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Hey Buddy
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Quote: Originally posted by Microtek  |
They are said to be fairly strong acids, so you might want to make some ammonium-, hydrazinium- or hydroxylammonium salts... |
It seems like there may be two products depending on the molarity of formic acid. I assume a formate results under 2x formic acid conditions. If the
cyclization product is acidic, does a formate even seem possible or realistic? There are definitely two different materials formed from the respective
formic ratios.
The difference between 1x formic and 2x is the following:
1x: Material remains off white. Material separates from water/acid to bottom of beaker.
2x: Material becomes white. Material expands in volume becoming almost fibrous in appearance.
If a formate is produced, then perhaps a nitrate/perchlorate could be coordinated by a metal cation?
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Hey Buddy
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I think I have some oxalic sitting around. I also have some sodium oxalate...
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MineMan
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Any update, or do you think NAP is so good there isn’t a point to the lead complex?
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MineMan
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Any update, or do you think NAP is so good there isn’t a point to the lead complex?
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Hey Buddy
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Well, I think in terms of what's known and available, NAP is the most practical and useful of primaries. I think NAP is an equal jump from lead azide,
as lead azide was from mercury fulminate, IMO.
This Pb(NATz)2 is a different material with different character entirely. It is more powerful, and insensitive, somewhat high temp, so if that is
needed then it can fill that role. The azoles I have no idea of, so far they seem like secondary explosives. Still working on it...
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underground
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Well, i tried a reaction of 0,3mol of diaminourea with 0,3mol of Nano2 and 16ml of 30% HCL for the DAU neutralization and acidification. I used a
magnetic stirrer and an ice bath. Then the addition of Nano2 started. The clear liquid become opaque meaning a reaction was taking place. After adding
a few drops of Nano2 solution i did not noticed any increase in temperature and i felt quite confident to do the reaction out of the ice bath, since
the temperature of the liquids was already too low and the best temp for ATz is about 15-20c. After removing the small beaker from the ice bath i let
it mix without adding any further Nano2 solution. Luckily i was away from the vessel because a very small but bristant detonation occured. The
detonation wasnt very loud because obviously it happend inside the solution but the beaker broke into pieces.
I dunno if i have messed up so hard or if a different kind of tetrazole is produced that it is so sensitive
[Edited on 16-5-2023 by underground]
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Hey Buddy
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Exciting. --Glad you are unscathed. You can use polypropylene for HNO2, just fyi, for detonations when testing random energetics. A PP beaker is very
cheap. They can even handle diluted nitric acid to a certain degree (they phase change to brittle under 0 C).
I don't know what cyclization of carbohydrazide produces. If it is detonating in solution, there is a possibility it could be a sensitive tetrazole,
or it could also be an intermediate prior to tetrazole formation, and the intermediate is detonating. Maybe something like an unstable organic azide
carbonyl intermediate. I'm not sure. Surely someone will know. If you are already detonating in solution under NaNO2/HCl, you may get a different
route or product from NaNO2/Acetic acid or NaNO2/H2O. It couldn't get any worse or more violent... well, i suppose with all that nitrogen and acid
involving unknown products, I suppose it may be possible to release HN3. But if small reactions, it is probably not a great threat. HN3 has a very
alarming potent smell and you cannot mistake it. the body will involuntarily avoid it when it is smelled. It's not like HNO2 which in my opinion
smells a bit like bleach.
[Edited on 17-5-2023 by Hey Buddy]
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underground
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After searching a bit on net about the reaction of DAU and nitrous acid i found this.
"With nitrous acid it forms the highly explosive carbonyl azide CO(N3)2"
So DAU does not cycle to form tetrazoles. Most likely this is the reason why AGu is used. Actually the NH-NH2 group reacts to form -N=N-N=. So because
DAU got 2 NH-NH2 groups, CO(N3)2 is formed. Most like the same would happened with diaminoguanidine forming HNC(N3)2. I bet monoaminourea would form
tetrazoles or aminonitrourea.
[Edited on 19-5-2023 by underground]
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Microtek
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Hey Buddy:
Regarding the cyclization of aminonitroguanidine, I found by reading the attached paper and US patent 2744116 that heating with formic acid (or other
organic acids) produces a stable addition compound, not a cyclic molecule.
It is only when you heat the addition compound with alkali (eg. K2CO3) that the heterocycle is formed.
