Esterification or Thioesterification of Carboxylic Acids with Alcohols or Thiols Using Amphipathic Monolith-SO3H Resin

Abstract

We have developed a method for the esterification of carboxylic acids with alcohols using amphipathic, monolithic-resin bearing sulfonic acid moieties as cation exchange functions (monolith-SO₃H). Monolith-SO₃H efficiently catalyzed the esterification of aromatic and aliphatic carboxylic acids with various primary and secondary alcohols (1.5–5.0 equiv) in toluene at 60–80 °C without the need to remove water generated during the reaction. The amphipathic property of monolith-SO₃H facilitates dehydration due to its capacity for water absorption. This reaction was also applicable to thioesterification, wherein the corresponding thioesters were obtained in excellent yield using only 2.0 equiv of thiol in toluene, although heating at 120 °C was required. Moreover, monolith-SO₃H was separable from the reaction mixtures by simple filtration and reused for at least five runs without decreasing the catalytic activity.