Anodic oxidation of amines. Part II. Electrochemical dealkylation of aliphatic tertiary amines

Abstract

NN-Dimethyl tertiary amines undergo oxidative dealkylation on anodic oxidation in aqueous alkaline solution at a glassy-carbon electrode, and the major products are secondary amines and the appropriate aldehydes. On prolonged electrolysis the secondary amines produced undergo partial oxidative deal kylation to give primary amines and the appropriate aldehydes. The relative amount of dealkylation in unsymmetrical amines is predominantly governed by the acidity and the number of a-protons, but is also affected by the ease of oxidation of the radical Rl2N=CH Ra. Decarboxylation of the cation radical Me2N+CH2C0,-is involved in the anodic oxidation of NN-dimethylglycine. 6 R. M. Herbest and H. T. Clarke, J . B i d Chem., 1934, 104, 769;

Electrochemical and spectroscopic characterisation of amphetamine-like drugs: Application to the screening of 3,4-methylenedioxymethamphetamine (MDMA) and its synthetic precursors

“…The appearance of a peak at this E p value resulting from the oxidation of aliphatic secondary amines has also been described in the literature for other aliphatic amines [36,37]. Previous published works using compounds structurally related with MDMA also showed the occurrence of an anodic wave that has been undoubtedly attributed to the oxidation of the secondary amine [37][38][39].…”

Electropolymerization of Methylene Blue Investigated Using On-Line Electrochemistry/Electrospray Mass Spectrometry

“…However, there is the possibility that the small amount of Azure B observed was generated by electrochemical demethylation in the ES emitter. Oxidative demethylation of tertiary amines including phenothiazines is known to be a facile process [35][36][37][38][39]. Figure 2b presents the same portions of the ES mass spectrum of MB as in Figure 2a, but with the potential of the working electrode held at þ1.2 V (vs. Ag=AgCl).…”

Voltammetric Oxidation of Drugs of Abuse I. Morphine and Metabolites

“…The appearance of this wave is related with the oxidation of the secondary amine group present in the molecular structure. Although this oxidative pattern is already referred to in the literature for secondary amines [25,26], further evidence was obtained by studying a closely structurally related compound, norheroin (data not shown).…”