Oxidation of citronellal to citronellic acid by molecular oxygen using supported gold catalysts

The oxidation of citronellal to citronellic acid was studied using molecular oxygen as oxidant and gold-containing supported catalysts under aqueous conditions. The reactions were carried out at 60-90 degrees C, with 200 Nml min(-1) O2 and at pH values from 9 to 12. The alumina- or titania-supported catalysts were synthesized according to the deposition-precipitation procedure using urea or NaOH. Mechanistic studies have revealed that radical-initiated reactions lead to undesired by-products especially at pH <9, that is, the C=C bond is attacked and a diol is primarily formed probably via an epoxide intermediate. This side reaction can be suppressed to a large extent by increasing the pH to 12 and by raising the catalyst/oxygen ratio. Furthermore, detailed studies on the influence of reaction time, pH value, reactant concentration and amount of catalyst show that citronellic acid can be obtained in over 90% yield with total conversion of citronellal at pH 12 and a temperature of 80 degrees C.