Sciencemadness Discussion Board - 5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends

5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends

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MineMan - 19-12-2018 at 21:52

Why so much love for DBX-1? It’s VOD is high, it’s lead free but is it not still pretty sensitive?

snooby - 20-12-2018 at 03:25

https://www.researchgate.net/publication/288871303_Recent_Ad...

This article include some detailed info about impurities in raw nantz.

wessonsmith - 29-6-2019 at 10:03

Quote: Originally posted by MineMan

Why so much love for DBX-1? It’s VOD is high, it’s lead free but is it not still pretty sensitive?

Yeah, I agree. I have made some of the nitrotetrazole salts, silver(AgNTz), copper(DBX-1), and Sodium(NaNTz). I have even made the Nickel salt from NaNTz. The Nickel looks very similar to NHN in color but will not separate out into a fine powder when suction filtered.

They are all very sensitive with NaNTz being the exception. NaNTz can't be used by itself in the Dihydtare form, it's too difficult to set off.

The nitrotetrazole salts are more stable and less reactive then Lead Azide but just as sensitive. So for those companies who use LA, DBX-1 is a direct replacement, and no machinery changes are necessary. For the rest of us, they still don't offer any advantage over primaries like NHN and are more expensive to manufacture.

wessonsmith - 29-6-2019 at 10:11

Quote: Originally posted by snooby

https://www.researchgate.net/publication/288871303_Recent_Ad...

This article includes some detailed info about impurities in raw NaNTz.

This doesn't apply to those who are manufacturing NaNTz using the 2017 Batch Method patent.

Microtek - 29-6-2019 at 10:55

I have experimented with the complexes in the "Green primaries" paper (transition metal complexes with nitrotetrazole amine and water). They are about equivalent with NHN in sensitivity and power, but makes DDT more reliably.

Mychemlife - 21-7-2019 at 09:09

Has anyone ever crystalized out any Na,(NTZ)

snooby - 4-11-2019 at 09:47

Since there are sooo many synths about nant, what is your favoriete? The facile methode give me a very yellow end product. Still kt works, but not like this: https://youtu.be/U-1bNouTHhQ

My solution Just turns green.
Edit: i usde this one: https://patents.google.com/patent/US9598380B2/en

I notice a lot of red Times, no maybe to fast addition rate waht explanins the color.

[Edited on 4-11-2019 by snooby]

fusso - 4-11-2019 at 10:47

Great crystals!!!

snooby - 4-11-2019 at 11:00

Whats your method of maling the nantz and het the clear crystals?

B.D.E - 14-3-2020 at 13:39

nevermind, please delete.
apologies.

[Edited on 14-3-2020 by B.D.E]

Etanol - 13-4-2020 at 13:04

How to prepare the NH4-nitrotetrazole from Na-nitrotertazole?
Na-NTz+H2SO4=>NTz ?
NTz+NH3 (water)=>NH4NTz ?
Is exist the short way?
I wish green primaryes)

NeonPulse - 21-4-2020 at 08:00

Quote: Originally posted by Mychemlife

Has anyone ever crystalized out any Na,(NTZ)

Sure have. But via recrystallising crude product in minimal Water first and second from Acetone. The greenish tint was replaced by Snow White colour.
These crystals you have look very nice and quite well formed. Nice job.

B(a)P - 18-5-2020 at 16:21

Yesterday I conducted a synthesis of 5-ATZ. I have done this reaction 3 other times, always following the Engager method, starting with aminoguanidine bicarbonate, presented earlier in this thread. The only way I deviate from Engagers write up is to add sodium carbonate until my solution is at pH 5.5 rather than adding the exact mass presented in the paper. Each time my yield of 5-ATZ has been around 70 to 80% based on aminoguanidine bicarbonate.
This time the changes in colour that I noted on my previous attempts did not quite match up. I also needed less sodium carbonate than I had previously used. I didn't question this as much as I should have.
At the completion of reflux I adjusted the pH to 3 and left the solution to cool.
After cooling no product was visible, which is normal given 5-ATZ readily produces supersaturated solutions. I tried agitating, but this did not work. I drew off 3 mls and warmed it on an evaporating dish to produce a seed crystal then inserted that into the main solution. After about 8 hours a small mass of needle like crystals precipitated. At this point I stopped and reviewed what I had done. I reviewed my notes and other than the differences mentioned above I couldn't see where I had gone wrong. I tried checking my pH and my meter was toast. I checked it with indicator paper and found it to be at around 1! It seems my pH meter was on its last legs during the synthesis and so I likely refluxed at a less than optimal pH. The crystallisation would also have occurred at a pH that was sub-optimal, though I understand this is not so critical as the pH for the reflux.
My question is what have I ended up with? I have done some research and can't find much on side products that might dominate at lower temperates. Yield is very low. My crystalline product is transparent, colourless and needle like to 10 mm in length. For scale the stir bar is 25 mm in length. The melting point of the product seems about right for 5-ATZ and it decomposes at about the right temperature in a way I would expect it to. My thoughts are a very low yield and as a result the product has crystallised very slowly. Does anyone have any resources that go into depth on the side reactions that occur for this reaction? Thanks in advance for any assistance!

