Advantageous heterogeneously catalysed hydrogenation of carvone with supercritical carbon dioxide

Abstract

The hydrogenation of carvone was investigated for the first time in high-density carbon dioxide. The hydrogenation over 0.5 wt% Pd, or Rh, or Ru supported on alumina was found to be generally faster in a single supercritical (sc) phase (fluid reagents) than in a biphasic system (liquid + fluid reactants). The reaction with Pd produced fully hydrogenated products (isomers of carvomenthone) and carvacrol. The Rh catalyst was more selective and favoured carvomenthone isomers with higher selectivity and carvotanacetone as a secondary product. Additionally, the rhodium catalysed reaction exhibited high > 84% selectivity of carvotanacetone with the conversion of > 25% after only 2 min of reaction. The less active Ru catalyst gave significantly lower conversion and the product variety was greater as carvomenthone isomers, carvotanacetone and carvacrol were formed. The conversion and selectivity to carvomenthone within 2 h of the reaction starting followed the order: Pd > Rh > Ru and Rh > Pd > Ru, respectively. High conversion, and diverse and high selectivity accompanied by significant reduction in reaction time depending on the catalyst were achieved in supercritical CO₂ compared with hydrogenation occurring in conventional organic solvents.