The possibility of a structural modification of quinoxalines through 1,3-dipolar cycloaddition of 7-azido-6-fluoroquinoxaline to norbornenes, enamines of cyclic ketones, and dimethyl acetylenedicarboxylate was demonstarated. The stability of 1,2,3-triazoline adducts was studied and the structure of the products of their molecular rearrangements was established. The cycloadduct of azide with cyclohexanone enamine undergoes azapinacolone rearrangement involving a contruction of the cycloalkane ring by one member affording amidine of cyclopentanecarboxylic acid. The triazoline adduct of the azide with dicyclopentadiene as a result of the rearrangement affords the corresponding aziridinoquinoxaline.