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Microtek
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Interesting. I might try that at some point, though I will be away from the lab for some time.
About the synthesis of AZTR, there wasn't much foaming or effervescence when the SDIC, acetic acid and aminotriazole was added in small portions, but
there was a lot of precipitation of cyanuric acid (and AZTR, presumably). This is also the case when the SDIC and acetic acid are allowed to react
before the aminotriazole is added.
The reaction is fairly exothermic, but for the "three-drop" method, the optimal temp was found to be about 20 C, so temp control can be done with a
simple water bath (no ice if you have cold tap water).
Also, I tried the azide substitution on the chloro-derivative of AZTR that I had accidentally produced. The reaction did not give a very high yield
(about 65 mg from a 1 mmol basis, so about 20%), but the product is about as efficient an initiator as the copper bromate complex discussed above,
only much more vehemic. It has a sensitivity to match, but I will have to make a little dextrinated lead azide just to see how that performs in my
apparatus.
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Axt
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I've been defeated. I tried following the NaOCl route as closely as possible but apart from a small amount of white powdery precipitate in the initial
stages of the reaction there was nothing more on standing. The SDIC route has also killed me, I'll describe my process here as detailed as possible
SDIC·2H₂O ---------------- 25.7 g ----- 0.100 mol
Acetic acid (glacial) ------- 9.08 g ----- 0.151 mol
4-Amino-1,2,4-triazole ----8.8 g ------- 0.105 mol
Sodium hydroxide ---------12.0 g ------ 0.300 mol
Water (total) ---------------201.3 g ----- ~11.2 mol
25.7 g of sodium dichloroisocyanurate dihydrate was dissolved into 125 mL of water with stirring and brought down to 5C by placing it in a freezer, at
the same time 45.4 g of 20% acetic acid is cooled by the same means. The acetic acid is introduced to the SDIC in one portion at 5C and stirred as it
is allowed to come to room temperature over the following hour in which time a fine suspension of cyanuric acid forms turning the solution milky
white. In the mean time 8.8 g of 4-amino-1,2,4-triazole was dissolved into 40 mL of water.
Into a 400 mL beaker with stir bar sitting in a cold water bath is injected by way of a 3 mL pipette 1 squirt of the 4-ATZ solution followed by 4
squirts of the SDIC/AcOH solution. The additions in that order are continued at a pace to maintain the temperature at 20C. This takes approximately 30
minutes. The solution is seen to turn orange with slight effervescence and foaming which was easily dissipated by turning the stir speed from 250rpm
to 400rpm. After the final addition the solution was allowed to stir for a further 30 minutes then vacuum filtered. The product was stirred into 12 g
of sodium hydroxide in 300 mL of water and vacuum re-applied. Only a small amount of brown-buff coloured residue remained.
This light brown residue was energetic, flaring off on ignition leaving little residue. Presumably that the desired product but the yield is abysmal.
The only thing i can see to change in a re-attempt is to well cool the reaction solution to 5C then filter then cool the hydroxide to 5C too and
re-filter. Frankly I should have thought to do that this time, but do you cold filter Microtek? I just re-read your round abouts solubility figures.
[Edited on 1-7-2025 by Axt]
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Microtek
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Hmm, I don't cool it much before filtering, just to about room temp. I do cool the hydroxide soln since I have a feeling it does slowly react with the
product (though that may not be an issue when the cyanuric acid is there to absorb it). I will say that my yields haven't been up to the claimed 90 %
mark either, and just getting to the ~50 % level took some tinkering.
You could maybe try the method where SDIC and acetic acid is combined and stirred for 6 hours before the aminotriazole is introduced. I would still
modify that procedure by adding the SDIC/HOAc to the aminotriazole rather than the other way round, which they seem to have done in the paper.
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Axt
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I tried the exact same procedure as above with cooling but had the exact same result. Does your crude product look the same? Does it match the
deflagratory properties of the attached vid?
What solvent did you use for the azide substitution? Article mentions DMF, closest I'd have to that is NMP. Curious if just acetone would fill the
role as it does for cyanuric triazide.
I found a fascinating route to the N-nitroimide, by the reaction of 4-ATZ with sodium ethoxide and a nitrate ester (ethyl nitrate, diethyleneglycol
dinitrate and PETN are examples given). Gives a calculated density 1.82 and confirms that its zwitterionic nature can be broken and precipitated as
its metal salts. Melts at 172C with explosion.
[Edited on 1-7-2025 by Axt]
Attachment: 4-Nitramino-124-triazole (4-NRTZ).pdf (260kB)
This file has been downloaded 117 times
Attachment: azotriazole.mp4 (7.6MB)
This file has been downloaded 121 times
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Microtek
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Yes, my crude does look something like that. I recommend a recrystallization from water. It makes beautiful needles that are similar to
nitroguanidine, but smaller.
