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

To those who really think verdigris is Cu(NTAz)2, Cu(NTAz)2.HNTAz or HO-Cu-NTAz;
--> no its just the colour of women jealous from envy to NeonPulse's compound

or more seriously a similarity of colour between the beautiful pictures of NeonPulse's compound
and
Cu(OH)2.CuCO3 (from the old french vert-de-Grèce (green from Greece) or vert-de-gris (green of grey))

[Edited on 25-4-2016 by PHILOU Zrealone]

roof

Of course, for everybody. On roofs is NOT! Cu (NTAz) 2 as energetic materials. On copper roofs is nothing explosive material. It is only joy and joke during comunication in this thread. And of course jealousy that someone managed to synthesize it. From available compounds. ( However, I keep thinking, that the energetic materials NeonPulse always scratches from himself the roof ).......LL

Quote: Originally posted by a nitrogen rich explosive

bis(5-nitrotetrazolylazide)? I'm not very experienced in tetrazole chemistry, but I think that is what it would be. Let me elucidate... A 5-aminotetrazole ring, with the NH2 group at 5 substituted with an NO2 group. By the action of HNO2, the NH group at 4 ridded of hydrogen and with an extra nitrogen double-bonded outwards (like diazonium compounds.) Another 5-nitrotetrazole group with only a nitrogen atom at the fourth position bonded to the diazonium group of the other complex. 252g/mol. Wow. [Edited on 3-5-2016 by a nitrogen rich explosive]

Quote: Originally posted by a nitrogen rich explosive

So diazobis(5-aminotetrazole) would exist?

Make a drawing of it first, post it and we discuss!

About your screenshot (retaken here as a jpeg picture for convenience purpose):


You will notice that you have a lot of mistakes...usually N is trivalent in organic chemistry; in your drawing
-if it is tetravalent, then it must display a charge like ammonium for example (NH4(+)) (cf. A and B)
-if it is pentavalent then it should display a double charge (cf. C)

--> You made a molecule charged with 4(+) charges and no balancing so repulsion forces will be against its existance.

The position C is even more concerning because you are able to put a N atom in sp conformation (180° linear):
1°) with an extra lateral sp3 bond
2°) into a ring with angle strain 109°

Try to buy a ball and sticks molecular model and do a first test with it.

Quote: Originally posted by a nitrogen rich explosive

Also, by the way, I just put up my findings on my hands-on crash course on tetrazoles up on Prepublications, with syntheses of the 5 most explosive tetrazoles I have done yet.

Quote: Originally posted by a nitrogen rich explosive

I don't have the same language quirks,

Hmmm..........

I watched a rabbit running through the woods

I'm a wolf

https://www.youtube.com/watch?v=br4ES2JDu-k

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Quote: Originally posted by DubaiAmateurRocketry

I thought I was leading the bullshit in this forum until reading nitrogen rich explosive's posts lol

Quote: Originally posted by ShotBored

Hey Fellas, I'm relatively new to the pyrotechnics field, but my education background is in chemistry, namely inorganics, coordination chem, catalysis etc. I'm going to be fairly active in my forays into tetrazole chemistry, mostly in pursuit of blue, smokeless, perchlorate-free comps (the pyro quest for holy grail, I know). I was curious if any of you had delved either: 1) 3,6-dihydrazino-1,2,4,5-tetrazine (DHT); or 2)Triazoloaminotriazinyl-1,2,3,5-tetrazine (TATT) salts TATT was mentioned by Klapotke/Steinhauser as being investigated by Koppes et al, but they never reported on flame colors of any of the salts, which included Al, Co, Ni, Cu, and Ba. My particular interest in the Cupric complex. However, the current synthesis pathway includes the use of cyanogen bromide which makes me tremble a little at the the thought of using. DHT has many obvious applications in pyro and Klapotke called it "one of the most promising materials for smokeless colored pyrotechnics". Naturally, I have a few reservations in working with hydrazine, plus DHT has hydrazine functional groups that I'm sure make it toxic as all hell. I'd be interested in any light you guys could shed if you've done any research in this area yourselves. P.S. Enjoy this awesome new article on the effects of adding NQ to your 5-AT propellant mixes! Cheers pubs.rsc.org/en/content/articlepdf/2017/ra/c7ra01607g

