5-Aminotetrazole (5-ATZ) synth.

[Mr Cool]

I was expecting a sample of this stuff, but I'm not sure if that's going to arrive or not so I've started making it.
It is a cyclic compound, =C(NH2)-NH-N=N-N= (join the ends up), having a very high nitrogen content of 82%. It can form salts with acids such as HNO3, HClO4, and can form complexes with copper, nickel etc. It is being used / developed for gas generators in airbags and monopropellants.
I intend to make ammonium dinitramide with sulphamic acid, following the synth posted by Alchemist, and try to get a dinitramide salt of 5-ATZ. But first, the 5-ATZ must be made!

The patents I am using for reference are #'s 5,424,449 and 5,594,146, except that I am making aminoguanidine by reducing nitroguanidine with Zn/acid. The aminoguanidine is reacted with HNO2, and the product is then cyclised to form 5-ATZ.

I am just about to make the aminoguanidine, using 30g Zn, 14g nitroguanidine and 60mL 70% HNO3 (probably diluted to c. 100mL with H2O). I'll let you know how it goes...

[Mr Cool]

Well, it has been confirmed that the sample IS coming! 2kg, for free! :D
But, I shall continue trying to make it anyway.

I used 30g of Zn (5um), 14g of Nitroguanidine (NG) and 60mL of HNO3.

The NG is long crystals which have a habit of clumping together. To ensure that it was mixed well with the Zn (screened to remove lumps), I mixed it up before I added any water. This caused slight accident #1. Residual H2SO4 in the NG disagreed with the Zn, and the mixture started smoking... I dumped it into c. 100mL of cold water, this seemed to help. A slight fizzing for c. 3 seconds, then quiet.
I cooled it to c. 5*C, and started adding HNO3. At this point I realised that HNO3 probably wasn't the best choice since it releases NO2 when reacting with metals, and I'm trying to reduce the NG, but I carried on regardless.
All the HNO3 was added at such a rate as to keep the temp below 30*C. The mixture initially turned yellow due to nitrosoguanidine (fun stuff, burns like HMTD but without flame, releasing a cloud of smoke), then the yellow colour was reduced as the nitrosoG was reduced to aminoG. It's now slightly yellow.

Next step: purify the aminoguanidine...
I think I'll try adding NH3 (g), this should complex with the zinc and make it more soluble, I hope...
Any ideas on purification?

[Alchemist]

Hello all,

Mr. Cool, did you make the Nitroguanidine also? If so did you use one of the methods from the
pat's you posted to get Guanidine Nitrate. Again if so, did you go straight to Guanidine No3 or to
a So4 or HCL first then to the No3? Thanks!

[Mr Cool]

No, I got it from a chem company. Sorry!
If you want to buy some, try <a href="http://www.omikron-online.de/cyberchem." target="_blank">www.omikron-online.de/cyberchem.</a> I haven't used them, but they sell all over the world, their GN is quite cheap, and appear to sell to individuals.

[Rhadon]

I doubt that Omikron will ship the GN, because it is marked with **. That indicates a substance which they don't like to give to private persons. In order to get it, you will either have to order to a company or fill a special form that tells them about your "abilities to work with dangerous chemicals". See <a href="http://www.omikron-online.de/cyberchem/" target="_blank">this</a> site for further information (German language).

Has anyone ever tried to order ** chemicals from Omikron?

[vulture]

Mr. Cool, i'm a bit confused. I found a compound in my chemistry encyclopedia described as tetrazene, with the formula C2H6N10 and it seems a bit similar to what you describe, however searching chemfinder for it results in a compound with formula N4H4.

Unfortunatly I cannot find an image of tetrazene.

[PrimoPyro]

Tetrazole Analogues

Preface: If this topic should go into a new thread, go ahead and delete this post, and email me about it, and I will report it in it's own thread. Or just leave it here. :p

Has the synthesis of 5-methyltetrazole been documented here? It should be very easy from the simple reaction of acetonitrile with sodium azide. This looks slightly less powerful than 5-ATZ but should still pack quite the punch as long as it doesn't have an abnormally low density.

Also, is the 5-amino position the only nitrogen that forms ammonium salts? If so, then the 5-methyl analogue shouldn't form any salts. But looking at a compound with another such imino group, the NH function, perhaps this too forms iminium species, thus resulting in salt formation?

I think I'm hoping for too much when I propose using sodium cyanide and sodium azide to, upon quenching with water, form 5-H tetrazole. Another interesting possibility is to incorporate a trimer of this tetrazole into a nitrogen core, by either reacting 3M cyanogen bromide with 1M ammonia, or reacting 1M NCl3 with 3M NaCN (speculation warning on that last reaction.)

This compound, N(CN)3 would likely be very poisonous on it's own, but if used in conjunction with simple sodium azide, you end up with a nitrogen core with three tetrazole functions dangling off it (or two if three provides too much steric hindrance for reaction) bonded at the 5-position. Extreme power density.

Bang!

<img src="http://www.aerojetfinechemicals.com/azide.gif" alt=" - " />

PrimoPyro

[Microtek]

I just stumbled on another high nitrogen explosive which may interest you; hydrazine azide N5H5, nitrogen content 93.3 %.
I have found the following properties:
Density 1.30 g/cc ( not so good )
Heat of formation 3043 J/g
Melting point about 75 C
Quoted as "completely insensitive to ordinary mechanical stimulus"
Decomposition temp about 100 C

Using simple approximations, I have found a VOD of 7200 m/s and detonation pressure of 184 Kbar, but on the other hand the Berthelot approximation gives a gas volume*energy release product of 170 % relative to TNT.
Synthesis is relatively simple. One method was to react ammonium azide with hydrazine hydrate and let the produced NH4OH and water evaporate.

