Nucleophilic Attack of Azide at Electrophilic Azides: Formation of N₆ Units in Hexazene and Aminopentazole Derivatives

Abstract

With the help of selective 15N labeling experiments, it has been confirmed that nucleophilic attack of azide at iminium‐activated organic azides leads to short‐lived hexazene intermediates. Such species do not only tend to a cleavage reaction with formation of N‐azido compounds, but also undergo ring closure to generate unprecedented amidino‐functionalized pentazoles. Thus, treatment of the parent Vilsmeier reagent with two equivalents of sodium azide creates an aminopentazole derivative as the main product, which is easily characterized by NMR spectroscopy.

Unexpected Electronic Behavior of Organic Azide and Metal‐Carbyne in Their 1,3‐Dipolar Cycloaddition Reaction

“…One very recent case reported by Banert and coworker involves an interesting reaction between electrophilic and nucleophilic azides, affording a novel aminopentazole derivative in one step. [ 24 ]…”

Evolving the Scope of 5,5’‐Azobistetrazoles in the Search for High Performing Green Energetic Materials

“…The most nitrogen‐rich azole, pentazole, is currently only used as a salt and is extremely difficult to access [10–11] . The first 5‐aminopentazole derivative was only recently detected by NMR spectroscopy by Bannert et al [12] . However, tetrazoles represent a more stable alternative.…”

Heterocyclic Nitrilimines and Their Use in the Synthesis of Complex High-Nitrogen Materials

“…Energetic materials (all of propellants, explosives, and pyrotechnics) fundamentally straddle both academic and practical realms. On the one hand, we have materials that are on the borderline of existence, where unique structures of these materials can contribute to the fundamental understanding of molecular stability, − and, on the other hand, ever-higher-performing and higher-stability propellants and explosives are sought for real-world applications. − …”