Non-photochemical rearrangements of o-nitrobenzyl compounds

Abstract

Three rearrangements of 2-nitrobenzyl compounds with increasingly complex structural changes are described. The first is a remarkably facile conversion of 2-nitrobenzyl triflate to 2-nitrosobenzaldehyde. The second is an unexpected formation of 1-acetyl-2,1-benzisoxazolone 7 during attempted preparation of the tert-butyl ester of O-acetyl 2-nitromandelic acid. The third, found in the reaction of 2-nitrobenzaldehyde cyanohydrin TMS ether 10 with cyclic secondary amines, results in oxidative cyanation of the position alpha to the amino group, giving the novel N-arylamino-α-cyanoamines 12a–e.