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Author: Subject: NIHT/NHHT Synth Suxess!
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[*] posted on 11-7-2023 at 08:31


You can test a sample of ETN or RDX or whatever and compare to anything else. Note that density play a big role on performance.
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[*] posted on 11-7-2023 at 08:54


I've got 1" 6061 Al block cubes. I think 500mg is common for a test like that. I can compare to melt ETN. I don't have a way to measure pressure for loading, but can try to just press it "real good".
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[*] posted on 11-7-2023 at 10:29


After pressing don´t forgot do it mesurement of density of this 500mg. Radius x radius (in cm) x 3.14 x height (in cm)......:cool:



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[*] posted on 11-7-2023 at 11:11


I filtered off some of the precipitate. unless it is very dense, it appears a low yield, small amount of material recovered. Gray contamination from silver in product.
In paper it is claimed dilute HCl 18% gives freebase product. Since the NHHT itself is not energetic, and requires minimally an oxidizer anion, it seems HNO3 would be more direct. Why not skip NHHT HCl and attempt nitrate from hex+NQ+HNO3? Further more, if HNO3 is used, HDN could be used in leu of hexamine, then use HNO3 as acid source...

I wonder if citric acid or acetic and ammonium nitrate could be used for NHHT*NO3


[Edited on 11-7-2023 by Hey Buddy]
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[*] posted on 11-7-2023 at 11:16


Quote: Originally posted by Laboratory of Liptakov  
After pressing don´t forgot do it mesurement of density of this 500mg. Radius x radius (in cm) x 3.14 x height (in cm)......:cool:


Yes I will caliper the vessel and index the depth of load after pressing. Is 500 mg the standard that you use? ~8mm cylinder, SS? I hope there is enough NHHT NO3 to make 500mg...
BTW, what does "cool" emoji face mean? I always see you use it, but I don't understand. I imagine you are sun-bathing at a pool while typing on SM.
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[*] posted on 11-7-2023 at 12:17


Most likely the nitrate salt is quite soluble in water. Try to evaporate more water or to clean it up, redissolve, filter the contamination and evaporate. Did you use sticiometric amount of silver nitrate to NHHT HCL. ?

AgNO3 169,8g/mol
NHHT HCL 181,5 g/mol

So for every 1,8g of NHHT HCL you have to add 1,7g of AgNO3


You should have end up with more product when you convert it to HNO3 salt from HCL since the molar mass of the molecule have been increased. The crystal structure of nitrate salt may be quite dense

From metathesis you get 100% yields. If you did not then something is off. Maybe your NHHT HCL is not pure or something.

I am not sure if HNO3 can be used. HCL is used to break up Hexamine to methylamine. RDX is actually an isomer of 3 molecules of nitromethylamine so maybe HNO3 will work. Hexamine broke up in process to methylamine and react with NQ to form NHHT HCL. 2 moles of methylamine and 1 mole of NQ form NHHT. If the temperature go high other methylamine products may produced like dimethylamine and trymethylamine. Maybe you got some ammonium HCl as contamination.


[Edited on 11-7-2023 by underground]
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[*] posted on 11-7-2023 at 14:25


Quote: Originally posted by underground  
Most likely the nitrate salt is quite soluble in water. Try to evaporate more water or to clean it up, redissolve, filter the contamination and evaporate. Did you use sticiometric amount of silver nitrate to NHHT HCL. ?

AgNO3 169,8g/mol
NHHT HCL 181,5 g/mol

So for every 1,8g of NHHT HCL you have to add 1,7g of AgNO3


You should have end up with more product when you convert it to HNO3 salt from HCL since the molar mass of the molecule have been increased. The crystal structure of nitrate salt may be quite dense

From metathesis you get 100% yields. If you did not then something is off. Maybe your NHHT HCL is not pure or something.

I am not sure if HNO3 can be used. HCL is used to break up Hexamine to methylamine. RDX is actually an isomer of 3 molecules of nitromethylamine so maybe HNO3 will work. Hexamine broke up in process to methylamine and react with NQ to form NHHT HCL. 2 moles of methylamine and 1 mole of NQ form NHHT. If the temperature go high other methylamine products may produced like dimethylamine and trymethylamine. Maybe you got some ammonium HCl as contamination.


