N‐Alkylation of imides in the reaction of imides and alkylhalides, catalyzed by PT catalysts under solvent‐free conditions, has been developed. The reaction occurs in the presence of K2CO3, and in many cases it takes place spontaneously. In the N‐benzylation reaction, it has been recognized that TBAB (tetrabutylammonium bromide) and TBATFB (tetrabutylammonium tetrafluoroborate) show highest catalytic effect. Versatility and synthetic capacity of the solvent‐free alkylation has been confirmed by N‐benzylation and N‐ethylation of various imides. The developed procedure gives easy access to N‐(ω‐bromoalkyl)imides.
