Generation of Cyanonitrene: Study of the Reaction of Sodium Hydrogen Cyanamide, tert-Butyl Hypochlorite, and Tertiary Amines

Article abstract of DOI:10.1021/jo00146a005

Reaction of sodium hydrogen cyanamide, tert-butyl hypochlorite (BHC), and tertiary amines at low temperatures (<-30 deg C) does not yield the anticipated aminimides (R3N⁺-^-NCN), but when the reaction mixtures were warmed to approximately 0-10 deg C, aminimides are formed in fair to good yields.At 0-10 deg C an abrupt and complete precipitation of sodium chloride occurs, and it is concluded that cyanonitrene or a cyanonitrene-like species is formed by α-elimination from the BHC/sodium hydrogen cyanamide reaction product .Compound 5 is stable at low temperatures, and reaction with tertiary amines is not observed.If the intercepting nucleophile is omitted, however, and the BHC/sodium hydrogen cyanamide reaction product is allowed to warm up, at 0-10 deg C the color of the solution changes from pale yellow to deep orange, concomitant with precipitation of sodium chloride.The workup yields dicyanodiazene (caution: explosive when neat), the known dimerization product of cyanonitrene. 1H and 13C NMR and ESR spectra have been used to monitor the reactions and also to characterize products and intermediates.