[Edited on 11-7-2023 by underground]


Of course, stoichiometric. There must be something wrong with this NHHT. The remaining filtrate was left to evaporate, the last time I looked at it, it had some additional salt precipitating. Went back to check again, decomposition, brown syrup. It has to be the NHHT. The silver was made from bullion dissolved in HNO3. The stuff I use for SADS. That leaves bad NHHT as the only possibility, drying temp was pretty low. Recovered salt is very little, I haven't weighed it but it's too little to do repeat tests. Will have to try some other methods and prepare new NHHT. Might as well just try other simple methods to find out if any of them work


Update:
Made a batch of HDN. Plan to test:
1) NQ/HDN/HNO3
2) NQ/hexamine/HNO3
3) NQ/hexamine/HClO4

There are a lot of compounds in this series. Have to parse logical potentials.
I figure with possible issues of NHHT HCl to NO3, due to possible bad NHHT, eliminate crossover of HCl to NO3 for now, instead focus on unknown products from plausible routes, and since it isn't really known what the products are, just perform the process and fire the resulting products into Al witness blocks and compare effect. RDX and etn as controls for comparison.
After the effects are compared from the various products, simple processes like nitrate displacement from HCl can be attempted and those products fired to compare against the known witness blocks.
I need a break from demoralizing amino acids for a bit anyways...

[Edited on 12-7-2023 by Hey Buddy]
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[*] posted on 11-7-2023 at 20:55


I do not this there would be any different using HDN over Hexamine since you are going to reflux it wil 65% NA. You will just end up with the same products. It will be just like using a stronger acid like 67% NA. You just adding more HNO3 moles into the mixture. HDN is good when used for RDX

[Edited on 12-7-2023 by underground]
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[*] posted on 11-7-2023 at 21:03


Quote: Originally posted by underground  
I do not this there would be any different using HDN over Hexamine since you are going to reflux it wil 65% NA. You will just end up with the same products. It will be just like using a stronger acid like 67% NA. You just adding more HNO3 moles into the mixture. HDN is good when used for RDX

[Edited on 12-7-2023 by underground]


Are you certain there is no possibility of a dinitrimine nitrimino triazine? Via HDN?-- I need to prepare rdx, so I just made a big batch of hdn, so there is plenty of extra for tests. And for Al block controls for anything comparable to rdx. For tests of NQ/hexamine, I would use 99% HNO3 not 65% as in a nitrate. Surely there is a potential of a dinitramine, there is a trinitramine and a mononitramine, the tri is from acetic anhydride in their limited tests, analogous to Bachmans rdx, then they find a mono nitramine from mixed acid, it seems that HDN and high test HNO3 would derive a dinitramine if not a trinitramine analogous to KA process for RDX via HDN. Is that not logical?
It seems worth a look since HDN is so fast to make

[Edited on 12-7-2023 by Hey Buddy]

[Edited on 12-7-2023 by Hey Buddy]
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[*] posted on 11-7-2023 at 21:37


If you are going to use 99% NA then yes it is worth it. I was talking about 65% NA. You could even try to Add H2SO4 to the mixture since with NQ you will end up with Z-RDX.
I was just thinking to try the compounts step by step for example NHHT nitrate/perch then NNHT etc compare them, check there properties and performance then decide with worth the most.

Purification/recrystallization of NHHT HCl could end up with better understanding and progress of the derivatives. Most of the contamination comes from the Hex/NQ rnx. The next steps are clear

99% NA needs equipment and it would be hard to make in big quantities. On the other hand NHHT HNO3 / NNHT can be made without special equipment from cheap and available materials at large quantities. If NHHT HNO3 has better performance than TNT then it is worth it. Even if it will end up with poor performance NNHT is one step dehydration from NHHT HNO3 with H2SO4.
The only issue for NNHT production is to find out the best way of NHHT HCL production and purification.

AgCL can be converted back to Ag metal with NaOH and table sugar. Ag powder/ Ag2O could possibly react with AN to make AgHNO3 again

The H2SO4 used for the dehydration of QN to NQ and NHHT HNO3 to NNHT could be reused and reconcentrated by boiling. It is never consumed. So in theory only urea AN and Hexamine are going to be consumed for making NNHT without any special equipment.

