Development of a novel phase separable catalysts for oleochemistry

A novel amphiphilic dipyridinium peroxophosphotungstate ion pair was developed as a selective and recyclable catalyst for the biphasic epoxidation of fatty acids and esters with hydrogen peroxide, in collaboration with Greg Chatel in Grenoble (Green Chem. 2017). The synthesis of the catalyst was studied extensively by solid and liquid phase 31P nuclear magnetic resonance (NMR). The oxidation of vegetable oils is of prime importance for the production of lubricants, plasticizers, polymer stabilizers and other olefinic compounds. Based on the oxidizing activity of peroxophosphotungstates, we designed a lipophilic phase transfer agent that renders the active complex insoluble in the reaction media, without having to support it on a matrix. This affords a catalyst combining the activity of homogeneous catalysts and the recyclability of heterogeneous systems. We show that this catalyst is able to fully epoxidize methyl oleate with excellent selectivity, with a turnover frequency of 149 at 60 °C, and can be easily recycled, to reach a record turn over number of 1868. A large scale experiment on 13 grams and a scope including linoleic and ricinoleic acids were also demonstrated. The catalyst also shows excellent activity and selectivity for the oxidative cleavage of methyl oleate and the oxidation of small olefins.