2-Azido-2-nitropropane and 1-azido-1-nitrocyclohexane have been prepared by syntheses involving intermediate radicai-anions (SRN1 and oxidative addition). SRN1 Reactions between α-nitroazides and azide, benzenesulphinate, and p-chlorobenzenethiolate proceed with loss of nitrite. The SRN1 reaction between 1-azido-1-nitrocyclohexane and the anion of 2-nitropropane proceeds with loss of azide. Reactions between 2-azido-2-nitropropane and the anions of 2-nitropropane and diethyl ethylmalonate yield oxidative dimerisation. E.s.r. spectroscopy has been used to observe electron-capture by 2-azido-2-nitropropane and its dissociation to nitrite and an ill-defined radical which may be (Me2CN3)·. The addition of benzenesulphinate and the anion of 2-nitropropane to Me2ĊNO2, formed by a minor dissociation route from [Me2C(N3)NO2]–˙, has been observed by e.s.r. spectroscopy.