Cycloaddition of Biomass-Derived Furans for Catalytic Production of Renewable <i>p</i>-Xylene

Abstract

A renewable route to p -xylene from biomass-derived dimethylfuran and ethylene is investigated with zeolite catalysts. Cycloaddition of ethylene and 2,5-dimethylfuran and subsequent dehydration to p -xylene has been achieved with 75% selectivity using H–Y zeolite and an aliphatic solvent at 300 °C. Competitive side reactions include hydrolysis of dimethylfuran to 2,5-hexanedione, alkylation of p -xylene, and polymerization of 2,5-hexanedione. The observed reaction rates and computed energy barriers are consistent with a two-step reaction that proceeds through a bicyclic adduct prior to dehydration to p -xylene. Cycloaddition of ethylene and dimethylfuran occurs without a catalytic active site, but the reaction is promoted by confinement within microporous materials. The presence of Brønsted acid sites catalyzes dehydration of the Diels–Alder cycloadduct (to produce p -xylene and water), and this ultimately causes the rate-determining step to be the initial cycloaddition.