Quote: Originally posted by ShotBored

Sorry, I said "flame colors" but meant "flame characteristics". I have an understanding of the color emitters down, with the exceptions of some of the newer, rare earth metal emitters such as yttrium, etc. My concern is more so aimed at the established synthesis pathways: it seems self-defeating for me to be aimed at "green" chemistry, yet use such nasty synthesis components such as hydrazine or cyanogen bromide. I was curious if any of you had synthesized DHT or TATT or if you all had used different pathways. I can post the current general synthesis pathways for each if that would help. I would agree, though, that forays into those other color emitters could prove fruitful. I know the Klapotke paper talked about some great red-emission from Sr-DHT and Sr-TATT complexes, but I didnt see anything about B, Li, or Ca. I'll have to let you guys know how the research plays out once my lab is done being built =)

Not sure how easily other some other triazoles would form when acetic acid/acetate is present during the heating step. From what I've read, acylhydrazides need higher temperatures and anhydrous conditions to form (STUDIES OK THE FORMATION OF 4-AMINOTRIAZOLE DERIVATIVES FROM ACYL HYDRAZIDES, ROBERT M. HERBST AND JAMES A. GARRISON).

I've seen the cyanamide fertilizer bags for sale, just more fun going all the way from urea though. Cyanamide was homemade by pyrolysis of calcium cyanurate at 800-1000 deg C. Used a welded 150mm diameter stainless steel container with 5 cm of 20 mm stainless tubing protruding from one end by which it could be filled and emptied. A conically shaped stainless steel weight was placed on top of the 20 mm tubing so that when fired, gasses could escape by lifting the weight up, closing it again when no more gas is produced. Worked nicely and gave abundant amounts of silvercyanamide on testing (can this be used for quantification of purity?). Yield was 90% of theory from calcium cyanurate and got 360 grams calcium cyanamide in total from 2 firings, which is more than I need anyway. The original goal was to make dicyandiamide, but decided a small amount of 5-ATZ would also be nice.

Nice channel on YT, some clean looking EM chemistry video's there! The sythesis of CuNTZ was nice to see, some balls to produce it at this scale though, micro dets. and all. A vid on DBX-1 would certainly be cool as well!

Not sure what temperature range is acceptable for the pyrolysis of calcium cyanurate to calcium cyanamide indeed. Since the latter is produced commercially by reaction of nitrogen with calcium carbide at 1100 deg C or so, it would seem that at least the calcium cyanamide itself is reasonably stable at these higher temperatures, although this may be different for the pyrolysis reaction. For the pyrolysis I just used an airblown coal furnace from a hairdryer and a 10 liter old SS waste bin with lid that I dug into the ground for insulation. I did give the pyrolysis vessel some "legs" to keep the calcium cyanurate away from the really hot zone at the bottom of the can (where the air is blown in) and eyeballed for a red to dark-orange colour through a peakhole in the lid. Added a small amount of the calcium cyanamide to an excess of 10% HCl, which dissolved it completely and produced only very little gasses or smell, further did a qualitative test with silver nitrate as Engager desribed. The silver cyanamide does have a very low solubility, even from very dilute solutions of cyanamide and ammoniacal silver nitrate (~less than 0.1% for both) a strong yellow colour is obtained, even though it would probably be rather difficult to use the silver method as a really accurate purity assessment.

Also not sure what the exact purity of the AQB is from the acetate/acetic method. I did test the AQB melting/dec. point and the 5-ATZ of both methods, having roughly (together on hotplate test) same melting point, going from tranlucent to matt white at around 100 deg C, same decomposition temp (right after melting with many small bubbles forming) and similar crystal morphology (long glassy plates). Comparing the more energetic copper(II) salts of both batches would be most conclusive, but right now I have no direct plans for the 5-ATZ anyway, so some time perhaps. I did diazotize about 50 mg of the 5-ATZ (of the simultaneous addition batch) as a 0.7% solution and added some 1:1 hydrazine sulfate/NaOH solution to produce some ditetrazoylhexazadiene, truly amazing stuff but also indicative of how dangerous some of these tetrazoles can be.

