Generation of oxodiazonium ions 4.* Nitramine O-alkyl derivatives in the synthesis of benzotetrazine-1,3-dioxides

Article abstract of DOI:10.1007/s11172-011-0312-7

A new method for the synthesis of benzotetrazine-1,3-dioxides was developed from the 2-(tert-butyl-NNO-azoxy)-N-nitroaniline O-alkyl derivatives upon the action of strong acids (H₂SO₄, MeSO₃H, CF ₃CO₂H) or BF3·Et₂O. A mechanism suggested for these reactions includes transformation of the N=N(O)OR group (R = Me, Pri) to the oxodiazonium ion (N=N=O)⁺, which intramolecularly reacts with the neighboring tert-butyl-NNO-azoxy group, furnishing the tetrazine-1,3-dioxide ring.