Hydrodeoxygenation of aldehydes catalyzed by supported palladium catalysts

This contribution focuses on the hydrogenation and hydrodeoxygenation of aldehydes (benzaldehyde, 2-phenylpropionaldehyde, 3-phenylpropionaldehyde, cinnamaldehyde, 4-isopropylbenzaidehyde, heptanal) on supported palladium catalysts, namely zeolites and active carbon. The effects of the substrate structure, solvent, type of support and its acidity, reaction temperature and pressure on activity and selectivity of Pd catalysts were investigated in detail. Catalytic hydrodeoxygenation of aldehydes was carried out in a liquid phase in an autoclave in the temperature range from 30 to 130 degrees C and at pressure ranging from 1 to 6 MPa. Hydrogenation reactions performed in non-polar hexane proceeded with a significantly higher rate than in a polar methanol. The presence of isopropyl substituent in 4-isopropylbenzaldehyde increased both the reaction rate as well as the selectivity to hydrodeoxygenation. Hydrodeoxygenation of 2-phenylpropionaldehyde, 3-phenylpropionaldehyde, cinnamaldehyde, and heptanal did not proceed, the main products were dialkylethers, which evidences the importance of the direct attachment of C=O group to the benzene ring. The presence of hydrogenation-hydrogenolytic mechanism as well as the direct hydrogenolysis of C=O bond in the transformation of benzaldehyde was verified. (C) 2007 Elsevier B.V. All rights reserved.