Addition to nitrogen-oxygen double bonds

LINEAR ENERGY RELATIONSHIPS FOR SOME PERACID ADDITION REACTIONS 

Insofar as the reaction conditions can be considered comparable, the two oxidations are similar an electrophilic attack by the peracid seems to initiate the oxidation, it was also shown that peroxy-monochloroacetic acid (CICH2-CO2OH) reacted more rapidly than peracetic acid itselP which is consistent with an electrophilic attack by the reagent upon the nitrosobenzene. A similar reaction mechanism could be proposed viz. 

In this scheme electrophilic oxygen attacks the N=0 bond in an analogous way to the epoxidation of olefins the initially formed putative three-membered ring system then rearranges to the stable nitro-group. 

Many of the Diels-Alder type reactions may be described in terms of hetero-lytic mechanisms, some of which involve electrophilic attack as the first stage. The evidence for such mechanisms is, as yet, incomplete and such additions are discussed in Chapter 2. 

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