Ok I know this is really tangential post, but copper nitrotetrazolate has possibly the best acronym for an explosive Ive seen so far, maybe barium nitrotetrazolate could compete with it though (BaNTZ i.e. of the dank persuasion)

Made an inquiry at Gaylord chemical, said I was looking for CuNTZ, but just got an angry reply back.

Do you guys know how stable 5-ATZ is on prolonged storage? An MSDS I found mentioned that it should be kept in an airtight container? Also said it has a distinct smell ( I smell nothing), does it react with oxygen/moisture/sublimate or something? Dangerous?

[Edited on 3-8-2017 by nitro-genes]

Quote: Originally posted by nitro-genes

Made an inquiry at Gaylord chemical, said I was looking for CuNTZ, but just got an angry reply back.

Quote: Originally posted by Dornier 335A

NeonPulse, when you write CuNTZ, do you mean Cu(NTZ)2 or Cu(NTZ)2*NTZ? The second being the intermediate in NaNTZ synthesis. I synthesised DBX-1 with really good yield a few months back but didn't have time to record a video. It's a really nice primary in every way though so I really should do some tests with it. I also have a small sample of pure 5-nitrotetrazole drying over concentrated sulfuric acid. It was made by extracting an acidified solution of NaNTZ with diethyl ether.

It was the second one which I did need for the Na NTZ. When I first saw the acronym for the copper II NTZ I got a laugh out of that too. I did a little experimenting with recrystallising some and found the colour changed dramatically to a sky blue with a majority of the green being insoluble and removed by filtration. The junk left in the filter was Kahki green and when I attempted to light it up it was not very explosive and kind of crackled with green flames. The resulting filtrate was allowed to cool slowly in an attempt to grow crystals but they were tiny and there seemed to be an avalanche precipitation. The product was also much more flame sensitive than before. I wondered why Engager never mentioned this in his publication.

A sample of pure 5-NTZ would be great to have. I wanted to attempt it in the future- once I get enough of the sodium salt to experiment with. These compounds take quite some work to make as you know. It's extreme sensitivity and being very hygroscopic is a bother though. I don't want a repeat of the incident I had when trying to make the ditetrazoylhexazadiene. That shook me up good. I still haven't attempted to make it again since that. One day I am going to make it though. I'm fairly sure what went wrong for me there.

As for the 5-Aminotetrazole having a smell, I have not noticed any odour at all in my samples made from both methods. In solution they have a distinct smell though. As far as I know It is quite stable in storage under ambient conditions and slightly elevated temperatures too. I keep mine in an amber jar airtight in a normal temp range 15-30c.



[Edited on 7-8-2017 by NeonPulse]

You hydrolyse the copper acid salt during your recrystallisation! You end up with the pale blue Cu(NTZ)2 and 5-NTZ solution.



The picture is from Primary Explosives by Robert Matyas. There's more information about the salt on pages 201-203 but it's not as good as lead azide and not a very interesting primary.

Quote: Originally posted by Dornier 335A

You hydrolyse the copper acid salt during your recrystallisation! You end up with the pale blue Cu(NTZ)2 and 5-NTZ solution. The picture is from Primary Explosives by Robert Matyas. There's more information about the salt on pages 201-203 but it's not as good as lead azide and not a very interesting primary.

Quote: Originally posted by Dornier 335A

No Philou, "copper acid salt" is just an old name for the intermediate in nitrotetrazole synthesis, Cu(NTZ)2*HNTZ *(H2O)4. It's a pretty accepted term though. So you can see how this could decompose into Cu(NTZ)2 and 5-NTZ. The dibasic salt (Cu(NTZ)2*2Cu(OH)2) exists too but it lacks the properties of a primary.

