Synthesis of Halogenated Dibenzo[1,2,6]triazonines and Late-Stage Functionalization of the Triazonine Ring

Dibenzotriazonine represent a new class of nine-membered cyclic azobenzenes with a nitrogen atom embedded in the bridging chain. To enable future applications of this photoactive backbone, we propose in this study the synthesis of mono- and dihalogenated triazonines, that allow the late-stage introduction of different functionalized aryl groups and heteroatoms (N, O, and P) via palladium-catalyzed reactions. Indeed, different diphenylphosphoryl-triazonines were synthesized with functional groups such as aniline or phenol. Bis(diphenylphosphoryl)phenyl mono- and bis-carbamate-triazonines were also isolated in good yields.