ASYMMETRICAL NITROGEN-40; GEMINAL SYSTEM-26. N-CHLOROHYDRAZINES

Article abstract of DOI:10.1016/S0040-4020(01)96503-2

The factors determining the kinetic and thermodynamic stabilities of N-chlorohydrazines are discussed.Acyclic N-chlorohydrazines exist only as trialkyldiazenium chlorides 3a,b.Chlorination of 2-acyl-1,1-dimethylhydrazines 6a,b gave 1,4-diacyl-2,3-dimethylhexahydro-1,2,4,5-tetrazines 7a,b via hydrazyl radical intermediates, and chlorination of a 1-phenylpyrazolidin-5-one 8 gave phenylazoisovaleric esters 9a,b.Stable N-chlorohydrazines were obtained from bicyclic hydrazines; viz. the 2-chloro-1.2-diazabicyclo(2.2.2.)octan-3-one 12 and 7-chloro-1,7-diazabicyclo(2.2.1)heptane 16.The restricted inversion of N(7) in 16 and its 1-methyl quate rnary salt 21 were observed in the 13C-NMR spectra.The acyclic N-chlorohydrazinium salt 25 was isolated.