B(a)P - 19-9-2020 at 01:36

Cadmium nitrotetrazole
0.5 g of cadmium was dissolved in 1.5 g of 70 percent HNO3 and a little dH2O
The cadmium nitrate was added to a solution of 0.5 g of nitrotetrazole in 2 ml dH2O.
A white precipitate of cadmium nitrotetrazole (CdNTZ) formed immediately with a slight exotherm.
On drying the precipitate shrunk in size considerably.
The CdNTZ was readily soluble in water.
CdNTZ is slightly friction sensitive and moderately impact sensitive.
CdNTZ is sensitive to direct and indirect heating and donates before melting in amounts almost too small to see.

Question about NaNT purification

pdb - 6-5-2021 at 23:01

I refer to "Facile method for preparation of NaNT" (US9,598,380). It works well and is indeed very easy. But I am intrigued by the 1:2 molar ratio of 5-AT to NaNO2: this means that if one mole of Na gives NaNT, another mole of Na goes into the solution and pollutes it. But in what form? NaNO3, or an excess of NaNO2, or what else? We should know this before trying to find a method to purify NaNT. Does anyone know how to write the reaction between 5-AT, NaNO2 and HNO3?

[Edited on 7-5-21 by pdb]

Advice from someone who has successfully prepared crystalline DBX-1

pdb - 11-5-2021 at 05:30

I have prepared DBX-1 according to Fronabarger twice, with similar results. I have no doubt about the nature of the product, which deflagrates on contact with flame and detonates on heat or under light confinement. On the other hand, I observe that the product, when dried on a filter, appears as lumps, which leave a fine sticky dust on the finger when touched. Under the microscope, this powder appears amorphous. Moreover, its density is low, and even under high pressure it is difficult to reduce its volume: for the same weight, it is 4 to 5 times more voluminous when pressed than AgN3 for example. Also, I wonder if I missed the crystallisation step: according to Fronabarger, at about one third of the addition of the ascorbate, the product starts to precipitate and the solution takes on a rusty colour within a few minutes. I have observed these changes, but still my DBX-1 appears amorphous, and in this form I do not see how it could replace Pb(N3)2 according to the drop-in replacement principle.

Also, I would be interested in having someone who has obtained DBX-1 in crystalline form look at the attached photos to tell me if any differ from their own experience. Thank you!

(sorry, the pictures are in reverse order)
(the microscope pics are 1 mm in lenth)

DBX-1 1.jpg - 43kB

[Edited on 11-5-21 by pdb]

DBX Labs - 21-5-2021 at 14:39

From my experience making DBX-1, I'll get a near identical amorphous brown sludge most every time I run from scratch. The sludge dries into chunks just like yours that are flame sensitive and detonate when confined and heated. However, I have never been able to get this first product to detonate confined with a fuse, even as a powder.
What I've found and and have yet to publish in a video is that when I've taken a small amount (~2-3 grams) of this amorphous product and fed it into a repeated synthesis from scratch, the impure DBX-1 present in the first product catalyzes the formation of much more visible DBX-1 crystals that are red rather than brown. Additionally, it appears much less gelatinous sludge remains intermixed with the product in this case.
Hope this helps.

pdb - 22-5-2021 at 06:18

Quote: Originally posted by DBX Labs

the impure DBX-1 present in the first product catalyzes the formation of much more visible DBX-1 crystals that are red rather than brown. Additionally, it appears much less gelatinous sludge remains intermixed with the product in this case.

This effect is reported by Ford (from line 46). I'll give it a try myself.

Attachment: 2015 DBX-1-Ford.pdf (929kB)
This file has been downloaded 372 times

FanofYellow - 11-2-2022 at 21:47

Hi guys, if you're following DBX labs (ReactiveChem) procedure with NaNO2+H2SO4, make sure to keep your temps within +5c of specified temperature (65 degrees) or you're gonna get some micro detonations and have a scary time.

First one scared the hell out of me. Thought my Chinaware was preparing to shatter, did a quick recon and just about the time I put the pieces together and realized what was happening the SECOND one happened. This occurred with the following setup:

Solution 1:
2g 5-ATZ
1.36mL H2SO4 (93%)
10mL Water

Solution 2 (to be added to solution 1):
5.68g NaNO2
20mL Distilled Water

Temperature was about 72 degrees when I did maybe the fifth 1.5mL addition of solution 2 into solution 1. Being done on a round bottom flash inside of my stirring heating mantle.

edit: was also blowing air into reaction flask to help clear evolved NO2. Maybe that contributed to the micro detonations

[Edited on 12-2-2022 by FanofYellow]

FanofYellow - 12-2-2022 at 14:29

What do you guys think? NaNTZ synthesis I panicked over yesterday. I don't know if that's the final product though, methinks I might have made sodium nitrate, those big crystals decompose into NOx on heating, but they do crackle

Screenshot_20220212-162223-423.png - 855kB

B(a)P - 12-2-2022 at 23:22

That kind of looks like 5 aminotetrazole. Nitrotetrazole should do not then crackle.

