High Rate and Highly Selective Vinyl Acetate Hydroformylation in Ionic Liquids as Solvent or Cosolvent

Abstract

The hydroformylation of Vinyl acetate to form 2acetoxypropanal (an important intermediate in the synthesis of the enVironmentally friendly solVent ethyl lactate) catalyzed by Rh(CO) 2 (acac) using phosphite or phosphine ligands was inVestigated in ionic liquids as reaction media (neat and as blends) or as additiVes to organic solVents. The ionic liquid had a significant effect on the selectiVity of the hydroformylation of Vinyl acetate, with Very high TOFs being realized and selectiVities of oVer 99% being obtained for the desired branched product at >95% selectiVity for aldehyde products in reactions up to 0.3 mol scale. This effect could be obtained for relatiVely low Volumes of the ionic liquid in an organic solVent, and combinations of benefits were obserVed by blending ionic liquids. It was also shown that the ionic liquid/catalyst could be recycled without loss of actiVity.

Platinum complexes of malonate-derived monodentate phosphines and their application in the highly chemo- and regioselective hydroformylation of styrene

“…While the conversion is negligible under 80 bar pressure (CO/H 2 = 1:1), complete conversion may be obtained under 110 bar pressure (compare entries 7, 8 and 9). Ionic liquids have been found useful in a number of catalyst systems for several reactions including metathesis [25] and hydroformylation [26] reactions. Ligand 4 was expected to be a suitable ligand in ionic liquid catalysis due to the presence of the two polar hydroxyl groups enabling good solubility.…”

Synthesis and characterization of TiO2 nanotube supported Rh-nanoparticle catalysts for regioselective hydroformylation of vinyl acetate

“…vinyl acetate, is still a challenging topic and has drawn great attention. [2][3][4][5][6] With the regioselective hydroformylation of functionalized alkenes, target products having functional groups at different positions can be synthesized. 7,8 For example, the hydroformylation of vinyl acetate provides bifunctional products (Scheme 1), which can be further converted into synthetically useful compounds, e.g.…”

“…To date, though there are few reports concerning hydroformylation of functionalized alkenes with high regioselectivity carried out under mild conditions, a lot of effort has been made to increase the regioselectivity with high reaction rate in the past decades. 3,9 The key to achieve high regioselectivity for target product is to create a novel catalyst.…”

Characteristic reactions of group 9 transition metal compounds in organic synthesis

“…The product, acetoxypropanal, is utilized as an important intermediate in the synthesis of the environmentally friendly solvent ethyl lactate. [216]…”