I haven't tried burning as large amounts as demonstrated in the video, but it does flash when ignited.
Regarding the azidation, I used DMF since I had some (though it is quite old and has a certain yellow tint). The AZTR didn't fully dissolve in the
DMF, but the reaction worked anyway. This might be an indication that it is more important to use a solvent that promotes substitution, rather than
one that dissolves the substrate completely. I do have a lot more of the tetrachloroazobis(triazole) so I might experiment more at some point. I'm
particularly interested in seeing if less than all four of the chlorine atoms can be substituted, thus tuning the properties of the product.
The nitraminotriazole looks easy, and it would be interesting to explore both metal complexes and nitrogen rich salts. The only problem is time...
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Axt
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Hmmm. I recrystalised the azotriazole and yes, small matted felt-like needles that peel off the filter paper (attached), fast deflagration with no
residue. Attempted BLG-1 but used ATRZ, copper nitrate and sodium bromate, 1:1:2 the process matched your experience blue crystals precipitating not
immediately but on standing for an hour, but it is quite timid when ignited. Significantly slower than even the copper aminotriazole perchlorate
although faster than nickel aminoguanidine nitrate. It makes me think the nitrate has precipitated preferentially. I don't have much left to test, but
it would be good to run it again sans bromate and see if the nitrate product matches this product. It is still quite impact sensitive, but produces a
weak snap not an ear splitting crack that you'd expect.
[Edited on 6-7-2025 by Axt]
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Microtek
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How did you ignite it? When flame ignited from above on a piece of Al-foil it pops, but does not penetrate the foil. When heated from below, it
detonates and penetrates the foil. However, even then the detonation is not that impressive; it is not nearly as sharp as typical nitrotetrazolates or
azides. Nevertheless, it is impressively efficient as an initiator.
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Axt
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I kept the filtrate, and it deposited a small amount of extra precipitate. Much more vehemic than the first major crop, and yes about the equivalent
of NAP. Crystals are attached, what i presume to be the nitrate is quite jagged, whereas the bromate is quite cubic.
The first crop I would characterise as vehemic as blackpowder, when ignited with a smouldering splint even quite large quantities wouldn't do more
than puff. Very small quantities of the second crop give that distinctive loud POP. Further evidence is provided by the colour of the flash on
ignition, there is no blue tint like you should get from a Cu + Br reaction on the first but there is in the second.
I possible thought i had is even if the bromate is less soluble it may be less favourable to form its 3D structure, it doesn't get a chance before the
nitrate precipitates. I'll probably try precipitation from the acetate with excess bromate.
Regarding the chloro derivatives, did you use the fine white precipitate from NaOCl reaction? or run it again with the SDIC literature method?
[Edited on 7-7-2025 by Axt]
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Microtek
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I used the inadverdent NaOCl product. It gave quite a large amount of amorphous powder that seemed quite uniform and clean, though I haven't done any
kind of analysis of it beyond the melting point measurement. It could obviously be a mon-, di- or trichloro derivative as I can't find melting points
for those.
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Axt
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You could try dissolving some of the putative tetrachloro compound in Ethyl acetate and acetone, it won't mean much if it does dissolve but if it
doesn't it would be a qualitive test that it isn't the tetrachloride as they use ethyl acetate to extract it from the CA in the article and acetone
evaporation to form single crystals.
All the lower chloro compounds are also soluble in acetone, The only odd one out I see is DCM was used for the tetraazide whereas acetone was used for
the lower azides.
[Edited on 7-7-2025 by Axt]
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Axt
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Combining these two solutions while hot, leaving in fridge overnight seemingly gave the correct compound. Didn't measure yield but the filtrate was
clear. It's a distinct cyan colour rather than the light blue.
Approx molar ratio C₄H₄N₈ : NaBrO₃ : CH₃COOH : Cu₂(OH)₂CO₃ = 3 : 28 : 8 : 1
0.3 g ATRZ
2.5 g NaBrO3
25 mL Water
0.13 g basic copper carbonate
0.32 g 90% acetic acid
25 mL Water
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Microtek
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I see you use a large excess of bromate. Did that improve yields relative to what I got? I used the stoichiometric ratio for all reactants and noted a
slight blue tint to the filtrate, indicating that not all the copper ions were pricipitated.
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Axt
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I can't say anymore than the filtrate was clear.
I measured the filter paper vs a non-used paper and it come out a yield of about 180% :/ no amount of meddling with the reactive species will give
this. I didn't try scaping it all off to get a proper measurement. With such a small quantity (100% would be 0.57 g) the overshoot could easily be
explained by different paper weights and the excess bromate soaking into and drying in the paper (I just used kitchen absorbent paper to filter).
