Transformations on 2,3,4,5‐tetrahydrobenzo[b][1,4]‐dioxocin leading to substituted ortho‐nitroaryl azides, benzofuroxans, benzofurazans and related compounds

Nitration of the acetamido‐nitrobenzodioxocins 10 , prepared from the corresponding amino derivatives 9 , led to the acetamido‐dinitrobenzodioxocins 11 , hydrolysis of which furnished the corresponding amines 13 . Preparation of the dinitroazides 18 and acetamido‐nitroazides 21 as precursors to substituted dioxocino‐annelated benzofuroxans is described. Thermolysis of the dinitro‐azido derivatives 18a,c,e and/or direct nitration of the unsubstituted benzofuroxans 1a, 2a afforded the isomeric nitrobenzofuroxans 1b, 2b,c . Thermolysis of the acetamido‐nitroazides 21 gave the acetamidobenzofuroxans 1d, 2d,e . All benzofuroxans were deoxygenated to the corresponding benzofurazans 3b,d, 4b‐e . Some aspects of electrophilic and nucleophilic aromatic substitution are discussed.