β‐Funktionalisierte Hydrazine aus N ‐Phthalimidoaziridinen und ihre hydrogenolytische N,N‐Spaltung zu Aminen

β‐Functionalized Hydrazines from N ‐Phthalimidoaziridines and their Hydrogenolytic N,N‐Cleavage to Amines The three N ‐phthalimido‐aziridines 1–3 were reacted with phenol, thiophenol, aniline, p ‐toluenesulfonic acid, and H 2 O in selected combinations. These nucleophiles opened the 3‐membered ring to yield the N ‐phthalimidoamines 4a–d, 5a–d, 6a–c , and 6e ; all these products (except the carbinol 6e ) carry an aryl‐substituted functional group on the C‐atom vicinal to the N‐substituent. Hydrazinolysis of 4, 5, 6a–c , and 6e afforded the β‐functionalized hydrazines 7, 8, 9a–c , and 9e . The reducing medium Raney ‐Ni/N 2 H 4 transformed 4, 5, 6a–c , and 6e to the β‐functionalized amines 10, 11, 12a–c , and 12e . By a study with the hydrazide 6a and the hydrazine 9a , it was shown that the N,N‐cleavage is a catalytic hydrogenolysis by H 2 generated from N 2 H 4 with Raney ‐Ni and that it does not take place on the hydrazide 6 , but rather on the hydrazine 9 , generated as intermediate from 6 with N 2 H 4 . Spectroscopic data confirmed that the conversions of 1–3 to 4–6 occurred exclusively with inversion and that the resulting configurations remained fully intact during the transformations of 4, 5 , and 6 ( via 7, 8 , and 9 ) to 10, 11 , and 12 , respectively.