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Author: Subject: 5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends
PHILOU Zrealone
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[*] posted on 2-10-2017 at 16:26


Yeah nice process ... thanks Rosco for that gem of a finding.

Very smart to work on unsensitive amino aromatic hard to diazotize and to use heat to make the substitution faster... such deactivated aromatic ring diazoniums resist wel to heating... this is the case of trinitroanilin... the electronegativity of the NO2 into the aromatic ring is comparable to the N into the tetrazole heteroaromatic ring...

Addition could also be made via gravity and capillarity fall through a fabric ribon coming from a reservoir and flowing near the surface or just below the surface onto the wall of the beaker via the ribbon...

So no drops and no big increase of reactant concentration, laminar flow agitation, no shock from falling drop...pretty reproductible and no need of electronic or pump...


[Edited on 3-10-2017 by PHILOU Zrealone]




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Rosco Bodine
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[*] posted on 2-10-2017 at 16:46


This particular synthesis for NaNT is a good example of how an exacting method can be very important in its details and small changes in method used can produce surprisingly large changes in the result. Chemical reactions that are sensitive to exacting process conditions required for process optimization are not unusual. This appears to be one of those fickle reactions where the optimum reaction condition is a fairly narrow window. There are many other examples of optimized chemical processes for manufacture of various materials where the process patented is a better way to skin the cat.
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Rosco Bodine
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[*] posted on 2-10-2017 at 16:59


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]


It would be interesting to see if a nickel - potassium double salt would form. Gmelin has reported a double salt for the styphnate.

http://www.sciencemadness.org/talk/viewthread.php?tid=11105&...

Attachment: pages from Hand_book_of_chemistry 1857.pdf (392kB)

http://www.sciencemadness.org/talk/files.php?pid=162501&aid=...

Ethylenediamine nitrotetrazolate would probably be worth a look too. See US4552598 attached in an earlier post

http://www.sciencemadness.org/talk/viewthread.php?tid=8144&g...

Ethylenediamine nitrotetrazolate may form an interesting binary or double salt with Ethyleneditetrazylazide which was mentioned on page 1 of this thread

http://www.sciencemadness.org/talk/viewthread.php?tid=8144&g...

[Edited on 10/3/2017 by Rosco Bodine]
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nitro-genes
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[*] posted on 3-10-2017 at 16:00


A potassium double salt was also something I tried, though only in combination with Cu(II). Tried by slow addition of a strong copper sulfate solution to a near saturated solution of potassium NATZ in water and by cooling of a hot solution of both. Either way, the product seemed a mix of Cu(NATZ) hydrate (light green) and the potassium salt. The potassium salt washes out easily, so I'm quite sure it is a simple mix. NATZ being a diacid, the formation of these complexes can be difficult and highly depended on pH, though I doubt any more flame sensitive energetic complexes of NATZ have remained undiscovered. Something maybe worth mentioning is that instead of ether, NATZ can also be extracted using the more OTC solvents MEK and ethylacetate (from the diammonium salt after acidification with HCl).

That batch process for the nitrotetrazole synthesis would be really useful for small scale synthesis, give that no dangerous side products are formed such as azidotetrazole or something. Seeing it is absent from the patents, could HCl-NaCl-nitrite be a viable route to chlorotetrazole formation?
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Rosco Bodine
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[*] posted on 3-10-2017 at 18:16


The double styphnate of nickel and potassium also involves a dibasic acid (styphnic acid) so it caught my notice as a possibility likewise for nitraminotetrazole.

There was a patent US5516377 of interest attached to an earlier post
http://www.sciencemadness.org/talk/viewthread.php?tid=8144&g...

It is possible you could get complexation of copper, nickel, or cobalt, probably zinc and silver also, by adding the respective nitrate to an ammoniacal solution of diammonium nitraminotetrazole.
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Rosco Bodine
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[*] posted on 5-10-2017 at 00:36


Here is a related recent patent US9718791

Attachment: US9718791 Facile method for preparation of sodium 5-nitrotetrazolate using a flow system.pdf (686kB)
This file has been downloaded 75 times

A related developmental history patent is US7253288

Attachment: US7253288 Process for preparing substituted tetrazoles from aminotetrazole.pdf (900kB)
This file has been downloaded 72 times



[Edited on 10/5/2017 by Rosco Bodine]
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[*] posted on 11-10-2017 at 16:42


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&aid=... 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.