This did take more than the hour to precipitate, it was quite slow in this ratio and concentration.
I just hit the remainder of my azotriazole with a ball-peen hammer, it does respond quite similar to RDX ie. moderate hit creates a weak snap. I would
have liked to make enough to try and fire by itself but it's such a pain in the arse to make.
[Edited on 8-7-2025 by Axt]
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Axt
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The straight 4-amino-1,2-4-triazole complex of copper bromate is more vehemic that the azotriazole. Of course there are highly vehemic compounds that
have poor initiating ability, this may well be one of them being a very fuel heavy hydrate. It's highly insoluble, the fine sky-blue powder will drop
out from dilute solutions of the sulphate as [Cu2(4-ATRI)6](BrO3)4·H2O. Constitution is according to https://doi.org/10.1021/acs.inorgchem.8b01045 https://sci-hub.se/10.1021/acs.inorgchem.8b01045 .
CuSO4.5H2O + 3C2H4N4 + 2NaBrO3 --> Cu(C2H4N4)3(BrO3)2
NaBrO₃ --------- 1.0 g ----- 6.63 mmol
CuSO₄·5H₂O --- 0.8 g ----- 3.20 mmol
50 mL water
C₂H₄N₄ --------- 0.84 g ----- 9.99 mmol
50 mL water
--> theoretical 1.83 g copper 4-amino-1,2-4-triazole bromate.
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Axt
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This was 600mg low density NRTZ pressed just enough to hold together and 20mg BLG-1 not pressed at all, just poured in and matchhead pushed on top.
Definitely an NRTZ detonation, not as potent as the PETN at higher density and loading but that is to be expected.
EDIT: I just fired Copper 4-aminotriazole bromate under similar circumstances but with a primary loading of 35 mg (the weight of the caked lump) and
the results were practically identical so I cannot draw any conclusions. Should have picked a more sensible base charge as all this might be proving
is that NRTZ initiates easy, why I'm a bit dubious about pressing it.
[Edited on 8-7-2025 by Axt]
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Etanol
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Quote: Originally posted by Axt  | Thats essentially the same method I've used to make copper ethylenediamine bromate. Although the complex is formed before the ethanol extraction.
CuSO4.5H2O + 2NaBrO3 + 2C2H8N2 --> Cu(C2H8N2)2(BrO3)2.H2O + Na2SO4
Make a saturated solution, add ethanol, bring to boil, filter the sodium sulphate and cool to precipitate Cu(en)2(BrO3)2. It works with KClO3 too, but
in Cu(en)2(ClO3)2's case its very soluble in ethanol and needs to be evaporated out.
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Please clarify, did you obtain Cu(en)2(ClO3)2 from KClO3 and test its primary properties or did you obtain purple crystals that look like
Cu(en)2(ClO3)2?
Thanks to your advice I got the Cu(en)2(ClO3)2 from NaClO3 and successfully used it several times as primary explosives despite its hygroscopicity
and early dead pressing.
However, when I tried to repeat the reaction with KClO3, I did not get separation of SO4 and ClO3 ions in the solution and precipitate after dilution
with alcohol. Both the precipitate and the solute have no energetic properties, but only burn with nasty smoke.
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Axt
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I'm confident it was relatively pure. It seemed about as energetic as the bromate ie. a half pinch size quantity goes bang and tears the paper up,
although it is more of a muffled bang rather than the crack you'll get from the more vehemic primaries. It was never tested beyond that, it is
interesting that say it is actually a functional initiating explosive? I've a video, it's not overly exciting the frames are below.
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Etanol
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According to Urbansky, nitroguanidine does NOT form salts with metals, but forms complexes with salts of some metals.
Has anyone prepared Nitroguanidine complexes with silver, copper and nickel salts? What denticity does nitroguanidine have as a ligand?
[Ag(NQ)n]NO3
[Ag(NQ)n]ClO4
[Cu(NQ)m](NO3)2
[Cu(NQ)m](ClO4)2
[Ni(NQ)k](NO3)2
[Ni(NQ)k](ClO4)2
How about mixed nitroguanidine complexes with other ligands to get near-null oxygen balance?
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Axt
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I don't have an answer to that question, but I'm not convinced it doesn't form salts. If you dissolve NQ in NaOH with a bit of heating it will drop a
white precipitate from AgNO3 (white, not brown so it's not just the oxide). It's extremely feeble, it sputters a bit on heating but mainly just
decomposes to silver metal and some oily product. I did it to compare it to the silver salt of nitrosoguanidine which is much more energetic, flares
off violently but not explosively.