DBX-1

after thinking about my first attempt and failure of synthesizing DBX-1 last year i realized my problem was mostly due to the poor quality of copper I chloride i had used. it was old and there was far too much copper II present for it to work n this intended use.
So I made a fresh batch CuCl by reducing a fresh batch of CuCl2 with Na2SO3 and keeping it un exposed to oxygen as possible before use. satisfied with the result i set about making DBX-1 by using the preparation outlined in example 2 of the US patent No:2013/204005A1

0.9g CuCl was put into a 100ml RBf with a small oval stir bar added and 20ml distilled water was also added to suspend the CuCl. next a solution of 2.08g of NaNTZ in 30ml Dist H2O was added to the flask all at once. the resulting solution was at first an olive colour which quickly changed to light brown and then to orange upon heating being applied.
the flask was fitted with a reflux condenser with cold water running and heating was applied to the flask to bring the temp up to a steady reflux.
i had a worry about the contents being very thick and not stirring properly so i added more H2O to help it stir.
this was kept up for just short of an hour and heating was removed.
the result was a rust coloured precipitate in a fairly clear solution which was filtered on a buchner funnel, rinsed with portions of water and finally with Anhydrous IPA and left to dry overnight. the weight of my yield was exactly the same as the patent example- 1.12g.

upon testing my product i was surprised to find that when lit it flashed off very fast similar to mercury fulminate. i was expecting a sharp snap and torn foil like with it's silver counterpart. when heated from below though the story was different.
it's brisance was clear. it is a high performer.
with some impact testing it did not seem overly sensitive when hit between steel surfaces, taking a light blow to fire it - this changed to a minimal tap when hit on concrete though. same with a friction test- it barely crackled on steel when rubbed hard with a ball hammer but on concrete it went off with just dragging the weight of the hammer itself over the sample.
for some final testing though i plan to test a tiny amount of DBX-1 on top of well pressed 200mg samples of TNT,PETN,ETN and MHN.
quite happy with this stuff so far though.

DBX 1 is very sofistics energetic material. I am curious on compare testing with ETN...The Hat down....thanks for description. Dr.....:-)
Password of the day: Is there Copper? So it hit ......Dr.

Quote: Originally posted by greenlight

Nice work NP! I don't have any experience with tetrazoles but I know DBX 1 is going being looked at as the main replacement for lead azide being with it being non toxic and not heavy metal salt. It seems that green explosives is the way for the future commercial research. I look forward to seeing how it performs with initiation of secondaries.

Paradoxally when analysing soil for heavy metals (at least here into Europe)...
==> Copper (Cu) is into the list of the dozen of requested metal quantification...
==> Green explosive maybe refer to the color and not to the enviro-friendlyness

Better switch to Na, K, Ca, Fe, Mg, Al, ... NH4, N2H5, guanidinium, ...

[Edited on 27-8-2017 by PHILOU Zrealone]

Very nice! How sensitive is DBX-1 to flame or a glowing splint? Do the properties change upon storage? IIRC DBX-1 was sensitive to moisture upon storage, does DBX-1 itself also slowly oxidize to Cu(II) in contact with air?

After some reading... () solutions of Cu(II) and salts of NATZ form Cu(NATZ)2, which is a hydrate and unsuitable as a primary. It seems water of hydration is the main problem with salts of NATZ, while its difficultly obtained anhydrous salts (such as the calcium salt ) seem more useful and even been suggested as a lead azide replacement. Tried to make a putative Ni(II)(hydrazine)2(NATZ) salt to see if this would increase flame sensitivity. Its a lilac in colour (like NHN) but similarly insensitive to flame as the copper salt, and even more reluctant to make DDT upon heating. Wonder if potential double salts/complexes of 5-NATZ and styphnates or trinitrophloroglucinates would exist and be more interesting. Since most of these form hydrates itself, probably not, but who knows?