Just my opinion

[Edited on 12-7-2023 by underground]
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[*] posted on 12-7-2023 at 01:44


Hey Buddy
Usually I am at sun-bathing at a pool while typing on SM......:cool:
For basic measurement I use aluminium block and 1000mg in diameter 8 mm.
At this conditions should by give ETN at least 5 mm of deep of crater.

table deep.jpg - 995kB

[Edited on 12-7-2023 by Laboratory of Liptakov]




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[*] posted on 12-7-2023 at 03:29


Quote: Originally posted by underground  


99% NA needs equipment and it would be hard to make in big quantities. On the other hand NHHT HNO3 / NNHT can be made without special equipment from cheap and available materials at large quantities. If NHHT HNO3 has better performance than TNT then it is worth it. Even if it will end up with poor performance NNHT is one step dehydration from NHHT HNO3 with H2SO4.
The only issue for NNHT production is to find out the best way of NHHT HCL production and purification.

The H2SO4 used for the dehydration of QN to NQ and NHHT HNO3 to NNHT could be reused and reconcentrated by boiling. It is never consumed. So in theory only urea AN and Hexamine are going to be consumed for making NNHT without any special equipment.

Just my opinion

[Edited on 12-7-2023 by underground]


Good points, in that case the first one to test would indeed be NHHT nitrate. AgNO3 should be avoided because it is not as common of nitrate source. Should rather attempt route from common nitrate source such as Na/K or NH4NO3. HDN can be tested after hexamine is tested, I will just use to prepare RDX for control test on Al block for now.
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[*] posted on 12-7-2023 at 03:34


Quote: Originally posted by Laboratory of Liptakov  
Hey Buddy
Usually I am at sun-bathing at a pool while typing on SM......:cool:
For basic measurement I use aluminium block and 1000mg in diameter 8 mm.
At this conditions should by give ETN at least 5 mm of deep of crater.



[Edited on 12-7-2023 by Laboratory of Liptakov]


Do you know the type of Al you have used in past, if it is common like 6061 or something else? I have 6061 right now, but if you are using other one I should use that, because 6061 may yield differently than other Al under this pressure/force. I believe 6061 may be a bit softer than some others but is most common.
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[*] posted on 12-7-2023 at 04:43


Quote: Originally posted by Hey Buddy  
Quote: Originally posted by underground  


99% NA needs equipment and it would be hard to make in big quantities. On the other hand NHHT HNO3 / NNHT can be made without special equipment from cheap and available materials at large quantities. If NHHT HNO3 has better performance than TNT then it is worth it. Even if it will end up with poor performance NNHT is one step dehydration from NHHT HNO3 with H2SO4.
The only issue for NNHT production is to find out the best way of NHHT HCL production and purification.

The H2SO4 used for the dehydration of QN to NQ and NHHT HNO3 to NNHT could be reused and reconcentrated by boiling. It is never consumed. So in theory only urea AN and Hexamine are going to be consumed for making NNHT without any special equipment.

Just my opinion

[Edited on 12-7-2023 by underground]


Good points, in that case the first one to test would indeed be NHHT nitrate. AgNO3 should be avoided because it is not as common of nitrate source. Should rather attempt route from common nitrate source such as Na/K or NH4NO3. HDN can be tested after hexamine is tested, I will just use to prepare RDX for control test on Al block for now.


For metathesis to work you have to find a soluble nitrate salt and an isoluble HCL salt. If you want to avoid AgHNO3 then freebase the NHHT with NaOH is your best alternative.

How much NHHT HNO3 you got? Did you did a flame test ?

[Edited on 12-7-2023 by underground]
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[*] posted on 12-7-2023 at 10:25


Quote: Originally posted by underground  

For metathesis to work you have to find a soluble nitrate salt and an isoluble HCL salt. If you want to avoid AgHNO3 then freebase the NHHT with NaOH is your best alternative.

