Electroörganic Preparations. VI. Reduction of Compounds Containing the Azomethine Group.

Abstract

cf. CA 54, 22676a. The polarographic redn. in buffered medium of a no. of ketimines, anils, oximes, azines, phenylhydrazones, and semicarbazones by controlled-potential redns. gave the no. of electrons involved in the electrode reactions, the redn. products, and some indications of a probable redn. path. All investigations were carried out in 40% alc. contg. 1M KCl as supporting electrolyte and the reducible compd. in 20 γ/ml. amts. Cyclohexanone (in MeNH2) was reduced to N-methylcyclohexylamine-HCl, m. 175-6° (EtOH-Et2O), benzophenone anil to benzhydrylaniline-HCl, m. 201-3°, testosterone propionate oxime, m. 184° (aq. EtOH-C6H6-C6H14) (2,4-dinitrophenylhydrazone, m. 212-15° (from BuOH and tetra-hydrofuran-EtOH)) to the corresponding amine, m. 218-22° (HCl salt, m. 235-40°), anti-cinnamaldehyde to cinnamylamine-HCl (Bz deriv., m. 93-4°) and hydrocinnamaldehyde (2,4-dinitrophenylhydrazone, m. 149-51°), benzylideneacetone to N-(methylcinnamyl)benzamide, m. 135-7°, anti-benzaldoxime to PhCH2NH3Cl (I), m. 252-5° (EtOH-Et2O) (Bz deriv., m. 104-6°), N-benzylbenzaldoxime to dibenzylamine-HCl, m. 257-8°, mesoxalic acid ester oxime to (EtO2C)2CHNH3Cl, m. 159°, benzamide oxime to benzamidine (picrate, m. 233°), benzalazine to benzaldehyde benzylhydrazone, m. 68-70° (picrate, m. 130°), and I, PhCH:NNHPh to I, Ph2C:NNHPh to Ph2CHNH3Cl (II), sublimes 280°, p-Me2NC6H4CH:NNHPh to N4,N4-dimethyltoluene-α,4-diamine-di-HCl, cinnamaldehyde semicarbazone to hydrocinnamaldehyde semicarbazone, m. 124-6° (2,4-dinitrophenylhydrazone, m. 149° (aq. EtOH)), benzylideneacetone semicarbazone to benzylacetone semicarbazone, m. 142° (C6H6) (2,4-dinitrophenylhydrazone, m. 125-6.3°), PhCH:NNHCONH2 (III) to I, and Ph2C:NNHCONH2 to II. III was also reduced at pH 4 to 1-benzhydrylsemicarbazide, m. 164-5°. [on SciFinder(R)]