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dettoo456
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[*] posted on 28-5-2024 at 08:08


Has anyone carried out a destructive nitration procedure on a ketone before? I couldn’t find much information on them; it seems Russian chemists were messing around with the principles and kinetics in the mid 90s, but those journal entries are very hard to find, let alone translate.

As far as I can tell, it’s basically the same conditions as for the preparation of Nitroform from Acetone (or from the dehydration of IPA and subsequent nitration). Carbonyls, mainly ketones but apparently carboxylic acids as well, undergo decarboxylative nitration to yield the trinitromethyl or dinitromethyl derivative at the alpha position relative to the carbonyl.

This polynitromethyl product though, can be generated by the action of WFNA/H2SO4 with the ketone at 0C, and Hexanitroethane can even be prepared like this in up to a 75% yield from the terminal-trinitro ketone (authors reported using trinitropentanone, though I believe this was a mistake, and trinitrobutanone might have been used instead).

https://www.researchgate.net/publication/250556009_ChemInfor...

This abstract does not provide much insight as to the conditions (molar equivalent, addition rate, extraction), and I couldn’t find the article in the Russian Org Chem journal.

In short, is it plausible that this reaction could be applied to something like MEK, to yield 1,1,1-trinitroethane?
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Yorty2040
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[*] posted on 14-6-2024 at 17:44


So methazonic acid (2-nitroacetaldoxime) can be produced by the base-catalyzed self-condensation of nitromethane, followed by acid workup.

Is there any info on using sodium perborate + glacial AcOH to convert it to 1,2-dinitroethane? The procedure should work, but the devil (and yield) is in the details of the procedure and subsequent workup.
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dettoo456
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[*] posted on 14-6-2024 at 20:14


I’m assuming you’re referencing this paper (linked below) for the oxidation with perborate. As you mentioned though, the preparation will suffer in yields with the scope being so wide (small chain aldoxime already with a nitro substitutient compared to mainly aryl ketoximes reported being used).

A more sketchy method to yield 1,1,2-TRInitroethane could be the ponzio reaction; NO2 or N2O4 in ether or a suitable polar nonprotic at low temperature).

Or, some other, cleaner oxidizer like oxone or H2O2. Though, in any case, including the Perborate/GAA method, oxidation of the aldehyde to carboxylic acid and oxime to carbonyl is probably the reason for such low reported yields.

[Edited on 15-6-2024 by dettoo456]

Attachment: Oxime Oxidation to NO2.pdf (159kB)
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Yorty2040
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[*] posted on 17-6-2024 at 16:22


What's the technical, physicochemical explanation for why complexing the oxoacid salt of a nitrogenous base with a transition metal typically increases sensitivity compared to the uncomplexated salt?

[Edited on 18-6-2024 by Yorty2040]
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dettoo456
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[*] posted on 23-6-2024 at 13:44


The acidity of the acid itself may contribute to instability (the free H+). Or, since the main decomposition pathway of energetics is based on BDEs (bond disassociation energies) of different groups and bonds on a molecule, if the oxoacid has a lower BDE than other groups in the complex (ionic bonds between the metal and anion), it could kickstart a decomposition process. C, O, and N intermediates may also simply be easier for a group like ClO4-, NO3-, etc to oxidize than the metal itself too. OB% factors in to this as well, along with perhaps higher densities of the materials due to packing of the nitrogenous oxoacids in the complex’s lattice; such higher densities can affect sensitivity too.
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[*] posted on 30-6-2024 at 05:24


Can hexamine undergo hydrolysis with sodium hydroxide to form sodium formate, ammonia and methanol?
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dettoo456
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[*] posted on 3-7-2024 at 17:56


It’d likely form ammonia (or more likely urea) and formaldehyde (the formaldehyde quickly decomposing to formate), in a reverse reaction to the manner in which hexamine itself is prepared.

A controlled hydrolysis may yield (mono, di, or tri)methylamine.

I doubt the conditions would be anywhere close to reducing enough to reduce formaldehyde or formate to methanol.

[Edited on 4-7-2024 by dettoo456]
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[*] posted on 4-7-2024 at 16:03


..how to mono aminate 1,5-Dibromopentane....solo





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[*] posted on 16-7-2024 at 17:16


Explosion welding/cladding is usually carried out on thin metal sheeting (no greater than 1” or 25mm) with minimal explosive used per sq in (<50g in most cases, and low power EMs like ANFO at that).

