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β‐Funktionalisierte Hydrazine aus N ‐Phthalimidoaziridinen und ihre hydrogenolytische N,N‐Spaltung zu Aminen
Author(s) -
Egli Markus,
Hoesch Lienhard,
Dreiding André S.
Publication year - 1985
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19850680128
Subject(s) - chemistry , hydrogenolysis , medicinal chemistry , hydrazine (antidepressant) , hydrazide , substituent , aniline , cyclohexylamine , nucleophile , thiophenol , yield (engineering) , catalysis , organic chemistry , chromatography , materials science , metallurgy
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.