Sciencemadness Discussion Board
Not logged in [Login - Register]
Go To Bottom

Printable Version  
Author: Subject: Accidentally Powerful Tetrazole
Tdep
National Hazard
****




Posts: 382
Registered: 31-1-2013
Location: MOF-land. Land of the MOFs
Member Is Offline

Mood: Peroxidey

[*] posted on 19-11-2017 at 22:37
Accidentally Powerful Tetrazole


So a bit of context to this question.

Back in late 2015 I ran some 5-ATZ from the diazionation of aminoguanidine bicarbonate as written up by Engager. I would always get this weird yellow precipitate that i'd remove then continue on with the synthesis, all of which failed. Once or twice I ended up purifying soldium sulfate out of the reaction mix, getting excited about my yields and how good the crystals looked... very sad moments.

Fast forward to this year and I tried it again, got the same results and with the help of my uni's NMR I confirmed that the yellow precipitate was indeed the 5-ATZ, and there was no obvious contaminate that was making it yellow, the 1H NMR and 13C NMR was clean. This is all in a video I made recently here: https://youtu.be/4Q4jU-J3mKg

Sure, that's all fine. But somehow, i'd managed to keep the yellow precipitates from back in 2015! More 5-ATZ just lying around under my nose this whole time! I show the old precipitates in the video at 14:16
I recrystallised this from water, washed with ice cold water and a little bit of methanol (bad move, this dissolved quite a bit of it) but then on drying... this stuff isn't 5-ATZ.

5-ATZ melts and then burns on heating, as far as i'm aware. This is what the recently synthesised batch does. The newly recovered stuff just blows up. It undergoes DDT in very small amount. While not insanely powerful, I haven't seen this level of DDT outside of a heavy metal salt (I haven't done much tetrazole stuff yet).


VIDEO: https://youtu.be/CtncHnT5G7w


If it's not 5-ATZ, what is it? Did storing it slightly damp for nearly 2 years cause it to change? Could it have been something else the whole time... the diazonium intermediate? Nah, i've isolated that before I believe and it didn't do what this stuff does. So any ideas?

I should mention its the same colour as my 5-ATZ sample, so I fully expected it to be 5-ATZ until it exploded. I have approx 80mg I think after the recryst. Glad I don't have more or things might've got hairy...

It's also acidic so I don't believe it is a salt of any kind, it is a free acid tetrazole.

Thanks for your thoughts



tl;dr: I recovered what I thought was 5-ATZ, but instead of melting and burning it easily undergoes DDT, but i'm not sure what it is.

View user's profile View All Posts By User
Tetra
National Hazard
****




Posts: 259
Registered: 23-7-2015
Location: The Pseudo-boondocks
Member Is Offline

Mood: High Thermal Inertia

[*] posted on 20-11-2017 at 05:49


Dissolve it in water and feed it to your Epazote plants - make Supazotes :P :D



In a perpetual search for Nitric Acid :[

My YouTube channel is Rhodanide.
View user's profile View All Posts By User
The Volatile Chemist
International Hazard
*****




Posts: 1960
Registered: 22-3-2014
Location: 'Stil' in the lab...
Member Is Offline

Mood: Copious

[*] posted on 20-11-2017 at 10:17


I don't suppose you've got access to your uni NMR, since you've graduated now, right?



My write-ups are on here...
http://www.MeltThe.Ga or http://ptp.x10.mx
View user's profile Visit user's homepage View All Posts By User
nitro-genes
International Hazard
*****




Posts: 838
Registered: 5-4-2005
Member Is Offline


[*] posted on 20-11-2017 at 12:10


It's makes DDT too quick to be tetrazene or MTX-1, which was my first guess...hmmm... guanylazide itself? Maybe nitrotetrazole, a diazotization product of diaminoguandine or some guanazole derivative? Could be a lot of things probably.

[Edited on 20-11-2017 by nitro-genes]
View user's profile View All Posts By User
NeonPulse
National Hazard
****




Posts: 383
Registered: 29-6-2013
Location: The other end of the internet.
Member Is Offline

Mood: thinking outside the box...

[*] posted on 20-11-2017 at 17:11


Very interesting! Did you make the original batch with nitric acid? Perhaps while storing it wet and with residual nitric left it created nitrotetrazole of sorts over time. I was also going to guess tetrazene at first but as nitrogenes above said it undergoes DDT too fast. Did you try mix it with silver nitrate in minute amount and see if you get a result.



Where there is a will
there is a way.

Like many of us i also do Youtube.... AllCheMystery!
https://www.youtube.com/channel/UCWbbidIY4v57uczsl0Fgv7w?vie... Fixed link. You can see it now!
View user's profile View All Posts By User
Tdep
National Hazard
****




Posts: 382
Registered: 31-1-2013
Location: MOF-land. Land of the MOFs
Member Is Offline

Mood: Peroxidey

[*] posted on 24-11-2017 at 05:06


I don't have access to the NMR anymore no, which is sad.

I didn't believe I had made it with nitric acid, but I went back and checked the footage and surprisingly, I had used nitric acid for the final acid pH adjustment to 4 for tetrazole crystallisation! (This was to avoid crystallisation of sodium sulfate)

So it was stored damp with nitric acid for 2 years... So nitrotetrazole is my current theory too. Given the high acidity of the product as well. Any specific tests? It's quite interesting that nitrotetrazole appears to have formed this way, this hasn't previously been reported in the literature I'm sure
View user's profile View All Posts By User
Dornier 335A
Hazard to Others
***




Posts: 202
Registered: 10-5-2013
Location: Northern Europe
Member Is Offline


[*] posted on 26-11-2017 at 14:21


5-Nitrotetrazole is extremely hygroscopic so that should be a clue. I dried mine over conc. sulfuric acid for a few weeks and got crystals, but they turned into puddles in less than five minutes after I opened my desiccator. My first thought was that it might be something like 5,5'-diazoaminotetrazole or azotetrazole. Both form from oxidation of 5-ATZ followed by condensation with another 5-ATZ. The latter even decomposes to 5-azidotetrazole in contact with nitric acid.
View user's profile View All Posts By User

  Go To Top