Negative catalysis by salts of variable valence metals in reactions for oxidation of aliphatic amines by molecular oxygen

Abstract

1. It was found that the salts of the variable valence metals act as negative catalysts in the initiated oxidation of primary and secondary aliphatic amines. The negative catalysis is due to the oxidation-reduction properties of the amino peroxide radicals. 2. The ratios of the rate constants:\({{k(RO_{\dot 2} + MX_n )} \mathord{\left/ {\vphantom {{k(RO_{\dot 2} + MX_n )} k}} \right. \kern-\nulldelimiterspace} k} (RO_2^. + RO_{\dot 2} )\) in cyclohexylamine and di-n-butyl-amine were measured for the salts of Co, Mn, Cu, Fe and Ce.