Attachment: aminonitroguanidine_reactions_Henry.pdf (414kB)
This file has been downloaded 188 times
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Hey Buddy
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Great catch. I haven't been working on the triazole because it was unclear what was going on. Maybe this explanation will get it on track. Thanks.
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dettoo456
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@Hey Buddy Have you made TAGN before? I was thinking about ANGN and such, and it seems good but if there are stability issues (as others have
mentioned about it in the past), and it’s prep requires only GN, 98% H2SO4, Hydrazine, and HNO3, then why not just try to make TAGN, and then try
formylation with cheap CH2O2? Afaik, the rxn hasn’t been done before, but in any case it’d cyclize to the hydrazinotetrazine or
5-hydrazino-4-amino-1,2,4-triazole; both great EM building blocks. The TAGN synth from GN & N2H4 is easy and high yielding too (>80%). The
stability of both tetrazine and triazole aren’t known but I’m guessing they be better than a disubstituted amidine like ANGN (although I know ANG
is useful to work towards 5-NATz).
Anyway though, food for thought. Good luck with the 5-NATz primaries.
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Hey Buddy
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| Quote: Originally posted by dettoo456 | @Hey Buddy Have you made TAGN before? I was thinking about ANGN and such, and it seems good but if there are stability issues (as others have
mentioned about it in the past), and it’s prep requires only GN, 98% H2SO4, Hydrazine, and HNO3, then why not just try to make TAGN, and then try
formylation with cheap CH2O2? Afaik, the rxn hasn’t been done before, but in any case it’d cyclize to the hydrazinotetrazine or
5-hydrazino-4-amino-1,2,4-triazole; both great EM building blocks. The TAGN synth from GN & N2H4 is easy and high yielding too (>80%). The
stability of both tetrazine and triazole aren’t known but I’m guessing they be better than a disubstituted amidine like ANGN (although I know ANG
is useful to work towards 5-NATz).
Anyway though, food for thought. Good luck with the 5-NATz primaries. |
I've made DAGN and TAGN from GN + 2/3N2H4 but it was in search of unknown primary explosives and I thought they didnt seem to fit that bill when
testing, so I didnt revisit it. IIRC it was good yield. I used alcoholic hydrazine so that Guanidine never even went into solution really. made it
easy to filter. Cyclization with that would be interesting...
NAP is so good that it has stalled my motivation to investigate primaries.
[Edited on 22-5-2023 by Hey Buddy]
[Edited on 22-5-2023 by Hey Buddy]
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Microtek
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Do you have a reference for a good synthesis of a diaminoguanidine salt (or the free base I suppose)? I'm worried that I will get a mix of mono-, di-,
and triaminoguanidine if I just do the hydrazinolysis with 2 equivalents of hydrazine.
I found a paper (chinese, so it requires checking) that claimed condensing DAG with oxalic acid and cyclicizing with base yields a bi(1,2,4-triazole)
with four amino groups. These can then be nitrated and the product can form di- or tetra valent salts. The dihydroxylammonium salt is close to CL-20
in VOD and Pcj, with similar thermal stability and lower sensitivity. At a glance, their methods look OK, but it remains to be seen if their results
can be reproduced.
Attachment: Tetranitramino-bis(1,2,4-triazole)_and_salts.pdf (1.2MB)
This file has been downloaded 189 times
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Hey Buddy
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| Quote: Originally posted by Microtek | Do you have a reference for a good synthesis of a diaminoguanidine salt (or the free base I suppose)? I'm worried that I will get a mix of mono-, di-,
and triaminoguanidine if I just do the hydrazinolysis with 2 equivalents of hydrazine.
I found a paper (chinese, so it requires checking) that claimed condensing DAG with oxalic acid and cyclicizing with base yields a bi(1,2,4-triazole)
with four amino groups. These can then be nitrated and the product can form di- or tetra valent salts. The dihydroxylammonium salt is close to CL-20
in VOD and Pcj, with similar thermal stability and lower sensitivity. At a glance, their methods look OK, but it remains to be seen if their results
can be reproduced. |
Wow, that bi triazole sounds neat. --I don't have any references for DAGu/TAGu. I think there are some patents floating around. I believe you do get
mixed products in hydrazinolysis from guanidine. I think the time of reaction is the influencer on how much of each is produced. There is a patent of
carbohydrazide production from hydrazinolysis of cyanuric acid which responds with a higher yield than going from urea alone. I would guess there is a
parallel route to DAGu and TAGu from melamine... I dont think ive ever seen it on a patent though. It may not have ever been attempted..
