Three kinds of alkoxy group‐functionalized acidic ionic liquids (ILs) are reported in this work, namely, 1‐(methoxyethyl)‐3‐methylimidazolium hydrogen sulphate [MOE‐MIM]HSO4, 1‐(ethyoxyethyl)‐3‐methylimidazolium hydrogen sulphate [EOE‐MIM]HSO4, and 1‐(propyoxyethyl)‐3‐methylimidazolium hydrogen sulphate [POE‐MIM]HSO4. The short side chain on the cation of [MOE‐MIM]HSO4 decreases the solubility of the IL in butanol and butyric acid and facilitates the separation of the IL from a reaction medium. The yield of butyl butyrate is up to 99.5%. After 10 rounds of recycling, the catalytic performance of [MOE‐MIM]HSO4 shows no significant changes.
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