Solid‐State Melt Rearrangement/Acetylation Reaction of Primary Amides and PhI(OAc) 2 in Reactive Eutectic Medium

A novel solid‐state melt rearrangement reaction from primary amides and PhI(OAc) 2 without any solvents in reactive eutectic medium was established. Compared with traditional solvent‐involved or high‐temperature solid‐state reactions, this reaction features lower temperature, shorter time, and higher efficiency. Especially for the aliphatic diamides and PhI(OAc) 2 , they could easily form a reactive eutectic mixture and undergo double Hofmann‐type rearrangement reactions, giving the diamine diacetylated products in high yields. Notably, the products can be easily isolated through a direct precipitation–filtration method.