Solid acid-catalyzed carboxymethylation of bio-derived alcohols: an efficient process for the synthesis of alkyl methyl carbonates

Acid-catalyzed carboxymethylation of alcohols is an emerging organic transformation that has grabbed the attention of scientific community in recent years. In the present study, sulfonated mesoporous polymer (MP-SO₃H) is presented as a highly active solid acid catalyst to convert a wide range of alcohols into alkyl methyl carbonates. The remarkable catalytic activity of MP-SO₃H is comparable to that of reported homogeneous acid catalysts. A good correlation was established between the catalytic activity and textural properties of the material. An exceptional catalytic activity of MP-SO₃H was observed for DMC mediated carboxymethylation of bio-derived alcohols which is unmatchable to conventional resins and zeolites. This superior activity of MP-SO₃H is ascribed to its intrinsic mesoporosity, high acid strength and uniform coverage of surface area by active sites. The catalyst is recyclable, resistant towards leaching and can be used in successive runs without losing the original activity. To the best of our knowledge, MP-SO₃H is the first solid acid catalyst to exemplify highest activity for the synthesis of different alkyl methyl carbonates using DMC. The protocol developed herein opens up new avenues to transform wide range of bio-alcohols into useful organic carbonates in the future.