Mono‐Alkyl Etherification of Glycerol Acetonide as Glycerol Alternative with Epoxides

Abstract The mono‐alkyl etherification of glycerol to bio‐based and non‐EO (ethylene oxide) based monoalkylglyceryl ethers (MAGEs) has been of interest for scientists owing to the growing demand for surfactants in recent years. However, poor miscibility of glycerol with long‐chain hydrophobic building block and low selectivity resulting from further etherification of MAGEs remain challenges. Here, we report the mono‐alkyl etherification of glycerol acetonide as glycerol alternative, reacted with various epoxides by using conventional acid–base catalysts under solvent‐free conditions to provide a comprehensive solution that is capable of preparing MAGEs with good selectivity, high yields (70%‒97%) and low E‐factor values (0.033–0.34). The utilization of NaOH as a catalyst demonstrates favorable effects on the conversion of alkyl glycidyl ethers, 1,2‐epoxyalkanes, medium‐cycloalkyl epoxides (C 5 /C 6 ). However, for macro‐cycloalkyl epoxide (C 12 ) and alkyl internal epoxides, significantly enhanced conversion is achieved by BF 3 ·Et 2 O employed as the catalyst through acid‐activated ring‐opening processes. The protocol paves a way toward several types of MAGEs, such as alkyl diglycerol ethers, cycloalkylglyceryl ethers (CAGEs), and dialkyl‐chain glyceryl ethers, all of which have potential applications due to their unique structures.