Would there be any way to feasibly weld 2” (50mm) or thicker mild steel with much larger quantities of explosive or higher VoD explosives?

As the size of the EM charge itself is increased, I’d assume a kicker charge design might be able to increase the total energy transferred to the witness plate from the flyer plate. But as the EM performance rises, and brisance along with it, I’d be worried about the flyer plate just being shattered or shock hardening to the point that it’d be too brittle to weld to the witness.

For context, I have lot of thick steel bar scrap and am too cheap to buy an anvil.
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UndermineBriarEverglade
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[*] posted on 30-7-2024 at 11:01


Do I need to purify monkfruit sweetener for use in ETN? I'm not able to buy pure erythritol online or find it locally. I have Lankato brand, ingredients erythritol and "monk fruit extract" (mogrosides). They don't publish an exact percent, but their website says that monkfruit is 200x as sweet as sugar and erythritol is 70% as sweet. For the mix to match sugar, this would imply 99.6% erythritol. 1.5g of crud per pound of sweetener.

If I want to avoid nitrating mogroside V, how do I get it out? Can't find solubility figures for it.

[Edited on 2024-7-30 by UndermineBriarEverglade]
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[*] posted on 30-7-2024 at 21:53


If I were faced with the same question, I would do the nitration of 2g Lankato as is. The behavior and returns of ETNs are very well known. I would determine the usability of Lankato based on the differences in the behavior of the final product. Yes or no....:cool:.....Only my opinion, not more.



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dettoo456
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[*] posted on 1-8-2024 at 11:42


Most food grade erythritol is pure enough for direct nitration. If the ingredients are just “Erythritol” then you’ll be fine. The small impurities are likely silica dust or some other agent to prevent clumping and/or hygroscopicity.
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[*] posted on 1-8-2024 at 12:59


LL, I am considering it. I would like to store the ETN and I'm nervous about impurities causing deterioration. Easier to test immediate sensitivity characteristics. dettoo, the second ingredient is "monk fruit extract". Unfortunately I can't find food grade erythritol in my region and I'm not able to purchase it online.

Now that I think of it, one more simple question. ETN becomes much more sensitive over the melting point, so you must be extremely careful when meltcasting. When recrystallizing ETN, so putting it in solution but it's below 61C, do I need to take the same level of precaution?
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dettoo456
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[*] posted on 2-8-2024 at 08:23


ETN in solution (Acetone, IPA, and/or EtOH) at the solvents’ bp can be dangerous if spilled on a hot surface - which is why a water bath is recommended. Though it isn’t nearly as sensitive to shock, friction, etc. as the pure melted ETN.

Monk fruit extract in and of itself shouldn’t present any problems in nitration. It is primarily erythritol stereoisomers with small impurities of other polyols, so no real concern is warranted IMO.
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[*] posted on 4-8-2024 at 20:40


Nitrated 9g of "Lankato". Unfortunately I got <35% yield (ETN is still damp). More simple questions:

  • Does anyone have solubility figures for ETN in IPA?
  • Do US hardware stores carry methanol anymore? Are there options besides small HEET bottles?
  • Is there a way to gauge nitration progress? Using the nitrate salt method with KNO3, I ran it for 2 hours at 5C with continuous stirring.
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[*] posted on 4-8-2024 at 21:31


Quote: Originally posted by UndermineBriarEverglade  
Do US hardware stores carry methanol anymore? Are there options besides small HEET bottles?

Methanol can be distilled from windshield wiper fluid. Usually the lower the temperature rating, the more methanol. Also, most “denatured alcohol” is about 50/50 ethanol/methanol which can easily be separated by distillation.




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[*] posted on 4-8-2024 at 22:35


If you have yield 5g final pure dry ETN (from recrystallization proces), is it pretty good yield. If you used method H2SO4 + KNO3 + 9g Lankato......:cool:
With pure reagents HNO3 / H2SO4 is yield usually 18g from pure 9g E.




