Science of Synthesis

Kubik, S., Science of Synthesis, (2010) 41, 512.

N-Alkyl-N-nitrosoamides rearrange upon heating to form unstable E-diazenolate esters, which fragment into close ion pairs of alkanediazonium carboxylates according to ‌Scheme 11‌.[‌55‌] Mechanistic studies show that increasing the steric bulk of the alkyl and acyl substituents of N-alkyl-N-nitrosoamides promotes their rearrangement, which is the rate-determining step in the reaction sequence.[‌56‌,‌57‌] In addition, the rate of reaction has been shown to be also affected by electronic effects indicating that a high-energy, four-membered oxadiazetyl species acts as an intermediate or transition state.[‌58‌]

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M eeeeee eeeeeee ee eeeeeeeee eee eeeeeeeee eeee M-eeeee-M-eeeeeeeeeeeee ee eee eeeeeeeee ee M-eeeeeeeeeeee eeee eeee eeeee eeeeeeeeeeeeeee eeeeeeeeeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee M-Meeeeeeeeeee[‌88‌]

References