Heteropoly acid catalysts for the synthesis of fragrance compounds from biorenewables: isomerization of limonene oxide

Abstract

The liquid-phase isomerization of limonene oxide was studied in the presence of heteropoly acid catalysts in aprotic solvents in homogeneous and heterogeneous systems. Among the catalysts were bulk and silica-supported tungstophosphoric acid H₃PW₁₂O₄₀ and its acidic Cs salt Cs_0.5H_0.5PW₁₂O₄₀ (CsPW). The reaction gave dihydrocarvone, a valuable fragrance intermediate, as the main product with turnover numbers of up to 8000. The nature of the solvent had a strong effect on reaction rate and selectivity. CsPW (0.1 mol%) was found to be a highly efficient and truly heterogeneous catalyst for this reaction, providing 82% yield of dihydrocarvone in 1,4-dioxane as a solvent under ambient conditions. This simple catalytic method represents economically attractive route to industrially important compounds starting from bio-renewable substrates easily available from essential oils.