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dettoo456
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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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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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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)
This file has been downloaded 110 times
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Yorty2040
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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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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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Fluorite
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Can hexamine undergo hydrolysis with sodium hydroxide to form sodium formate, ammonia and methanol?
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dettoo456
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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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solo
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..how to mono aminate 1,5-Dibromopentane....solo
It's better to die on your feet, than live on your knees....Emiliano Zapata.
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dettoo456
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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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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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Laboratory of Liptakov
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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.... .....Only my opinion, not more.
Development of primarily - secondary substances CHP (2015) Lithex (2022) Brightelite (2023) Nitrocelite and KC primer (2024)
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dettoo456
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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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UndermineBriarEverglade
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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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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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UndermineBriarEverglade
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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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Sir_Gawain
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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.
“Alchemy is trying to turn things yellow; chemistry is trying to avoid things turning yellow.” -Tom deP.
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Laboratory of Liptakov
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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......
With pure reagents HNO3 / H2SO4 is yield usually 18g from pure 9g E.
Development of primarily - secondary substances CHP (2015) Lithex (2022) Brightelite (2023) Nitrocelite and KC primer (2024)
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charley1957
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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.
You can’t claim you drank all day if you didn’t start early in the morning.
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greenlight
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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.
Be good, otherwise be good at it 
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UndermineBriarEverglade
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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:
Slowly (20m?) poured KNO3 into freezer-chilled sulfuric acid in ice bath. Max temp ~20C
Let mixture cool to 5C. Slowly (7m) added erythritol and held at this temperature while stirring
This formed an opaque white syrup with some grains. Added 17g of 96[?]% sulfuric acid to smooth it out a bit
Stirred for two hours after adding erythritol
crashed into water and filtered to get bulk ETN
rinsed bulk ETN in water and filtered again. rinsed with 5% baking soda solution
dissolved washed ETN in acetone. filtered out some brown gunk that didn't dissolve
crashed acetone solution into water and filtered
dissolved in min qty acetone (approx 20g) and filtered out some hair and dust that had gotten in
crashed into 3.7% aqueous urea solution
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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greenlight
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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.
Be good, otherwise be good at it
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UndermineBriarEverglade
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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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greenlight
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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.
Be good, otherwise be good at it
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UndermineBriarEverglade
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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.
With external heating called for, I assume this reaction is not exothermic. Are there any dangers?
Does urea nitrate need to be mixed with a fuel like AN or does it explode alone?
Rather than using urea nitrate, would it be better to dehydrate it to nitrourea for a higher VOD?
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?
Does anyone know the critical diameters of urea nitrate and nitrourea?
Are both chemicals resistant to shock/friction/heat/static, in other words stable enough to carry to my test site?
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Sir_Gawain
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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.
“Alchemy is trying to turn things yellow; chemistry is trying to avoid things turning yellow.” -Tom deP.
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