FanofYellow - 14-2-2022 at 12:00

Quote: Originally posted by FanofYellow

What do you guys think? NaNTZ synthesis I panicked over yesterday. I don't know if that's the final product though, methinks I might have made sodium nitrate, those big crystals decompose into NOx on heating, but they do crackle

Quote: Originally posted by B(a)P

That kind of looks like 5 aminotetrazole. Nitrotetrazole should do not then crackle.

My beautiful crystals nooooo.... Instead of crackling on heating my (formerly) beautiful crystals turned to completely nonflammable white powder. Testing my end product with Silver Nitrate solution precipitated out some insoluble white stuff which pretty much confirms I've made sodium sulfate... Oh well, back to the bench to try again.

B(a)P - 14-2-2022 at 13:58

Quote: Originally posted by FanofYellow

Hi guys, if you're following DBX labs (ReactiveChem) procedure with NaNO2+H2SO4, make sure to keep your temps within +5c of specified temperature (65 degrees) or you're gonna get some micro detonations and have a scary time.

First one scared the hell out of me. Thought my Chinaware was preparing to shatter, did a quick recon and just about the time I put the pieces together and realized what was happening the SECOND one happened. This occurred with the following setup:

Solution 1:
2g 5-ATZ
1.36mL H2SO4 (93%)
10mL Water

Solution 2 (to be added to solution 1):
5.68g NaNO2
20mL Distilled Water

Temperature was about 72 degrees when I did maybe the fifth 1.5mL addition of solution 2 into solution 1. Being done on a round bottom flash inside of my stirring heating mantle.

edit: was also blowing air into reaction flask to help clear evolved NO2. Maybe that contributed to the micro detonations

[Edited on 12-2-2022 by FanofYellow]

I only just read this first post properly. You should not get detonations with this reaction, nor should it be so touchy within 5C of the recommended temperature. You should have added the ATZ solution to the nitrite, not the other way around, that is your problem.

magneet - 16-10-2022 at 11:34

Quote:

Question about NaNT purification

I refer to "Facile method for preparation of NaNT" (US9,598,380). It works well and is indeed very easy. But I am intrigued by the 1:2 molar ratio of 5-AT to NaNO2: this means that if one mole of Na gives NaNT, another mole of Na goes into the solution and pollutes it. But in what form? NaNO3, or an excess of NaNO2, or what else? We should know this before trying to find a method to purify NaNT. Does anyone know how to write the reaction between 5-AT, NaNO2 and HNO3?

[Edited on 7-5-21 by pdb]

According to this patent:
https://patents.google.com/patent/US9718791B2/en
Here the slight excess of nitrite is added to control PH somewhat during the reaction in the "continuous flow system" (not to be confused with the batch method).

From that same patent:

Quote:

In the embodiments where the nitrite reactant is added in excess for pH control, the excess nitrite is still present in the reactant mixture 26 after the substitution reaction has reached completion. To remove the excess nitrites, additional acid may be added to the reactant mixture 26 at any one or more of various suitable locations, which include but are not limited to a late stage of the reaction zone 28 at a point where the reaction is nearing or at completion; at the point where the reactant mixture 26 exits the processing zone 18; and/or after the reactant mixture 26 is being held the receiving vessel. The excess nitrite and acid forms N2O3, which then bubbles out of the reactant mixture 26, thus removing the excess nitrite as a potential impurity in the final product.

Looking at the table of impurities in that patent NaNO2/NaNO3 are the main impurities I guess.

So since this method uses the same reactants

, if using the batch method with nitric acid it should be purified like this right?: 2HNO3 + 2NaNO2 → N2O3 + 2NaNO3 + H2O adding HNO3 until bubbling stops?

Since they use the end product to synth BNCP directly I assume the NaNO3 doesn't play a big role? like for example by the addition of AgNO3 solution?

Can anyone tell if the extraction method with acetone is sufficient to remove the NaNO3 impurity ? I did a batch with CUNT method years ago and didn't find many residu when i did acetone extraction on evaporated NaNT solution left after CuO removal step.

dettoo456 - 30-11-2022 at 10:51

@magneet There shouldn’t be any (if there is it’d be negligible) NaNO3 after Acetone extraction. The NaNTz has good solubility compared to the NaNO3 in Acetone; vice-versa with H2O. If you need a really pure product then routing through with AgNTz can work.

B(a)P - 8-12-2022 at 15:47

Some 5,5'-azotetrazolate salts, via double displacement of sodium 5,5'-azotetrazolate.
The cadmium salt was attempted, the reaction failed as the pH of the cadmium nitrate solution was too high or contained too much dissolved NO₂ and the 5,5'-azotetrazolate decomposed.
The ammonium salt was attempted, the reaction failed to produce a precipitate and when taken to dryness decomposed.

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