Catalyst-Free Epoxidation of Limonene to Limonene Dioxide

Limonene dioxide is a platform molecule for the production of new biopolymers. First attempts at limonene epoxidation were made by using low-coordination titanium supported on SBA-16 as the catalyst using tert-butyl hydroperoxide as the oxidizing agent, but no limonene dioxide was obtained. When limonene was substituted by 1,2-limonene oxide, the yield of limonene dioxide was only 13% in the same conditions. Two other techniques, both using in situ generated dimethyl dioxirane by the reaction of acetone with Oxone, have been studied and compared. These reactions are carried out in semibatch conditions and at room temperature. The first double epoxidation of limonene was performed in a conventional biphasic organic-water system and the other in excess acetone. The former epoxidation of limonene using ethyl acetate as the organic phase allowed reaching 95% conversion and yielding 33% of limonene dioxide. In comparison, when the reaction was performed in acetone, a limonene dioxide yield of 97% was observed under optimized conditions. The double epoxidation of limonene should be carried out at room temperature with a flowrate of 4 mL min(-1) of aqueous Oxone for a period of 45 min with a stoichiometric excess of 30% of Oxone.