AZOBRIDGES FROM AZINES .13. AZOBRIDGED POLYCYCLES - SKELETAL REARRANGEMENTS BY DENITROGENATION OF TRIAZOLINES AND SOLVOLYSES OF AZIRIDINES

Triazolines (2, 6 and. 12) derived from the corresponding azobridged p olycycles undergo rapid denitrogenation in the presence of several het erogeneous acids (e.g. silica gel) with formation of the aziridines (3 , 7, and 13) together with the rearrangement products (4) and (8). In addition to 7 and 8, further products are formed on extrusion of nitro gen from 6 by dissolved acids, especially formic acid. In these reacti ons the azo group of 6 is involved, and hydrazine (9) and enamine (10) are produced. These two products are also isolated from the very slow acid catalyzed rearrangement of aziridine (7). The most likely reacti on paths are exemplified with triazoline (6) in Scheme 1.