A probe for homolytic reactions in solution. Part VI. Reactions of polyhalogenomethyl radicals with nitrosobutane

Spectroscopic evidence (e.s.r.) has been obtained to show that the spin-adduct of a radical ·CX2Y (where X is Cl or Br) with nitrosobutane is converted into a carbonyl nitroxide (YC:O)N(But)O·. A radical mechanism is outlined which can accommodate this.When Y in the carbonyl nitroxide is F, Cl, or Br, it can be displaced by methanol, ethanol, or dimethylamine to give alkoxycarbonyl or aminocarbonyl nitroxides. The structure of these is compared with that of vinyl nitroxides.Attempts to trap propenyl radicals from crotonyl peroxide using nitrosobutane led to a dialkyl nitroxide tentatively formulated as (7).