Electrochemical Generation of Unstable Nitrogen Species. Part 4. Electrochemical and Chemical Oxidation of cyclic and Open-chain Diamines. The Formation of Cyclic Hydrazine Derivatives

Article abstract of DOI:10.1246/bcsj.53.2040

Intramolecular N,N-coupling by the electrochemical oxidation of cyclic and open-chain diamines such as 3,3,7,7-tetraethylperhydro-1,5-diazocine (1) and N,N-dimethyl-2,2-diethyl-1,3-diaminopropane (2) was investigated with the use of platinum, silver, nickel, and carbon anodes.In the case of 1, cyclic hydrazine derivatives, 3,3,7,7-tetraethyl-1,5-diazabicyclo<3.3.0>octane and 1-(2-ethyl-2-formylbutyl)-4,4-diethyl-4,5-dihydropyrazole were formed in high current efficiency.In the case of 2, the corresponding hydrazines, 1,2-dimethyl-4,4-diethylpyrazolidine and1-methyl-3,3-diethyl-4,5-dihydropyrazole, were obtained in low current efficiency, because C-N bond cleavage took place before N,N-coupling.A carbon anode was found to be effective for N,N-coupling of such diamines.Chemical oxidative N,N-coupling of 1 and 2 was studied by using sodium peroxodisulfate and lead tetraacetate.