The oxidation of the alpha-carbon of amines in hydrothermal condition: an alternative synthetic route of compounds containing amide bond

Here we report experimental evidence for the simple synthesis of N,N-diethylhydroxylamine and an amide bond formation reaction from oxidation of the alpha-carbon of tertiary amines by the reaction of triethylamine and hydrogen peroxide in hydrothermal conditions. It is proved that 120 degrees C is a turning point: when the temperature is lower than that, the main product is N,N-diethylhydroxylamine as a result of a cope rearrangement reaction mechanism; on the contrary, the product is more complex and the main products are amides via a radical chain mechanism involving three steps: initiation, propagation, and oxidation, followed by decarbonylation and electrocyclization because the radical is easier to form under high temperature. (C) 2013 Elsevier Ltd. All rights reserved.