β-Functionalized Hydrazines from N-Phthalimidoaziridines and their Hydrogenolytic N,N-Cleavage to Amines

Article abstract of DOI:10.1002/hlca.19850680128

The three N-phthalimido-aziridines 1-3 were reacted with phenol, thiophenol, aniline, p-toluenesulfonic acid, and H2O 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.Hydrazonolysis of 4, 5, 6a-c afforded the β-functionalized hydrazines 7, 8, 9a-c, and 9e.The reducing medium Raney-Ni/N2H4 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 H2 generated from N2H4 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 N2H4.Spectroscopic data confirmed that the conversions of 1-3 to 4-6 occurred exclusively with inversion and that the resulting configuration remained fully intact during the transformations of 4, 5, and 6 (via 7, 8, and 9) to 10, 11, and 12, respectively.