Synthesis and NMR investigation of 3,4-diazabicyclo[4.3.0]non-2-ene and N,N'-azo-3-azabicyclo[3.3.0]octane. X-ray crystal structure analysis of a new tetrazene derivative

✍ Scribed by H. Delalu; M. Elkhatib; L. Peyrot; B. Fenet; B. F. Mentzen

• Publisher: Journal of Heterocyclic Chemistry
• Year: 1999
• Tongue: English
• Weight: 433 KB
• Volume: 36
• Category: Article
• ISSN: 0022-152X
• DOI: 10.1002/jhet.5570360317

✦ Synopsis

Abstract

3,4‐Diazabicyclo[4.3.0]non‐2‐ene and N,N'‐azo‐3‐azabicyclo[3.3.0]octane are the main products of the oxidation of N‐amino‐3‐azabicyclo[3.3.0]octane by chloramine. These new compounds have been isolated and characterized. A structural study has been performed with the goal of establishing the cis—trans configuration at the bicyclic junction. Multinuclear proton decoupling carried out on the endocyclic hydrazone has allowed the determination of the coupling constant of the bridgehead hydrogens. A low temperature conformational study shows splitting of the ^13^C signal of the carbon atom located α with respect to the ammonia nitrogen. This result, consistent with a cis structure, was confirmed by a nmr analysis conducted on the solid tetrazene derivative. The X‐ray data collection on a single cyrstal of the tetrazene has permitted us to determine the crystallographic properties of this compound. Data processing by direct methods reveals that the geometry of the molecule presents a cis configuration for the bicyclic bridge link and a trans one for the azo group, confirming thus the main results obtained by nmr studies.