Radical-nucleophilic (SRN1) reactions. Part 4. Preparation, reactions, and electron spin resonance studies of α-nitro azides

Abstract

2-Azido-2-nitropropane and 1-azido-1-nitrocyclohexane have been prepared by syntheses involving intermediate radicai-anions (S_RN1 and oxidative addition). S_RN1 Reactions between α-nitroazides and azide, benzenesulphinate, and p-chlorobenzenethiolate proceed with loss of nitrite. The S_RN1 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.