[Edited on 28-8-2017 by nitro-genes]

Quote: Originally posted by nitro-genes

Not sure how easily other some other triazoles would form when acetic acid/acetate is present during the heating step. From what I've read, acylhydrazides need higher temperatures and anhydrous conditions to form (STUDIES OK THE FORMATION OF 4-AMINOTRIAZOLE DERIVATIVES FROM ACYL HYDRAZIDES, ROBERT M. HERBST AND JAMES A. GARRISON). I've seen the cyanamide fertilizer bags for sale, just more fun going all the way from urea though. Cyanamide was homemade by pyrolysis of calcium cyanurate at 800-1000 deg C. Used a welded 150mm diameter stainless steel container with 5 cm of 20 mm stainless tubing protruding from one end by which it could be filled and emptied. A conically shaped stainless steel weight was placed on top of the 20 mm tubing so that when fired, gasses could escape by lifting the weight up, closing it again when no more gas is produced. Worked nicely and gave abundant amounts of silvercyanamide on testing (can this be used for quantification of purity?). Yield was 90% of theory from calcium cyanurate and got 360 grams calcium cyanamide in total from 2 firings, which is more than I need anyway. The original goal was to make dicyandiamide, but decided a small amount of 5-ATZ would also be nice.[/ I Managed to find that reference where Engager tested his product for purity using this method: from his post in the prepublications:'ve managed to preform quantitative analysis of product produced as described above. 1g of product was added to 150 ml of cold water and stirred for several minute, 2-3 ml of 70% HNO3 is added and mixture is stirred until all solid is dissolved and transparent solution is obtained. After this solution is complemented with 4 ml of 25% ammonia, and solution of 4.5g of silver nitrate in 50 ml of water with stirring. On addition of ~40 ml more of 25% ammonia silver cyanamide is precipitated as pale yellow mircrocrystalline solid. Mixture is stirred for 10 minutes, precipitate is filtered off, washed with water and alcohol and dried. Silver cyanamide is weighted and checked against theoretical of 3,197g for 100% calcium cyanamide. Analysis for my sample shown that is gives 2.85g of silver precipitate, indicating that sample contained 89.15% of pure calcium cyanamide, corresponding to nitrogen content of 31.2% (vs 34% calculated for formula CaNCN) Also in reference to the DBX-1 I had made recently,?i tested its sensitivity to an ember on a splint and it is very easy to set it off this way. Flame is the same. Holding the flame just away from the sample also sets it off but with a slight delay. It has the characteristic whump of mercury fulminate or DDNP leaving a small patch of copper metal as a residual coating on the surface it was on before igniting. I'm just waiting for my new .001 scales to accurately measure amounts I'm working with. It is pretty snappy and I could easily see a small amount doing nasty damage if an unwanted detonation did occur so using small amounts Is a wise choice. I should have results of further tests in the next week or so, once I get rid of this rootkit on my PC which is consuming what little time I have spare lately. Darn computers. I'd have thrown it out the window if it didn't cost so much.

Sounds like DBX-1 is even more flame sensitive as lead azide and pretty friction sensitive as well, crystal shape probably being an important factor.

Considering the reaction is a pyrolysis at ~1000 deg C, a product of 90% purity in 90% yield is still amazing. Dilute solutions of calcium cyanamide in cold water and precipitating the silvercyanamide as a more course crystalline solid would help. Due to it's very low solubility it seems to form a really fine precipitate, easily partially escaping the filter. Been wondering if you could precipitate silvercyanamide as an extremely fine precipitate in very dilute solutions, maybe light extinction of the suspension could also be measured somehow.

Quote: Originally posted by nitro-genes

Sounds like DBX-1 is even more flame sensitive as lead azide and pretty friction sensitive as well, crystal shape probably being an important factor. Considering the reaction is a pyrolysis at ~1000 deg C, a product of 90% purity in 90% yield is still amazing. Dilute solutions of calcium cyanamide in cold water and precipitating the silvercyanamide as a more course crystalline solid would help. Due to it's very low solubility it seems to form a really fine precipitate, easily partially escaping the filter. Been wondering if you could precipitate silvercyanamide as an extremely fine precipitate in very dilute solutions, maybe light extinction of the suspension could also be measured somehow.

