α-Dicarbonylmonohydrazone und ihre Acylderivate als Nucleophile und Nachbargruppen/α-Dicarbonylmonohydrazones and their Acylderivatives as Nucleophiles and Neighbouring Groups

Abstract

The aminomethylation of the α-carbonylhydrazones 1 and 14 with N,N,N′,N′-tetralkylaminals yields only N,N- or C,N-bis-aminomethyl products, but no C-mono-aminomethyl compounds. Phenylglyoxal N-methylhydrazone (24) yields the Mannich bases 27, while anilinocarbonyl hydrazone 29 dependent on the conditions gives rise to the N-aminomethyl derivatives 30 or to the Mannich bases 31. From benzoylhydrazone 33 and semicarbazone 35 the Mannich bases 34 and 36, respectively, are available. Mercury-EDTA reacts with 27 and 31 by twofold dehydrogenation and cyclization to form the lactams 46 and 47, respectively, whose treatment with perchloric acid yields the triazinium salts 45 and 51. When Mannich base 34 is exposed to the same oxidation conditions, the products of both dehydrogenation steps, 54 and 55, may be isolated. From the semicarbazones 36 only the triazines 56 are produced after a single dehydrogenation step.