Hydrohydroxymethylation of Ethyl Ricinoleate and Castor Oil

International audienceThe direct functionalization of the carbon–carbon double bonds of castor oil and its derivatives is of major interest to access biosourced building blocks. In particular, polyol derivatives can be produced in this way and find application in the field of bio-based polyesters and polyurethanes. In this study, we described the synthesis of polyhydroxylated derivatives via a hydrohydroxymethylation reaction consisting of two consecutive Rh-catalyzed reactions: a hydroformylation reaction followed by a hydrogenation reaction of formyl groups. A catalytic system based on Rh(acac)(CO)2 and a trialkylamine proved to be active both in hydroformylation of carbon–carbon double bonds and reduction of the resulting aldehydes into primary alcohols. By optimizing the reaction conditions, yields in alcohols of 74 and 80% were reached for castor oil and ethyl ricinoleate, respectivel

Synthesis of Diols from Jojoba Oil via Rhodium-Catalyzed Reductive Hydroformylation: a Smart Way to Access Biobased Polyurethanes

International audienceJojoba oil ester has been functionalized with alcohol groups via hydrohydroxymethylation (HHM) catalyzed by a Rh/amine system. In the optimized conditions, a full conversion together with a 99% yield in alcohol products were obtained. The catalytic system has been recycled via a chromatographic technique at least 10 times without notable loss of activity. The hydrohydroxymethylated products have been succesfully used as monomers for the synthesis of a new biobased polyurethane possessing good thermal and mechanical properties

Aqueous Biphasic Hydroaminomethylation Enabled by Methylated Cyclodextrins: Sensitivity Analysis for Transfer into a Continuous Process

International audienceHydroaminomethylation (HAM) is a highly efficient homogeneously catalyzed autotandem reaction converting alkenes into valuable amine products with water being the only coproduct. This work reports for the first time the scale-up of the highly regioselective HAM of 1-decene with diethylamine for a potential continuous process application in a green and sustainable aqueous biphasic medium. The catalytic system Rh/SulfoXantphos and randomly methylated β-cyclodextrin (RAME-β-CD) were herein dissolved in the plain aqueous phase. The addition of cyclodextrins as a green mass transfer agent remarkably increases the reaction rate as well as the selectivity toward linear amines, but they can also support solid content precipitation in this reaction system due to up-scaling effects. Therefore, parameters such as catalyst concentration, organic volume fraction, cyclodextrin concentration, and recyclability were investigated regarding the stability and activity of the system. Especially the organic volume fraction had a decisive influence on solid content precipitation. High regio- and chemoselectivities of 35 and 82%, respectively, at nearly full conversion were achieved toward the linear product amine. The catalytic system was further recycled in batch and scaled up into a 2100 mL autoclave without loss in activity and selectivity. Finally, a continuous process concept was proposed for an extensive investigation regarding long-term stability of the catalytic system

Promising Recyclable Ionic Liquid-Soluble Catalytic System for Reductive Hydroformylation

We report here the reductive hydroformylation of methyl 10-undecenoate (issued from castor oil) in a biphasic liquid/liquid system. The rhodium/amine catalytic system is immobilized in an ionic liquid phase, whereas the olefin and the products are in a nonpolar layer. The effects of various reaction parameters (nature and concentration of amines, nature of ionic liquids, temperature and syngas pressure or composition) were studied to increase the production of primary alcohols. Under optimized conditions, potassium N,N-dimethyltaurinate salt associated with rhodium, immobilized in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, allowed us to attain 93% of alcohol yield. With only 2 equiv of amine with respect to rhodium, the catalytic system can be efficiently immobilized in the ionic liquid and recycled due to the ionic nature of the involved catalytic species