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[*] posted on 5-8-2024 at 03:26


I just ordered methanol from Amazon. I’m using it as a solvent for the extraction of a plant alkaloid. It came in 1L plastic containers. I think I got 8 of them. Price wasn’t too bad IIRC.



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[*] posted on 7-8-2024 at 08:10


    Quote: Originally posted by UndermineBriarEverglade  

  • Is there a way to gauge nitration progress? Using the nitrate salt method with KNO3, I ran it for 2 hours at 5C with continuous stirring.


  • Nitration is a pretty instantaneous reaction which is evident by the ice bath required for ETN. Forming bonds releases energy which is why you notice a temperature increase upon erythritol addition to mixed acids.
    You will probably notice as you near the end of the additions that the temperature fluctuates much less. The majority of your product is fully reacted at this time. You will probably still have a small amount that is undernitrated and this is why you have the warming step for PETN for example before crashing into ice. The reason you xan warm this mixture at the end is because the majority of the reaction had already occurred. Try applying any warmth at the start and you will have a certain runaway.

    Also, different nitrations require different conditions and baths.
    For example, C-nitration (TNT, Trinitrophenol) usually involves heating and then more heating to get subsequent nitro groups attached.
    O-nitration (PETN, NG) generally is done with no heat on ice and can usually be done with weaker nitric.
    N-nitration (HMX, RDX) is generally done cold as well but usuallY only with highly concentrated nitric acid and no sulfuric.

    That's just the basic gist of it, your 2 hours at 5 C sounds plenty. You c9ukd bring to room temperature with stirring before crashing too if you want.




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UndermineBriarEverglade
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[*] posted on 7-8-2024 at 10:27


Thanks. Next time I'll nitrate the same length, but take it out of the ice bath and let it come up to room temp before crashing. After a couple days drying with silica gel my yield appears to be 32% which is far below the 70%, 60% I have seen described for the nitrate salt method.
I attempted to purify my 93.2% drain cleaner sulfuric acid by adding hydrogen peroxide to make piranha solution and then boiling until the azeotrope, but wasn't sure I boiled it long enough. I added my acid as if it was 93.2%, hoping that if all went well it would be in excess. Next time I will measure the concentration or just use it as received.

9g erythritol C4H10O4 122.121 g/mol
- 0.0737 mol (call this "E")
67.059g potassium nitrate KNO3 101.10324 g/mol
- 9 * E = 0.663 mol
- I wanted an excess of KNO3 to avoid undernitration. Dugan recommends 8 mols per mol erythritol. But I see some people using the minimum 4? Nitrates are the most difficult ingredient for me to obtain.
86.738g sulfuric acid H2SO4 98.07948 g/mol
- 12 * E = 0.884 mol
- 93g of 93.2% acid
- Added more during procedure to make it more stirrable.

theoretical yield:
22.264g ETN C4H6N4O12 302.1 g/mol
- 0.0737 mol

actual yield:
7.09g = 32%

Procedure:

  1. Slowly (20m?) poured KNO3 into freezer-chilled sulfuric acid in ice bath. Max temp ~20C
  2. Let mixture cool to 5C. Slowly (7m) added erythritol and held at this temperature while stirring
  3. This formed an opaque white syrup with some grains. Added 17g of 96[?]% sulfuric acid to smooth it out a bit
  4. Stirred for two hours after adding erythritol
  5. crashed into water and filtered to get bulk ETN
  6. rinsed bulk ETN in water and filtered again. rinsed with 5% baking soda solution
  7. dissolved washed ETN in acetone. filtered out some brown gunk that didn't dissolve
  8. crashed acetone solution into water and filtered
  9. dissolved in min qty acetone (approx 20g) and filtered out some hair and dust that had gotten in
  10. crashed into 3.7% aqueous urea solution
  11. filtered and dried


The syrup was so thick that my overhead stirrer wanted to pull the thermometer out of its clamp. I had to remove the thermometer while stirring and regularly insert to check temp.

The crystals from crashing the acetone solution into water were extremely annoying. Many floated or adhered to the sides of the crash bucket, and the vacuum filtering was very slow even at -25 inHg. I will try another solvent.

Also does anyone have Dugan's ETN part 2 video? Youtube took it down

[Edited on 2024-8-7 by UndermineBriarEverglade]
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[*] posted on 8-8-2024 at 08:57


I have read that ETN is quite finnicky with wildly varying yields when multiple individuals follow the exact same synthesis methods.

