Cage reaction hyponitrites

I he hyponitrites generally appear somewhat more efficient with respect to radical generation than the dialkyldiazenes (see 3.3.1.1). However, a proportion of radicals is lost through cage reaction with formation of the corresponding dialkyl peroxides or ketone plus alcohol (Scheme The disproportionation... 

Another example, discussed with the dioxetans later, which involves cage reaction of triplet radicals is that of the decomposition of hyponitrite esters [48]. Hydrogen abstraction from one radical R2CH-0 by another leads to triplet carbonyl products in high yield. 

The most interesting product from the decomposition of this hyponitrite was -butyl perbenzoate. The fact that free radicals accounted for the balance of the reaction products made it seem likely that the perester was formed by cage combination. This was supported by the observation that the yield of this product Increased with Increased solvent viscosity S). Furthermore, oxygen-18 labelling studies showed that the perester was formed with essentially complete randomization of the benzoyloxy oxygen atoms and that this randomization did not occur in any step preceding the decomposition of the hyponitrite ( ). All of these observations are consistent with a cage combination process for the formation of the perester product. 

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