“On‐Water” Interfacial Acidification Enhances Direct Ammonolysis of Triglycerides

Direct ammonolysis of triglycerides with liquid ammonia is a well‐established technology for the industrial manufacture of aliphatic amides typically requiring a large excess of ammonia. In this study, using glyceryl trilaurate (GTL) as a model triglyceride, we demonstrate that the rate of lauramide formation can be enhanced sevenfold at 150 °C and low ammonia excess (47:1 mol/mol ammonia/GTL) when the reaction is carried out in GTL‐in‐water(acetonitrile) (50:50 v/v) emulsions stabilized by surface‐active Aquivion perfluorosulfonic superacid (PFSA) particles, compared to a non‐emulsified system. Moreover, the lauramide yield after 5 h is nine times higher than that achieved with conventional ammonolysis in liquid ammonia at higher ammonia excess (148:1 mol/mol ammonia/GTL). This significant increase in activity is attributed to the “on‐water” selective acidification at the microstructured oil–water interface facilitated by adsorbed Aquivion PFSA particles, in combination with enhanced ammonia solubilization and selective glycerol extraction by the water(acetonitrile) phase.