Effect of acid modification of kaolin and metakaolin on Brønsted acidity and catalytic properties in the synthesis of octahydro-2H-chromen-4-ol from vanillin and isopulegol

• Kaolin and metakaolin were modified by 0.25–3.0 mol/dm3 HCl.
• The concentration of HCl affects the textural and acid-base properties.
• Acid-activated clays were used as catalyst for the Prins cyclization of (−)-isopulegol with vanillin.
• 90% selectivity toward octahydro-2H-chromen-4-ol was observed in the presence of HCl-metakaolin.
• HCl-kaolin systems were more active than HCl-metakaolin solids.

Natural kaolin and the metakaolin obtained by calcination of kaolin at 650 °C were chemically activated using 0.25–3.0 mol/dm3 HCl solutions. Structural and textural properties of samples were characterized by X-ray diffraction, elemental analysis and N2-adsorption/desorption analyses. The amount of Brønsted acid sites (BAS) was determined by infrared spectroscopy using pyridine as probe molecule. The amount of BAS for kaolin rose with increasing HCl concentration up to 1.0 M, and decreased for higher concentrations, that is related with the leaching of Al from the solid. Effect of HCl concentration on amount of BAS was negligible for metakaolin. The catalytic performance of these materials was investigated in the Prins cyclization of (−)-isopulegol with vanillin to form octahydro-2H-chromen-4-ol, carried out in toluene at 50 °C. The reaction rate and the selectivity toward octahydro-2H-chromen-4-ol depended on the Bronsted acidity, structural and textural properties of the catalysts. The reaction rate in the presence of kaolin modified by HCl correlated with the amount of BAS. HCl-kaolin samples were more active compared with HCl-metakaolin, while selectivity reaction toward octahydro-2H-chromen-4-ol was larger in the presence of HCl-metakaolin.

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