How much NHHT HNO3 you got? Did you did a flame test ?
[Edited on 12-7-2023 by underground]


of nitrate sources, NH4NO3 should be considered firstly because it's most common and has gaseous cation. K/Na are second most common. For those two salts with metal cation, K/NaNO3 metathesis seems best route.
For NH4NO3 however, it seems possible that free based NHHT could be heated with ammonium nitrate, or alternatively, a method from Metelkina:

"...heating the reagents in 18% hydrochloric
acid at 50–55°C for 3 h we isolated a compound which
was assigned the structure of nitrimine (IX)"

they are referring to the free base NHHT via dilute HCl, therefore it may be possible to simply heat NQ/Hexamine/18% HCl to 55 C for 3 hours, and isolate the freebase, followed by boiling with NH4NO3 (NHHT decomp is reported at 200 C). Or perhaps even heating NH4NO3 along with the other reagents initially. Or maybe a combination of the two, heating the reagents to produce NHHT, then without separating NHHT, add the NH4NO3 to the solution.

If any of that were possible, it would be the absolute minimum process to achieve the nitrate salt. And dead easy. It seems too simple to be possible, but it may be possible, with the catalytic action of heat and the fragmenting of the hexamine into a triazine in solution. NH4NO3 may just release NH3 and produce the nitrate on the triazine.

As for AgNO3 attempt, there isnt much. Most decomposed. What's there has Ag contamination not worth separating. I can try a burn test, to see if it is different than the NHHT... over all, need to simply use fresh materals to eliminate variables. NHHT sample is a year old...


Burned the attempted NHHT*NO3 it had no notable energetic reaction. Assumption is a bad sample...

[Edited on 13-7-2023 by Hey Buddy]
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[*] posted on 12-7-2023 at 19:28


Updates please!

And this out performs HMX? 9000m/s @ 1.8 when crystal density is 1.95?
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[*] posted on 12-7-2023 at 19:32


Guanidine and urea with Hexamine most likely will yield the corresponding triazine. The dinitrate salt of the triazine into H2SO4 will yield 3 freebase ( NNHT ) and 10 freebase skipping the QN to NQ step. 10 freebase has the same OB as RDX

The most important part obviously is to cyclise urea/guanidine with hexamine to form the corresponding triazine. From that point on you can choose how much you want to nitrate it.

[Edited on 13-7-2023 by underground]
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[*] posted on 12-7-2023 at 20:27


Quote: Originally posted by MineMan  
Updates please!

And this out performs HMX? 9000m/s @ 1.8 when crystal density is 1.95?


We don't know. There is also a dinitrimino dinitramine reported at 9250m/s @1.88 out of possible 1.96.
I botched a metathesis of Silver nitrate with an old NHHT sample back from beginning of this thread. Now back to square one.
Discussing strategy to test the family tree of possible molecules from this NQ/hexamine root. There are lots of things to test. The literature isn't accurate, metalkina is probably the most accurate. He doesn't give characteristics of the compounds. the pyro, prop. & explosives article appears to be inaccurate on reported performance, however, there appear to be several possible 9km+ compounds from NQ/hexamine. Triazines and broken triazines, and an oxadiazine.

I think Underground and I agree it best to begin simple and try least effort/complexity to most. In search of easy quick high velocity explosive. I'm going even further trying to get a nitrate from NH4NO3 boiling.

Made a big batch of HDN for a control comparison with rdx, but
I thought HDN decomposed at 170 C. Apparently it exhumes nitric acid at lower temp because I tried drying over elevated temperature and this morning the hexamine was in a puddle of nitric acid in the drying dish. I should have just let the acetone dry out on vacuum.

It seems the order of testing is nhht salts like nitrate and perchlorate, then attempt higher nitrated variants all the way up to the z-rdx with a nitrimino in the triazine #6 position, low temp 50c decomp, but high performance. Then comes fractured NNHT via base, then (bis)NQ, after that (bis)NQ heterocycles.
At least, it seems like thats the plan. I'm wiring a residential house, so I'm preoccupied at the moment, but thinking about this at night. I think thats about everything for update up to speed.

[Edited on 13-7-2023 by Hey Buddy]
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[*] posted on 12-7-2023 at 20:43


Quote: Originally posted by underground  
Guanidine and urea with Hexamine most likely will yield the corresponding triazine. The dinitrate salt of the triazine into H2SO4 will yield 3 freebase ( NNHT ) and 10 freebase skipping the QN to NQ step. 10 freebase has the same OB as RDX

The most important part obviously is to cyclise urea/guanidine with hexamine to form the corresponding triazine. From that point on you can choose how much you want to nitrate it.

