ELECTROCHEMICALLY INITIATED HYDROCYANOMETHYLATION OF N-HETEROARYL-SUBSTITUTED AZOMETHINES

The acetonitrile anion (1(-)), generated by electrochemical initiation and chemical regeneration, may be used as cyanomethylation reagent fo r C,N double bond structures, e.g, for hydrocyanomethylation of pi-def icient N-heteroaryl-substituted Schiff bases (2-12) yielding the beta- aminonitriles (2a-12a). The synthesis is initiated by deprotonation of acetonitrile (1) to 1(-) by cathodically generated azomethine radical anions (2(-.)-12(-.)) followed by nucleophilic reaction of 1-with 2-1 2 up to its complete consumption, in a cyclic self-reproducing process of 1(-). Besides 2a-12a, 3,4-heteroarylsubstituted 4-amino-3-butenoni triles and 1,3-heteroaryl-substituted 1,3-diaminoisobutyronitiles are formed in the course of a nearly currentless reaction.