Active and deactive modes of modified montmorillonite in p-cresol acylation

• Montmorillonite clay was modified by p-TSA-treatment under microwave irradiation.
• Catalyst used to study acylation reaction under microwave and conventional heating.
• Catalytic activity dropped more than 50% in conventional heating showing deactivation.
• Catalyst deactivation occurs during O-acylation not in subsequent Fries rearrangement.
• Coke formation retarded in microwave heating due to polar sites changing orientation.

para-Toluene sulphonic acid (p-TSA)-treated montmorillonite clay used as heterogeneous catalyst in acylation of para-cresol (PC) with aliphatic carboxylic acids. Reactions were studied under microwave and conventional modes of heating and reaction conditions were optimized by varying mole ratio, temperature, amount of catalyst and reaction time. Under optimized conditions the reaction was carried out involving p-cresol and decanoic acid. The reaction involved two steps, O-acylation involving ester formation followed by the Fries rearrangement involving C-acylation resulting in ketone product. Microwave heating mode showed higher conversion and the catalytic activity almost retained in repeated use. On the other hand the catalytic activity dropped by more than 50% in the case of conventional heating indicating rapid deactivation. A change in the color of the used catalyst was more intense in the case of conventional than in the microwave heating. Used catalysts were characterized for surface area and pore volume by BET technique, acidity by FTIR spectroscopy and amount of coke by TGA. Further investigations on the catalyst used in conventional heating revealed that the deactivation occurred during the O-acylation and not in the subsequent Fries rearrangement. However, the catalyst in the microwave irradiated reaction, exhibited a retarded rate of formation of coke precursors on the surface during O-acylation, thus preventing any decrease in catalytic activity. Present study indicates that the technique chosen for heating the reaction medium plays an important role in suppressing deactivation.

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