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

Abstract

AbstractNitration 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.