[Edited on 13-7-2023 by underground]


Will simply have to attempt each compound and fire it into Al to compare effect. Theory is good for planning but in practice, it will have little bearing on effect. Must fire them all and compare.:cool:

Now I understand cool face emoji. Feels gud man.
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[*] posted on 12-7-2023 at 21:12


Quote: Originally posted by Hey Buddy  

Now I understand cool face emoji. Feels gud man.


LoL
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[*] posted on 12-7-2023 at 22:09


Hey Buddy........Most likely it is 6061. But you still need a reference crater from ETN. At least one, preferably two. Whatever the aluminum, soft or hard, it is always essential to have a reference sample of known EM. And perform all other tests under the same conditions with the same aluminum. Same pad, same blast pit, same sawdust cover, same amount of primary and so on.

I'm explaining it here for at least the tenth time. And then someone comes with a picture of an old rotten wooden board with a gaping hole and a pile of chips around it.




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[*] posted on 13-7-2023 at 14:56


Quote: Originally posted by Laboratory of Liptakov  
Hey Buddy........Most likely it is 6061. But you still need a reference crater from ETN. At least one, preferably two. Whatever the aluminum, soft or hard, it is always essential to have a reference sample of known EM. And perform all other tests under the same conditions with the same aluminum. Same pad, same blast pit, same sawdust cover, same amount of primary and so on.

I'm explaining it here for at least the tenth time. And then someone comes with a picture of an old rotten wooden board with a gaping hole and a pile of chips around it.


Patience is the virtue of the master. --I noticed that you are measuring depth of crater, have you attempted measuring water volume by either weighing mass of water from a filled crater on a scale? It may give more resolution in reading for comparisons.
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[*] posted on 19-7-2023 at 02:42


I found a Chinese paper for NNHT production. They claim that NNHT det Velocity is 9094m/s. I managed to translate it with an online Chinese to English translator.




Quote:

