Insight into the electrochemical oxidation of N,N-dialkyl-p-phenylenediamines in the presence of malononitrile and methyl cyanoacetate. A convergent paired electrochemical method for the synthesis of cyanide and dicyanide derivatives of phenylcarbonimidoy

•Electrochemical study of N,N-dialkyl-p-phenylenediamines•Convergent paired electrochemical synthesis of cyanide and dicyanide derivatives of phenylcarbonimidoyl•Mechanistic study using cyclic voltammetry, chronoamperometry, chronocoulometry and controlled-potential coulometry•Green electroorganic synthesis

The electrochemical oxidation of N,N-dialkyl-p-phenylenediamines has been studied in the presence of malononitrile and methyl cyanoacetate as nucleophiles in water/ethanol (80:20, v/v) mixture using some electrochemical techniques (cyclic voltammetry, chronoamperometry, chronocoulometry and controlled-potential coulometry). Diagnostic criteria of the electrochemical methods in keeping with spectroscopic data of the isolated products revealed that N,N-dialkyl-p-phenylenediamines in the presence of malononitrile and methyl cyanoacetate via a convergent paired electrochemical process are converted to cyanide and dicyanide derivatives of phenylcarbonimidoyl. The present work has led to development of a green and one-pot method for the synthesis of the title compounds.

Graphical abstractDiagnostic criteria revealed that N,N-dialkyl-p-phenylenediamines in the presence of malononitrile and methyl cyanoacetate via a convergent paired electrochemical process are converted to cyanide and dicyanide derivatives of phenylcarbonimidoyl.Figure optionsDownload full-size imageDownload as PowerPoint slide