Quote: Originally posted by nitro-genes

Could only find some info on the diammonium, sodium, potassium and silver salt of 5-nitraminotetrazole, so I decided to make about 100 mg's of a copper(II) salt of NATZ by reaction of diammonium 5-nitraminotetrazolate and copper(II) sulfate, which precipitates a light green amorphous precipitate. Not sure if this would be Cu(II)(NATZ) or Cu(II)(NATZ)2, probably the former. It only crackles when touched by flame, but when heated over a flame it first turns brownish/black then detonates with great brisance at around 300 deg C. Also tried to make the Cu(I) salt by reduction with ascorbic, but just got some mustard yellow coloured gel-like crud that wouldn't filter, perhaps the Cu(I) salt is too soluble or too fine a precipitate. It seems Cu(II)(NATZ) doesn't need too much to make DDT, has a Cu(II)(NATZ)(NTZ) complex ever been made? The nickel(II) salt of 5-nitraminotetrazole also seems very soluble, still would like to try if NATZ may form some more water insoluble and more flame sensitive complexes with nickel(II) nitrate and hydrazine. Are any of these already known? [Edited on 9-8-2017 by nitro-genes]

Was wondering if anyone has more information on Guanylazide Picrate? (VOD, lead expansion,sand test,ect) All I have found is this : http://www.sciencemadness.org/talk/files.php?pid=131275&... and a small paragraph in Federoff ‘s encyclopaedia I did expect to find a bit more info since there was a patent which would suggest that some tests were done.
Anyway I used this patent as a rough guide to synthesise some myself. Firstly I diazotised Aminoguanidine Bicarbonate as per a synthesis for 5-ATZ but instead of using base and heat to complete it I instead neutralised it with a hot sodium picrate solution. This formed an immediate precipitation of a bright yellow micro crystalline substance which I believe is the product. This was filtered off on a Büchner funnel, rinsed several times with ice cold water and set aside to dry. In a burn test it caught fire very easily and burnt much faster than picric acid alone with the trademark yellow smoke and carbon left behind. It is very insensitive and much like picric acid it needs to be wrapped in foil and belted very hard to get any visible result.

It seems guanylazide picrate is only mentioned few times in literature indeed, couldn't find anything either. Nice video on DBX-1 btw!

Tried the batch 5-NTZ production process from US9598380 today, the reaction went exactly as mentioned in the patent, no hard to filter, sticky, explosive CUNTZ, copper oxides or m(i/a)cro explosions during the additions, hooray!

I did downscale the reaction to 0.5 grams of 5-AT monohydrate instead of 1 gram, keeping the reaction volumes similar (Don't have <20 ml beakers) so not sure if this affected the end product somewhat. Still wonder how this reaction can supposedly produce such good yields, as I would have guessed the pH during the early additions would be too high to form the diazonium precursor in the first place and OH- or even water would be competing with nitrite.

Reaction:

1.18 grams of sodium nitrite in 10 ml distilled water were added to a 20 ml beaker, temperature was kept at 65 deg C. using a waterbath. To another 20 ml beaker, 0.73 grams of 98% sulfuric was added to 5 ml of water. Then 0.5 grams of 5-AT*H2O was dissolved in the dilute sulfuric and put next to the other beaker in the waterbath. The 5-AT/SA solution was added in the smallest increments possible, using a pipette, over the course of 45 minutes. The effervescence was only slight and proceeded steadily. There was a very noticable decline in effervescence with the addition of the last few drops of the 5-AT solution. After the effervescence had mostly stopped (another 5-10 minutes of stirring), the beaker was removed from the waterbath and allowed to cool down. As indicated in the patent, the reaction mixture had attained a very slight yellow colour and total volume (due to evaporation) was around 10 ml, end pH was between 2 and 2.5.

Sodium bicarbonate was added to bring the pH up to around 7, then a slight excess of calcium nitrate added and the calcium sulfate filtered off. The solution attained a noticeably darker yellow colour upon neutralization. A few mg's of silver nitrate in disitilled water was used to precipitate some silver 5-NTZ, which precipitated as a slightly beige coloured product. I was unable to remove the beige colour by washing with water as the silver salt of 5-NTZ should be completely white. It does behave very flame sensitive, detonates in microscopic amounts, blackens at around 240 deg C and explodes only when dropped on a hotplate >300 deg C, so probably reasonably pure silver salt of 5-NTZ. Yields were not determined due to small scale.

