- Wednesday, January 1, 1986
- Radical-nucleophilic (SRN1) reactions. Part 4. Preparation, reactions, and electron spin resonance studies of -nitro azides
- Published at:J. Chem. Soc., Perkin Trans. 1, 1986, 555 - 565, DOI: 10.1039/P19860000555
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 -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 Me2NO2, formed by a minor dissociation route from [Me2C(N3)NO2]–, has been observed by e.s.r. spectroscopy.