2-Nitroamino-5-nitro-hexahydro-1,3,5-triazine (NNHT) is a
It is a new type of insensitive explosive, which has attracted people's attention in recent years[1,2].
The molecular structure of NNHT contains both nitro and amino groups, both of which can form
Intermolecular and intramolecular hydrogen bonds have low sensitivity; its density, collision
The impact sensitivity, detonation velocity and specific impulse are respectively 1.88 g·cm-3
, 89 cm, 9094
m•s-1 and 238 s[3~5], it can be seen that it is an insensitive and
Energetic materials with high energy density.
Currently, the United States uses it in gun propellants to make it weapon-resistant
can be improved. The application of NNHT in the M30A1 formulation can make the propellant
The propellant power of propellant is increased by 8%. While NNHT increases the burning rate of propellant, it also
The flame temperature is lowered, and the gunpowder power is increased[6].
In 1990, Huang et al. [3] first designed and synthesized 2-nitroamino-5-
Nitro-hexahydro-1,3,5-triazine (NNHT), its synthesis[7], crystal structure
and molecular geometry[8] have been reported in China. The literature[9, 10] reports are based on
Nitroguanidine, terbutylamine and formaldehyde as raw materials, through Mannich condensation reaction
To obtain 2-nitroamino-5-tert-butyl-hexahydro-1,3,5-triazine (NBHTA),
Then the target compound was obtained through chloride ion catalyzed nitrification reaction (Scheme
1). Wang Bozhou et al. [9] improved the process to increase the Mannich shrinkage
When the combined reaction temperature reaches 82 ℃, the yield can reach up to 89%;
NBHTA was nitrated with industrial nitric acid instead of pure nitric acid, and at 20 °C, the yield
No. 2 Li Yongxiang et al.: A new method for the synthesis of 2-nitroamino-5-nitro-hexahydro-1,3,5-triazine (NNHT) 257
up to 88%; the total yield of the reaction was up to 78%.
Scheme 1
In order to reduce the cost, a new synthetic route (Scheme 2) was adopted in this paper.
NNHT was synthesized from urotropine, nitroguanidine and hydrochloric acid.
In the nitrification reaction, concentrated nitric acid is directly used for nitrification, which is less than the original process.
The raw material ammonium chloride; the raw material terbutylamine in the original process is more expensive, and the market price is
22,000 yuan/ton, while urotropine is much cheaper, and the market price is 99.9%
6800 yuan/ton, the cost of the product is greatly reduced; the revenue of the target product of this route
The yield can reach 64.3%, although the yield is lower than the original process, but the overall average
On balance, the new process is still very economical, saving costs while also
Facilitate the expansion of production scale.
Scheme 2
1 Experimental part
1.1 Instruments and reagents
Beijing Analytical Instrument Factory IR-8400S spectrometer (potassium bromide tablet
method) to test the infrared spectrum of the product; using Element2VARIOEL element
Determination of C, H, N content by element analyzer; Determination by Bruker-AV400
1HNMR and 13CNMR; using Dalian Elite P230 high performance liquid phase
Chromatography to test the purity of intermediates and target products, STA-449C heat fraction
The melting points of intermediates and target products were determined by analyzer.
Hexatropine, methanol, N,N-dimethylformamide, hydrochloric acid (37%)
All were analytically pure; concentrated nitric acid (98.5%) and nitroguanidine were all industrial grade.
1.2 Synthesis of hydrochloride NIHT•HCl (1)
Add 20 mL (0.239 mol) of 37% hydrochloric acid into 100 mL
In the flask, weigh 7 g (0.048 mol) urotropine and add it to hydrochloric acid, stir
Mix; weigh 5 g (0.048 mol) of nitroguanidine, slowly add four-port burner
bottle, stirred at room temperature; after mixing evenly, the temperature was raised to 38 °C, and stirred
Reacted for 3 h; during the reaction, the solution gradually turned milky white;
warmed, filtered, washed with 10 mL of methanol, and dried to obtain an intermediate product
NIHT•HCl is a white powder.
1.3 Purification of intermediate product NIHT•HCl (1)
The intermediate product NIHT•HCl is the hydrochloride, choose concentrated hydrochloric acid for
Purification, using analytically pure concentrated hydrochloric acid to dissolve the water-insoluble intermediate product,
Solubility is small at room temperature, it can be dissolved by heating, and dissolved when the temperature rises
The degree of solubility increased significantly, and then cooled down to room temperature, crystals were precipitated, washed and dried.
Yield 78.3%, purity 98.5%. m.p. 189 ℃.
1.4 Synthesis of NNHT (2)
Add 5 mL (0.118 mmol) of 98.5% concentrated nitric acid into a four-neck flask
medium, ice-salt bath (salt bath formula: 100 g H2O: 20 g NH4Cl: 40 g
NaCl) to -10~-12 ℃; then weigh 1 g (0.01 mmol)
Slowly add NIHT·HCl into concentrated nitric acid, and keep warm for 30 min to increase the reaction
The temperature was 2-3 °C, and the reaction time was 1 h; filtered, washed with water, and vacuum-dried,
The target product was obtained as light yellow powder with a yield of 82.1% and a purity of
98.3%. m.p. 207 ℃ (literature value [10] 207 ℃); 1
H NMR δ: 9.27
(s, 2H, 2×NH), 5.32 (s, 4H, 2×CH2); FT-IR (KBr) ν:
3330, 3216 (N—H), 3123, 3047, 2972 ​​(C—H), 1607 (C—
N), 1572 (NO2) cm-1
. Anal. calcd for C3H6N6O4: C 18.95,
N 44.20, H 3.18; found C 19.58, N 43.91, H 3.21.
2 Results and discussion
2.1 Factors affecting the synthesis of hydrochloride NIHT•HCl (1)
Synthesis of NNHT from Nitroguanidine (NQ) and Hexamethamine (HA)
The first step in the pathway is ring opening by HA, providing nitroguanidine
The CH2NHCH2 group forms a triazine ring, which is then combined with a molecule of HCl to form
Hydrochloride. It is also possible that methenamine reacts with concentrated hydrochloric acid to form formaldehyde and
Ammonium chloride and urotropine have the properties of tertiary amines, thus possessing
Mannich reaction conditions, so the reaction principle is fundamentally the same as Scheme 1
are consistent. The product formed, NIHT·HCl, is para to the N=C double bond
N—H combined with one molecule of hydrochloric acid.
When synthesizing NIHT•HCl, use industrial grade and analytical pure concentrated salt respectively
Acids were used for the synthesis reaction, and the two did not have much influence on the product yield, while
By changing the reaction time to 3, 5, 7, 9, 10 h and the reaction temperature to 30,
38, 50, 55, 70, 80 ℃. The effects of reaction time and temperature on the production
impact on yield.
258 Organic Chemistry Vol. 31, 2011
2.1.1 Effect of reaction time
The order of addition is: concentrated hydrochloric acid → urotropine → nitroguanidine, the reaction temperature
at 38°C

