How Many Nitrogens is Too Many Nitrogens? Part I

In a recently published article in ACIEE, a group from – I kid you not – Idaho reports the synthesis of several compounds that contain almost all nitrogen. Needless to say, these compounds are highly explosive and were, um, interesting to work with. Props to the students on this paper, assuming they still have a hand to perform a terrorist fist jab in the first place. This paper has been blogged about elsewhere, but it got me to thinking about other feisty compounds I’ve either heard about or prepared.

The first of these has to be octanitrocubane and its immediate cousin heptanitrocubane. Professor Philip Eaton was the first and maybe the last to prepare these compounds, and I was lucky enough to attend a “retrospective lecture” chronicling his career and life. It was probably the only seminar I’ve ever been to that made me pumped up to do chemistry and go scurrying back up into the lab to set up a bunch of reactions.

Anyway, much like nature makes berries bright red to warn you not to eat them, heptanitrocubane only successfully crystallizes in its anhydrous form from fuming nitric acid slowly diluted with sulfuric acid. Jesus that is the worst recrystallization ever. If that isn’t a warning to stop making the stuff, I don’t know what is. Even Ralph would know to turn heel and run.

My personal favorite is 5-diazotetrazole. Not only is the tetrazole nucleus explosive, so is the 5-aminotetrazole that the diazo compound is prepared from. A friend of mine (seriously, it wasn’t me, I have more sense than to work with this thing!) was trying to displace the diazo group with chloride. They performed the reaction on a tiny scale and still managed to blow a hole in the back of their hood and put a serious hurting on the blast shield they thankfully used. Needless to say, that analogue was set aside for another day. Sometimes that analogue just isn’t worth it…

Finally, there are the “explosive” compounds. The ones where your hands get sweaty and your heart races when you work with them. A short list might include: IBX, metal perchlorates, aryldiazonium salts, azides, and maybe KH, which is more burny than boomy. Anything I’m forgetting?