Régis Philippe

Insights in the aerobic oxidation of aldehydes

The hydroformylation of olefins (oxo synthesis) is the most important process for the production of higher aldehydes (>C4). The liquid phase oxidation of the latter to carboxylic acids by molecular oxygen or air has been known for more than 150 years and is an industrially important process. However, in the recent literature, several different oxidizing reagents and catalytic processes have been reported for this oxidation but most of them have limitations as they use environmentally unacceptable reagents or unnecessarily sophisticated conditions. Herein, we re-evaluated the air oxidation of aldehydes. We show that under mild conditions (air or oxygen and non-optimized stirring), reactions are transfer limited and thus catalyst has no effect on reaction rate. Using efficient stirring (self-suction turbine), uncatalysed air oxidation of 0.8 M aldehyde is possible in 50 min at room temperature whereas less than 10 min was necessary with 10 ppm Mn(II). Thus, recommendations for avoiding common pitfalls that may rise during the evaluation of new catalysts are made.