ELECTROCHEMICAL REDUCTIVE AMINATION. I. AMINATION OF ALIPHATIC KETONES BY PRIMARY AMINES
The reductive amination of aliphatic ketones in aqueous solutions of primary amines was realized by an electrochemical method.The best yields of the secondary amines were obtained at lead and cadmium cathodes in an aqueous electrolytic solution at pH 11-12.Elongation and branching in the carbon chain of the radicals both of the ketone and of the primary amine lead to a reduction in the yield of the secondary amine.The yield of the secondary amine is mainly determined by the rate of the chemical reaction leading to the formation of the azomethine compound, preceding the electrochemical reduction stage.
Smirnov, Yu. D.,Tomilov, A. P.
p. 42 - 48
(2007/10/02)
Configurational Prevalence at the Nitrogen Atom in Chiral, Open Chain, Secondary Amines
The stereochemistry of chiral, open chain, secondary amines has been studied by means of low-temperature (1)H and (13)C n.m.r. spectroscopy and by PCILO molecular-orbital calculations.The chiral nitrogen assumes a strongly prevalent configuration under the assymmetric induction of a vicinal asymmetric carbon atom.In the most probable conformation of the secondary amine the lone pair of the nitrogen is placed in the most crowded position.