When the temperature is low (<50 °C), with the increase of the reaction temperature, the reaction
The yield rate also increases. This is because the Mannich condensation reaction is a
Endothermic equilibrium reaction, the effect of temperature on the reaction yield depends on the reaction rate
and equilibrium conversion are two factors. When the temperature is lower, the reaction reaches equilibrium
When the conversion rate is low, and it takes a long time. Because the reaction at low temperature
It should be difficult to reach equilibrium, so the conversion rate is low, resulting in low reaction yield.
As the temperature increases, the reaction speed increases and the conversion rate increases accordingly. When
When the temperature rises above 50 °C, with the increase of reaction temperature, the reaction rate
The rate is accelerated, but hydrochloric acid will volatilize to a certain extent with the increase of temperature, resulting in the dissolution
The decrease of the acid concentration in the liquid makes the reverse reaction of the salt formation reaction possible,
On the contrary, it leads to the decrease of the yield of salt. Therefore, the reaction yield increases with the temperature
After the maximum value appears, it gradually decreases. In addition, due to the temperature rise of the reaction system
A certain side reaction occurs after high temperature, which also affects the yield to a certain extent.
Therefore, the yield of the intermediate product reaches the maximum at 50 °C


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[Edited on 19-7-2023 by underground]
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[*] posted on 25-7-2023 at 16:03


Considering the easy of making NNHT- NIHT HNO3/HCLO4 and their potential, it really amazes me the fact that still nobody want to explore those energetics
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[*] posted on 21-1-2024 at 06:44


I gave NIHT a shot recently:

Hexamine (3.5 g, 25 mmol) was added to hydrochloric acid (37%, 10 ml) with stirring. When the hexamine was mostly dissolved, nitroguanidine (2.5 g, 24 mmol) was added in small portions over the course of 10 minutes. No exothermicity was seen.
The temperature was raised to 38 C, and kept at 38.0-38.5 C with stirring for three hours. When the temperature was raised, almost all of the solids were dissolved, but after about 30 minutes, a white powdery precipitate was formed. The reaction was done in a fume hood as it evolves a lot of formaldehyde.

After three hours, the mix was allowed to cool to 5 C, and was filtered, washed with ethanol on the filter, resuspended in ethanol, refiltered and left to dry overnight. The collected product weighed 4.871 g, which is more than the used guanidine can account for. In an effort to purify the product, it was added to 50 ml of distilled water and heated to dissolve it (the Metelkina paper does this). On cooling, small, white crystals precipitated. These were collected by filtration, dried and weighed. Only 0.987 g had precipitated from the recrystallisation. In order to determine the solubility of the isolated compound, an excess of the solid was added to distilled water, stirred for 5 minutes at 21 C and centrifuged. The solution was then decanted into a pre-weighed petri dish, and the water was evaporated at 70 C. Re-weighing the petri dish showed 10 mg of solids had been dissolved in the water, indicating a solubility of 1 g per liter of water at 21 C.
A second saturated solution was prepared and treated with AgNO3 soln, but gave no AgCl precipitate. This indicates that the product recovered from the recrystallisation is not NIHT*HCl but probably the free base.

On the assumption that the solid was in fact NIHT free base, 0.15 g was mixed with an equivalent amount of HClO4, 50% and evaporated to dryness at 70 C. This gave a syrupy material that hardened to a candy like substance on cooling. It burns energetically and without smoke or residue, and is quite sensitive to hammer blows. It is also quite hygroscopic, and absorbed enough moisture to turn liquid after 12 hours at 45% relative humidity and 21 C.
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