5C2F259D-5F73-4822-9E08-9590895212EC.jpeg - 506kB2D527D88-E354-4F4D-B684-DE03FB1410EF.jpeg - 983kB




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[*] posted on 25-11-2017 at 11:39


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! :D

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]
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Rosco Bodine
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[*] posted on 25-11-2017 at 13:36


No more sloppy wet CUNT for you guys except maybe on special occasions :D:P;)
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[*] posted on 25-11-2017 at 19:37


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. ;)




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Rosco Bodine
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[*] posted on 26-11-2017 at 04:08


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]


Working from the diammonium 5-nitraminotetrazolate precursor you may be getting ammonia complexation in situ for the reacting Cu or Ni or Ag salts and this may be a partial complexation in absence of sufficient ammonia.

The nickel(II) NATZ salt being very soluble is interesting as a potential opportunity for that solubility to be upset by complexation with hydrazine and to form a Nickel tris-Hydrazine NATZ analogue of NiNHN. Also suggested is the possibility of a double salt with the NiNHN analogue where a mixed solution of nickel nitrate and nickel NTZ is treated gradually with hydrazine to coprecipitate a possible double salt of NiHN and NiNTZ. I think the NTZ compound has more promise than the NATZ compound for such a coprecipitation scheme if the solubility of NiNTZ is good also, but could react with hydrazine to form a low solubility complex.

A nickel hydrazine azide is also reported so it provides another possibility as a candidate in a double or multiple complex salt scheme where a coprecipitation may occur. Such schemes have the potential of enhancing the properties of NiHN.

Ethylene diamine has interest as a complexation agent as well as interest in double salt formation due to reported ability to undergo a half neutralization by one acid reacting with one of its amines and completion of neutralization by a second different acid reacting with the second amine.

Glycine is known to complex metals and might have interest particularly for the Cu salts or potential double salts. Methylamine is another candidate for potential Cu complexation schemes.

It is impossible to really predict what sort of solubility driven interactions may lead to formation of what complexes that may occur for resulting materials that could be complexed and or multiple salts having synergistic properties. This is an area of pure research and experimentation for compounds that may be possible but are undiscovered or unreported.

The half neutralization scheme for ethylene diamine being completely neutralized by a second different acid, may likewise be possible for basic salts of one acid which are half neutralized by formation by first one acid and then converted to neutral complex salts by a second acid.

Regarding the silver salts, excess ammonia may dissolve and allow for purification by reprecipitation on neutralizing the ammoniacal solution of the silver salt.

[Edited on 11/26/2017 by Rosco Bodine]
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[*] posted on 29-11-2017 at 05:31


I also tried the batch 5-NTZ production process from US9598380 yesterday, but on a 0.75g 5-ATZ scale. I made the silver salt, and it iss good, very similar to silver fulminate really, but what really blows me away is just the power of this reaction mix.

Ok, so the pH for me ended up at around 9... I might not have scaled the nitric exactly correctly (it was a weird concentration in the patent). But here's a video showing....

Firstly: The raw reaction mix. It's very hard to dry, but when I stick it in the freezer, the whole lot turns into a sticky mass of crystals. The water boils off, and everything detonates violently.

Next, what I did was try to recrystallise from acetone. When a lot didn't dissolve, it turned more into an extraction. The yellow solid left behind (i'd say like 90% of the mass of the reaction mix?) after the acetone extraction is not energetic. When put over a flame, it simply evaporates away, calmly, not even burning like 5-ATZ does. The acetone used to extract the mix though.....

The next two clips are me heating (or accidentally setting fire to) the acetone solutions. The acetone boils/burns off before the solid explodes, but when it does, it's phenomenal. Look how it shreds that aluminium foil......!

So... is this the sodium salt of nitrotetrazole? I mean it has to be, because the pH of the mix is basic, but gee, it goes hard. The sodium salt seems to outperform the silver salt almost... whats up with that?

VIDEO: https://youtu.be/j3ulrXukg6o
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[*] posted on 3-12-2017 at 11:35


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

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 56 times

[Edited on 3-12-2017 by nitro-genes]
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[*] posted on 3-12-2017 at 22:04


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.

A26D8224-538C-41F7-BA26-454E06F5996E.jpeg - 2.8MB

[Edited on 4-12-2017 by NeonPulse]

B6933215-77E7-4552-B766-9F67F1DE293B.jpeg - 1.4MB




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