Continuous flow homogeneous alkene metathesis using a supported ionic liquid phase (SILP) catalyst with CO(2) as a transport vector allows the self-metathesis of methyl oleate with only a slight loss of activity for at least 10 h; cross-metathesis of dimethyl maleate with methyl oleate ceases after 3 h, but the catalyst remains active for methyl oleate metathesis. The reasons for this unusual behaviour are explored and a practical system for the cross-metathesis of methyl oleate with dimethyl maleate, under batch conditions, is described
Abstract:The asymmetric hydrogenation of methyl acetoacetate (MAA) in methanol using dibromobis{(S)-4-phenyl-4,5-dihydro-3H-dinaphtho[2,1-c: 1',2'-e]phosphepine}-ruthenium was studied in detail. For the determination of the reaction network, data from kinetic experiments were compared to different possible reaction networks using the kinetic software Presto Kinetics. The simulation was optimised to describe the reaction accurately with a minimal set of process parameters and reaction equations. For the best model the reaction orders, collision factors and activation energy of all reaction steps were determined. Additionally, the influence of reaction temperature and hydrogen pressure on the enantiomeric excess (ee) of the reaction was studied. It was found that high reaction temperatures and high hydrogen pressures result in increasing enantioselectivities.
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