[Edited on 25-11-2017 by nitro-genes]

No more sloppy wet CUNT for you guys except maybe on special occasions

NeonPulse, I like your electric furnace seen in the sulfuric acid distillation video. Some interesting looking videos.

Hello Rosco, good to see you on here. Glad to see you still find chemistry sexy.

Quote: Originally posted by nitro-genes

Could only find some info on the diammonium, sodium, potassium and silver salt of 5-nitraminotetrazole, so I decided to make about 100 mg's of a copper(II) salt of NATZ by reaction of diammonium 5-nitraminotetrazolate and copper(II) sulfate, which precipitates a light green amorphous precipitate. Not sure if this would be Cu(II)(NATZ) or Cu(II)(NATZ)2, probably the former. It only crackles when touched by flame, but when heated over a flame it first turns brownish/black then detonates with great brisance at around 300 deg C. Also tried to make the Cu(I) salt by reduction with ascorbic, but just got some mustard yellow coloured gel-like crud that wouldn't filter, perhaps the Cu(I) salt is too soluble or too fine a precipitate. It seems Cu(II)(NATZ) doesn't need too much to make DDT, has a Cu(II)(NATZ)(NTZ) complex ever been made? The nickel(II) salt of 5-nitraminotetrazole also seems very soluble, still would like to try if NATZ may form some more water insoluble and more flame sensitive complexes with nickel(II) nitrate and hydrazine. Are any of these already known? [Edited on 9-8-2017 by nitro-genes]

Ooops, just noticed I got the ratios of sulfuric and nitrite wrong for the batch 5-NTZ proces... Shouldn't be doing this stuff late at night (or at all)

The potassium salt might be interesting as well, it doesn't form hydrates like the sodium salt. Read somewhere that the main reason it is unsuitable as a primary is it's "low" decomposition temperature of 195 deg C, although couldn find any sensitivity data.

Some interesting paper about DBX-1

Attachment: Development of a Lean Process to the Lead-Free Primary Explosive DBX-1 (929kB)
This file has been downloaded 931 times

[Edited on 3-12-2017 by nitro-genes]

Had a go at making mercuric Nitrotetrazolate according to the synthesis depicted in this document: http://www.dtic.mil/dtic/tr/fulltext/u2/a036086.pdf
I did it at 1/10th the scale - making large amounts of such a powerful primary makes me nervous. Followed the synthesis to a T including preparing the Mercury nitrate solution from HgO. The Solutions of HgNO3 and Sodium Nitrotetrazolate were mixed at 75c as directed and were left at a slow stir speed until 30c. Shortly after mixing not much seemed to be happening but at about 55-50c there was a gradual precipitation of the product in a microcrystalline snow in The beaker. Once it got to about 30c which was also the temp in my lab I left the solution for a few mins before gravity filtering and rinsing several times with ice water and finally with a small portion of Dichloromethane.

Now I must say that I was very impressed by this stuff. It flashes off with a dull thump like its fulminate cousin but a bit faster, with a white orange flash. when confined in foil I had perhaps a few Mg in a bit of foil and held it over my alcohol burner and the report was loud. It actually shocked me. The foil was atomised shiny glitter and my ears were ringing. I don’t recall the DBX-1 being quite as powerful. It’s also not super impact sensitive or friction sensitive but enough to be useful as a primer. Obviously a drawback is that it contains mercury. The little squares of foil that I lit it on showed the signs of amalgam formation in the way of the tiny fibers that formed when mercury is in contact with Aluminium.