[Mr Cool]

That reminds me, I was going to try making ammonium azide some time, but never got round to it though (like so many things :()
93.3%, lol, that's pretty high! I was wondering, how are those VoD's, det pressures etc calculated? I did a search, but only found things like "calculated VoD for explosive X is higher than that of RDX...", nothing that told me how to calculate it...

My sample did arrive, but I'll carry on with the synth anyway (I totally forgot about it!). I was able to seperate the aminoguanidine, I filtered unreacted zinc out of the solution (heated to 60*C, to dissolve everything soluble), and then reduced its volume to c. 50mL, then I acidified it strongly with 70% HNO3. Aminoguanidine nitrate ppted, I weighed it a few minutes ago and got just over 5g. That's as far as I got, I left it to dry and forgot about it!

So far I haven't done much with the 5-ATZ I recieved, the nitrate salt is rather fun (burns FIERCELY), I haven't tried the dinitramide yet. I was all set to make ADN, I even had the dry ice, then got distracted and all the dry ice sublimed before I remembered :(. I tried a very quick, half-arsed attempt at making 5-nitraminotetrazole, using 5-ATZN and H2SO4, but didn't get anything. I'm really not surprised though, I took literally no care when doing the experiment (a pinch of 5-ATZN, a mL or two of room temp H2SO4, I just mixed it together, waited until I got bored, and dumped it into a few mL of water).

[nbk2000]

Just curious as to how you got the sample. Did you use the sample scam where you're "Research Company X"? <img border="0" title="" alt="[Wink]" src="wink.gif" />

[Microtek]

If you do a search on the subject ( calculating detonation pressure or some such ) within alt.engr.explosives, I think you'll get something - that's where I found it ( though I've found it elsewhere since ).
You'll need to test the calculations against a few known explosives because the poster was not certain of, or did not bother with, the correct units cal/g or J/mol for the heat of detonation for instance.

[Mr Cool]

It was very easy to get the sample, I e-mailed the company from a myname@hotmail.com account, asking them if they would send me a 2kg sample so that we could test it before we placed an order, to see if it was suitable for our needs (always "we", "our" etc). Then add the usual "Thank you very much for your help", "we look forward to doing business with you", "with best regards, Mr. My Name (representative X of imaginary company X)" etc.

I've used this basic e-mail to succesfully get mannitol, semicarbazide*HCl and 5-ATZ, and I would've got a lot of other chems with it, but they often asked me to pay shipping for a 1.5kg parcel from China etc., which is normally around $80 and that defeats the object of getting free samples. Also I've found Indian companies to be more helpful than Chinese ones for some reason.

[Mr Cool]

Just synthed what I believe to be 1,4-ditetrazolyltriazine!
I was reading about tetrazene in COPAE, and discovered that something called 1,4-ditetrazolyltriazine could be made by reacting 5-ATZ with NaNO2 and excess CH3COOH. I used citric acid, since I had no acetic acid stronger than vinegar, and citric is the least useful of the carboxylic acids that I have.

I added the 5-ATZ and citric acid to 150mL of water, and stirred until the citric had dissolved. 5-ATZ isn't very soluble, but this didn't seem to matter. It all reacted in the end.
As the NaNO2 was slowly added, the solution turned to yellow, orange, red, and then a very fine (looks amorphous, but could just be cryptocrystalline) sandy-coloured ppte started to form, and eventually settled. I left it overnight (I started yesterday) to fully ppte, now there are also some slightly more reddish particles in the ppte, I think these are larger crystals of the same stuff. I'll try recrystalising it all soon to see what happens. Oh, and the only time I used cooling was when I added a bit too much NaNO2, and it started to fizz too much.

Anyway, the dried ppte is nicely flame sensitive, small amounts make "PUFF!", "CRACKLE!" kinda noises when put into a flame.

I'll try to recrystalise it and let you know what happens in case anyone's interested.

[Ricky]

I`ve searched a while and found 5-mercaptotetrazole-1-acetic acid is a explosive stuff. It dosen`t exist detailed informations about a mercaptan of a tetrazole or something like this but i belive it will give some interested suggestions. Does anyone have ideas to the synthesis way to 1-chlorotetrazole-5-tiol ?

[megalomania]

Is 1-chlorotetrazole-5-tiol the correct name for this compound? Do you happen to have a CAS number, or a reference that mentions this substance?

[Bradt]

I can`t found somewhat to 1-chlorotetrazole-5-tiol but i found some interested compounds to tetrazoles.

5-amino-1H-tetrazole monohydrate, Cas-Nr. 15454-54-3
N-(1H-tetrazol-5-yl)-guanidine, CAS-Nr. 66591-60-4
bis-(1H-tetrazol-5-yl)-amine, CAS-Nr. 127661-01-2
1-amino-4,5-dihydro-1H-tetrazole-5-one, CAS Number: 84143-61-3

I believe this will have interest,
5-amino-1H-tetrazole monohydrate and bis-(1H-tetrazol-5-yl)-amine in +99% HNO3 and N2O5 ->
1-nitro-5-aminotetrazole and bis-(1-nitro-tetrazol-5-yl)-amine.