N-Aryl hydroxamic acids represent a group of valuable synthetic intermediates. Their N-OH modification, by appending good leaving group (LG), triggers intramolecular rearrangement leading to the N-O bond cleavage and migration of the O-LG moiety into the aromatic ring. The developed reaction sequence is straightforward and affords variety of new organic molecules, otherwise inaccessible. Overall, thirty derivatives were synthesized, of which fourteen are completely new organic substances. Perspective applications of these novel organic substances is seen as valuable starting materials for organic synthesis, pharmacochemistry, biochemistry, materials chemistry, catalysis, drugs, polymers, etc.