I have never used the nitrate salt/sulfuric acid method, always mixed acids. I can imagine that the mixture with nitrate salt gets quite viscous, especially at low temperature.

A few ideas you can apply ne let run if you choose:

1. Try using nitric acid if available to you, doesn't have to be anhydrous.
2. I have read off higher yield success using ammonium nitrate instead of potassium nitrate if that is available.
3. Powder both the nitrate salt and erythritol before addition to increase surface area which will increase reactive surfaces and an increase of collisions within the nitration bath.
4. Constant stirring which also leads to increased rate of collisions.
5. As discussed previously, bring the reaction mixture out of the ice-bath, once the majority of the reaction has taken place, and let it warm on its own to room temperature with stirring before crashing on ice. Pay attention for any signs of runaway during the entire nitration.

If you had trouble filtering after recrystallisation I dont think it was so much the solvent being the issue if it all dissolved easily, you must have ended up with low density (fluffy when dry) final product proba ly due to the speed at which the crystals reformed. You mention it taking a long time to filter due to it most likely clogging the filter paper pores due to small particle size.

I used to achieve quite high quality PETN crystals by dissolving into hot acetone and then pouring very slowly into rapidly stirred cold water with some ice and a small amount of urea. The key was the speed it was poured in.




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UndermineBriarEverglade
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[*] posted on 8-8-2024 at 12:26


Thanks greenlight. I'd read that acetone resulted in large (=sensitive) crunchy crystals so I poured quickly. The result is fluffy and insensitive to impact. Perhaps clogged filter paper ate some of my yield?

I know potassium nitrate is one of the worst choices but unfortunately it's all I can get. Decided not to make nitric acid or AN unless I really can't get the nitrate salt method working.
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[*] posted on 12-8-2024 at 10:29


The reason for trying to achieve the more granular crystals was for preparing plastic explosive which involved a long rolling process to incorporate the binder and plasticiser.
This was with PETN though which is less sensitive than ETN.

And, yes, finer precipitates do clog the filter paper pores and become increasingly difficult to filter as the particle size gets smaller.




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[*] posted on 20-8-2024 at 14:46
Urea nitrate & nitrourea


I have built ETN caps and an EBW detonator and expect this to be reasonably reliable. Now I want to find a reliable secondary for my main interest: geometry of larger shaped charges. I don't want to make a lot of ETN since synthesis with KNO3 is tedious and that's the only nitrate I have.

I have aqueous urea. The wiki gives a route for urea nitrate: add hydrochloric acid to a hot solution of urea and potassium nitrate, heat til steaming, then freeze to precipitate urea nitrate.

  1. With external heating called for, I assume this reaction is not exothermic. Are there any dangers?
  2. Does urea nitrate need to be mixed with a fuel like AN or does it explode alone?
  3. Rather than using urea nitrate, would it be better to dehydrate it to nitrourea for a higher VOD?
  4. I read that nitrourea is hygroscopic. What happens when it hydrolyzes? Could I simply store it in a plastic bag? Are there chemical ways to stabilize it?
  5. Does anyone know the critical diameters of urea nitrate and nitrourea?
  6. Are both chemicals resistant to shock/friction/heat/static, in other words stable enough to carry to my test site?
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[*] posted on 20-8-2024 at 20:22


1. I’ve done this reaction before, although with ammonium nitrate instead of potassium nitrate. It’s not very exothermic and is pretty straight forward and safe. I didn’t get a very high yield though.

2. Urea nitrate can be detonated on its own, but I would suggest mixing with ammonium nitrate to make an oxygen balanced explosive. I’ve tested this mixture, and it’s cap sensitive and fairly powerful.

3. While nitrourea is said to be more powerful, I’ve heard it has poor stability. Nitroguanidine is more powerful and stable.

4. I don’t know.

5. I successfully detonated a charge of AN/UN with a diameter of 1cm.

6. Urea nitrate is very insensitive, don’t know about nitrourea.

If you’re trying to make shaped charges, pure urea nitrate is not a good choice. It has a low detonation velocity. A mixture of urea nitrate and ETN could work. You wouldn’t have to make nearly as much ETN.




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