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Etanol
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| Quote: Originally posted by Axt | | I don't have an answer to that question, but I'm not convinced it doesn't form salts. If you dissolve NQ in NaOH with a bit of heating it will drop a
white precipitate from AgNO3 (white, not brown so it's not just the oxide). It's extremely feeble, it sputters a bit on heating but mainly just
decomposes to silver metal and some oily product. I did it to compare it to the silver salt of nitrosoguanidine which is much more energetic, flares
off violently but not explosively. |
Why add NaOH? Wouldn't it be easier to add AgNO3 solution to NQ solution?
You probably got [Ag(NQ)n]OH, so it doesn't have explosive properties.
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Axt
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| Quote: Originally posted by Etanol |
Why add NaOH? Wouldn't it be easier to add AgNO3 solution to NQ solution?
You probably got [Ag(NQ)n]OH, so it doesn't have explosive properties. |
Because the intention was to form the salt, not a complex. NQ (I assume) would only deprotonate in highly basic solution. I've never attempted a
complex, but it's not going to be a silver hydroxide.
There is an article on aminonitroguanidine complexes, most are highly soluble and hydrated, I'm pretty sure it's already attached in here somewhere.
The silver nitrate complex Ag(ANQ)2NO3 is interesting for its mechanical sensitivity.
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Axt
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I was just looking at my copy of https://www.sciencemadness.org/member_publications/energetic... and it had an extra section on DAF complexes. I'm not sure why it wasn't in the
"published" article, frankly I don't even remember doing it now, but this is it.
[Edited on 22-9-2025 by Axt]
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Microtek
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I wanted to try out the copper 4-amino-1,2-4-triazole bromate complex, so I added 4-ATRI to a solution of CuSO4*5H2O in water. It immediately turned a
beautiful deep sapphire blue, indicating fast complexation. While I was preparing the bromate solution, large amounts of a pale blue precipitate
appeared in the solution, so I conlcuded that the sulfate complex also has a low solubility in water.
I was worried about contamination of the bromate complex by the sulfate, so I tested other copper salts to see if I could find something that would
not precipitate with 4-ATRI.
I found that both the chloride and the nitrate also precipitate, but the acetate does not. I prepared the putative bromate complex both from copper
sulfate and from acetate to see if there is a difference in performance, and the samples are drying at time of writing.
I also isolated the nitrate complex and dried a small sample at 90 C for a couple of hours. No visible change occurred (except for the drying
obviously), and the substance was found to detonate with a sharp report on heating from below Al foil (in sub mg amounts). It didn't penetrate the
foil in this test, but if the foil is folded around the sample, it is pulverised on detonation. It only pops when contacted with flame from above.
I haven't tested the initiation ability of this substance (and considering the disappointing performance of the perchlorate comlex, my expectations
are not very high), but nitrate complexes that DDT in such small amounts are quite rare so that at least is interesting.
[Edited on 25-9-2025 by Microtek]
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underground
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I have found here a synthesis of ATZ from ethyl formate and hydrazine. The structure is a bit different (4-AMINO-4H-1,2,4-TRIAZOLE) compare to the clasic
aminoguanidine route (3-AMINO-1H-1,2,4-TRIAZOLE). In 1st example the -NH2 group is attached to Nitrogen while in the 2nd classic example is attached
to Carbon.
I am not sure what the differences are going to be but the 1st synthesis is simpler than the classic one. 4-AMINO-4H-1,2,4-TRIAZOLE has a mp of
77-78°C while 3-AMINO-1H-1,2,4-TRIAZOLE has a mp of 152–156°C
Ethyl formate and hydrazine sulphate are much easier to make than aminoguanidine. Has anyone ever tried this method ?
[Edited on 25-9-2025 by underground]
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Axt
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| Quote: Originally posted by Microtek |
I also isolated the nitrate complex and dried a small sample at 90 C for a couple of hours. No visible change occurred (except for the drying
obviously), and the substance was found to detonate with a sharp report on heating from below Al foil (in sub mg amounts). It didn't penetrate the
foil in this test, but if the foil is folded around the sample, it is pulverised on detonation. It only pops when contacted with flame from above.
I haven't tested the initiation ability of this substance (and considering the disappointing performance of the perchlorate comlex, my expectations
are not very high), but nitrate complexes that DDT in such small amounts are quite rare so that at least is interesting. |
That's actually fascinating and not something I would have picked. I'll test it to see if my results match. The main issue with copper ATZ bromate was
the extremely fine hard caked lump that I received, not nicely crystalline like BLG-1.
Underground, its 4-aminotriazole that's being talked about here and can more easily be made by heating hydrazine hydrate with formic acid (ie.
hydrazine formate, with excess hydrazine 1:1.5 eq) until it reaches 200C then hold it at that temp for 4 hours. Recrystallise from ethanol (1.5 mL per
1 g 85% formic acid used) by addition of equal volume of ether with stirring and cooling.
[Edited on 25-9-2025 by Axt]
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