Biomass toward fine chemical products: Oxidation of α-pinene over sieves nanostructured modified with vanadium

•The catalytic activity of V-M(x) was tested for the oxidation of α-pinene using H2O2.•TON increased strongly with decreasing V content due to a high V dispersion.•The highest α-pinene conversions was obtained with the aprotic solvent: acetonitrile.•Recycling studies indicated that the material was structurally stable.•The catalyst did not show loss of activity and selectivity after several cycles.

Vanadium-containing molecular sieves (V-M(x)) were synthetized and applied as heterogeneous catalysts for the liquid phase oxidation of α-pinene with hydrogen peroxide at 70 °C. It has been found that the vanadium content in V-M(x) materials affected the conversion of α-pinene and product distribution. The turnover numbers increased strongly with the decreasing of V content probably caused by a high V dispersion. The major products were verbenone, trans-sobrerol and campholenic aldehyde. The acid–base properties of V-M(x) affected the distribution of products formed via the isomerization of α-pinene oxide over Lewis acid sites to campholenic aldehyde while Brønsted acid sites brought about the formation of 1,2 pinanediol and trans-sobrerol by hydrolysis and by the opening of oxirane ring. The increase in V content in V-M(x) led to the increase in campholenic aldehyde, 1,2 pinanediol, trans- sobrerol and over oxidation products. Moreover, the effect of several solvents on the reaction oxidation was studied. The results showed that the highest α-pinene conversions are obtained in the following order: acetonitrile > ethanol > isoamyl alcohol > methyl ethyl ketone. Thus, using aprotic solvents, the catalytic activity was increased and the formation of alkyl glycol ethers as by-product was not observed.

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