzed, cyclodextrin-mediated, aqueous biphasic hydroformylation of methyl 10-undecenoate (from castor oil) and methyl 9-decenoate (from rapeseed oil) to produce methyl 12-oxododecanoate and methyl 11-oxoundecanoate, respectively, with high yields and productivity. This system allows for efficient catalyst recycling via decantation, maintaining 30 % of its native activity in aqueous biphasic conditions. Reaction conditions were optimized using a tailored experimental design, reducing nearly 200 experiments to 39 without sacrificing predictive accuracy. The optimized conditions were transferred to a continuous miniplant, achieving a low rhodium loss of 0.018 % h^-1, with excellent space-time yields of 76.5 kg h^-1 m^-3. Rhodium in the product was as low as 79 ppb, with 4.4 kg of product per mg of catalyst lost, marking a significant step in combining hydroformylation-derived, bio-based platform chemicals with economic industrial potential.