A simple methodology has been developed for the synthesis of previously unstudied N‐substituted glutarimide derivatives ‐ (Z)‐1‐(aryl(arylimino)methyl)piperidine‐2,6‐diones 4 a–p obtained in one step from C,N‐diarylformamidines 1 a–p and glutaric anhydride 6 with product yields from 46 up to 88 % and chromatographic purity from 94 to 99 %. The structures of the obtained compounds were proved using NMR spectroscopy 1H, 13C, X‐ray diffraction analysis, mass spectroscopy, and elemental analysis. An in vivo study of the analgesic activity of a representative of series 4 a was carried out.