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Microtek
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Yes, I've found a couple of patents. CN104370776A:
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A preparation method of 1, 3-diaminoguanidine hydrochloride, the specific steps are as follows:
（1）Into the reaction vessel, guanidine hydrochloride (1 Kg) and water (2 Kg) were placed, stirred until the guanidine hydrochloride was completely
dissolved, then 1.0 kg of toluene (mass ratio of water: 1:0.5) was added, and then hydrazine hydrate (1.02 kg, The molar ratio of guanidine
hydrochloride to guanidine hydrochloride is 1:1.9,), and the dropping rate is 2.0 kg/h. After the reaction is completed, the reaction is carried out
at 60 ° C for 10 hours. The pH is adjusted to 2.5 with hydrochloric acid, and the mixture is allowed to stand for separation. The aqueous layer is
distilled and concentrated to the aqueous layer. There is a trace of precipitates, and a concentrated liquid (1.5Kg) is obtained. In the reaction, the
tail gas is introduced into the exhaust gas absorption device, and the by-product ammonia gas generated in the reaction is absorbed into the ammonium
salt solution by the tertiary acid solution, and the acid liquid is: a mass fraction of 85% phosphoric acid aqueous solution, a mass fraction of 50%
phosphoric acid aqueous solution, and a mass fraction of 30% phosphoric acid aqueous solution;
（2）The concentrate was added to the high tank of the reaction vessel, and anhydrous ethanol (6 Kg) was added to the reaction vessel. The
concentrate was added dropwise with stirring, and the dropping rate was 3 kg/h. The crystals were precipitated, allowed to stand for 30 minutes, and
then filtered. 4%。 The purity of the HPLC was 98.4%.
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However, there are some errors and some rather strange phrases (possibly from machine translation) that make me a little wary.
There is also this one, CN107721885A:
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In the reaction vessel, 2.6 Kg of 60% hydrazine hydrate and 2 Kg of the filter mother liquor were mixed and mixed thoroughly. The system was then
cooled to 20-30° C., and the pH was adjusted to 10 with hydrochloric acid. Then, the reactor was heated to 80° C. to start dropping. 2.2Kg 30%
aqueous solution of dicyandiamide, after completion of the dropwise addition, the system was kept at 100° C. for 8 hours, then the pH was adjusted to
6 with hydrochloric acid, then the system was cooled to 0° C. to start centrifugation, and the solid was rinsed with ethanol to dry the target
product. 1.88 Kg, the total yield was 95.9%, and the detection purity was 99.6%.
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This seems simpler, but again I'm a little wary of the translation of the patent. To give you an idea of what I'm referring to, here's an excerpt from
the introduction of the last patent:
| Quote: |
Germanium is a nitrogen-containing organic compound, also known as "carbamidine", which is strongly alkaline and strongly hygroscopic. Osmium is
unstable under alkaline conditions and is easily hydrolyzed. Solid tantalum is generally used in the form of salts such as guanidine hydrochloride,
guanidine nitrate, guanidine carbonate, guanidine sulfate, and lanthanum stearate. Terpenoids are widely used in medicine, agriculture, chemical
industry, etc. due to their excellent properties such as strong alkalinity, high stability, and good biological activity. Their synthesis methods have
also been continuously improved and improved. |
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dettoo456
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@Microtek I was wondering about DAG as well since the Eng patents I’ve seen on TAG all use seemingly random amounts of hydrazine to guanidine
nitrate ratios and generally run the rxn under reflux for about an hour. “ Kinetics of Triaminoguanidine Nitrate Synthesis” in Ind. Eng. Chem.
Res., Vol. 28, No. 4, 1989 pg431-437 references some info on competing rxns as well as a bunch of chem math that I don’t understand but you might
have luck with it. IMO, electroreduction of ANG might be the easiest route to DAG in terms of selectivity of the DAG over mixes of AG and TAG.
USPAT 5041661 shows the optimized conditions for TAGN
Also, when you talked about the oxalic acid ‘formylative cyclization’ of DAG to the polyaminotriazole, you meant that the formed product was a
bis(triazole), right? Not an annulated triazolyltriazole?
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