[Edited on 4-12-2017 by NeonPulse]

No experience with recrystallization from acetone, though recrystallizing NANTZ from hot methylethylketone (MEK) definitely resulted in a hydrate (melted and boiled first when heated, only then exploded). Even though this was tested at small scale first, I still added a few drops of water to the MEK for the main batch as a psychological reassurance. Wondered if MEK would not be an even better solvent for NaNTZ recrystallization, since it is more hydrophobic than acetone and has a higher boiling point, so maybe less likely to crystallize an anhydrate and better recovery efficiency?

Thinking some more about the patented batch process...what would be the most prominent impurities? I've noticed that a dark yellow impurity is formed along with the colourless NANTZ. The yellow impurity darkens in colour when basified further, so my guess would be that this would be mostly 5,5'-diazoaminotetrazole or 5,5' azotetrazole? Maybe the reaction is so fast that upon adding the 5-ATZ/Acid solution to the nitrite solution, the mixing efficiency becomes limiting in how much self-coupling takes place? The same thing applies for the reaction of hydrazine and nitrous acid to from hydrazoic. Apart from really strong mixing, would further dilution of the 5-ATZ/Acid solution not be more beneficial?

Also noticed that insufficiently purified NANTZ, immediately produces a fine green haze when cupric salts are added. IIRC, the solubility of the cupric salt of 5-NTZ is much higher than those of unreacted 5-ATZ, 5,5'-diazoaminotetrazole or 5,5' azotetrazole. Wonder if a first NANTZ enrichment step using cupric salts woudl be feasible. Don't know the exact solubility of all the cupric salts though, or if they even are all known...


[Edited on 3-12-2018 by nitro-genes]

It seems very difficult to get good DBX-1 crystals. The "gel" is a weird thing indeed... I remember trying some alternative synthesis schemes using the cupric/ascorbic method, and in one instance (using much lower temperatures during the synthesis), the entire solution became like a solid gelatin pudding. What I found really strange is that boiling this gelatin mass in some instances still refused to produce DBX-1. The gel doesn't form from the CuCl synthesis indeed, though even then the product seems a mix of well formed crystals and almost amorphous stuff. Could be the simultaneous presence of cupric and cuprous results in this gel (The cupric may allow more ligand binding, forming almost a polymer) and/or could relate to the ascorbic, though both would seem easy enough to exclude. Alternatively, the DBX-1 forms as very small crystals, and the formation of DBX-1 crystals from this colloid depends on a poorly understood self-assembly process maybe?

Interesting idea, using these gels to produce double salts... Strange phenomena these gels, noticed there was a paper posted on SMDB about the lead styphnate jelly, from what I read it seems to be controlled by pH mostly, so maybe is determined by how coordinated water interacts with the Pb2+ and styphnate to produce some hydroxide containing complex, though cannot picture how this would look like.

Can DBX-1 be produced at slighty lower pH? What happens if ascorbic acid is used instead of sodium ascorbate?

[Edited on 13-12-2018 by nitro-genes]

Seriously? Nice!!! Any microscopy pictures? Does the DBX-1 produced dissolve in HCl as a clear solution, no copper particle residual? Is it actually soluble in HCl?

5-NTZ is a very strong acid, coincidentally about as strong as picric () at a pKa of 0.8, so after performing the picric reductions using cupric/ascorbic I was contemplating before if a pH of about 2 would interfere with the formation/complexation of 5-NTZ to the cuprous salt indeed. Performing the entire reaction in dilute acetic might be even more beneficial. Similarly, the picramic and styphnamic complex of Cu(I) is only displaced at very low pH and high concentrations of competing ligands such as Cl- or NO3- (but not sulfuric), so was wondering if the same would apply for DBX-1 indeed. The reduction of picric/styphnic might be interesting for the production of DBX-1 as well, as it is sort of an optimized procedure for the steady production of Cu(I).

One of the important differences would be the question how hard that Cu(I) is "gripping" the 5-NTZ? Is there some measure or definition for that? Reading IIRC that DBX-1 is easily hydrolysed by water, my first guess was that it was a rather weak interaction. Silver azide is another surprising example, forming almost a completely ligand coordinated polymer that precipitates even from very acidic solutions, despite the azide ion being a rather weak base.

[Edited on 14-12-2018 by nitro-genes]