Axt
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1-Nitrohydantoin and Derivatives
This is really only of interest because it is a simple urea-glycine condensation product. There is no published information on its explosive
properties that I am aware of.
There is a few bits published on urea glycine condensation, US Patent 4647694 looks to be the simplest route by simply heating glycine with excess
urea then cyclising with sulphuric acid. I only found this after I'd already done everything presented here, I went with Chinese patent CN1958569A,
which uses glycine + urea + sodium hydroxide for the initial condensation, followed by sulphuric acid in a 1 pot reaction over 12 hours. This goes
well, my yield was 53%, down from the 73% claim but I was quite aggressive with the washing.
I did initially try Chem. Heterocycl. Compd. 14, 70–72 (1978). which gives straight heating urea and glycine in sulphuric acid (1:1:0.5eq) but I
didn't get crystallisation. And British patent GB991644 by directly fusing solid urea with glycine, this is gross and ugly forget his route.
Theres little information on nitrohydantoin itself other than GB991644, where it's used as an intermediate to 1-aminohydantoin. Its nitration uses
fuming HNO3 + P2O5, add hydantoin at 10C then stir as it returns to room temperature over the next 4 hours then dump in ice water and filter. This
works fine, I got 66% yield. m.p. crudely measured on hotplate coinciding with the 173C from the patent.
I also tried sulphuric acid + KNO3 nitration, 40g KNO3 + 65mL H2SO4, cooled to 10C and 11g hydantoin added. This gets really thick by the end and had
to be raised to 16C for stirring. It was left 30min after last addition then dunked for 22% yield with the same melting point.
It dissolved readily in acetone but I couldn't get it to precipitate on addition of water.
These nitrations are very smooth, no noticeable exotherm and hydantoin readily dissolves. The low yield from KNO3/H2SO4 may well be because it was run
too cool and too short, I'd forget i'd left the HNO3/P2O5 for 4 hours and dunked the KNO3/H2SO4 too early.
It does not seem like a dinitro derivative is possible. Dinitrodimethylhydantoin is known however uses a novel nitration process (trichloroacetic
anhydride, ammonium nitrate in nitromethane). dimethylhydantoin is available OTC as its chloro-bromo compound for pools, presumably this can be
dehalogenated via heating with NaOH.
As previously said, 1-nitrohydantoin has no published explosive properties. It's closest relative is dinitroglycoluril (DNGU), 1-nitrohydantoin in
effect being half DNGU with an extra carbonyl group. If its detonatable its likely insensitive, and relatively low powered owing to its oxygen
balance. Its saving grace may be its density, which is unknown, but has the possibility of being high (DNGU is 1.99g/cm3). On ignition it does sustain
deflagration leaving black residue.
It's acidic, I dissolved it into 1eq of sodium hydroxide and precipitated the silver salt, attempt at a lead salt failed. The silver salt deflagrated
energetically but not explosively leaving silver fluff residue.
I have not tried to detonate it.
Speculating where else it can be taken; it could probably be chlorinated resulting in the retarded child of RDX and TCCA. It can likely be hydrolysed
to nitraminoacetamide, which might condense with hydrazine followed by nitrous acid to yield nitraminoacetylazide, but I'm not even sure if that is a
known compound.
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Axt
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Chlorination proceeded as expected, 2.9 g (0.02 mol) of 1-nitrohydantoin is dissolved into 100 mL of cold water containing 0.8 g (0.02 mol) sodium
hydroxide formiing a pale yellow solution. Chlorine gas is bubbled through the until a large white deposit has formed which is filtered, flushed with
100 mL of water and dried.
Its melting point was lowered to approximately 140°C, from 175°C for the non-chlorinated parent. It takes fire easier and deflagrates more
vigorously than the non-chloro. It will initiate under the hammer on anvil, whereas the non-chloro will not. It still leaves a lot of black residue.
I haven't tried the hydrolysis as I don't think the primary nitramine group would survive the following projected abuse. It might be worth making EDNA
and seeing if it gasses off in hydrazine, and nitrous acid.
The nitration was again attempted using KNO3-H2SO4 and just adding it at room temperature and leaving it for 4hrs under stirring but with the same low
yield, about 3.5g from 11g hydantoin. I now think the problem is that it is too soluble, attempting to wash out the acids washes out most of the
yield. Using a minimum of fuming HNO3 is preferred.
[Edited on 1-4-2025 by Axt]
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dettoo456
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Following the use of amino acids as building blocks, have you looked at Sydnones at all? I don’t believe N-nitrosoglycine would be stable enough to
cyclize and stay as the unsubstituted sydnone, but perhaps N-nitroso-α-alanine could be dehydrated (with either Ac2O or a suitable strong dehydrating
proton donator like PPA) to the 5-Methylsydnone. The nitramine of that could yield what looks like a decent compound.
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Axt
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Nope sydnones were not on the radar at all, first I've heard of them. I had a quick search but couldn't find any stable sydnones without N
substitution, nor any energetic derivatives, although the sydnone ring would be an energetic "explosophore" moiety in itself.
An interesting one that did come up albeit off topic was the azasydnones which are annoying although approachable from an amateur perspective derived
from 5-ATZ.
I'm just ignoring the reactivity of the primary nitramine group here but the destination of nitrohydantoin could be Nitraminomethylamine as attached,
which may be an insensitive HE although I feel a simple molecule like this should be well known? and a possible building block, but for what I do not
know.
[Edited on 17-4-2025 by Axt]
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dettoo456
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Yes, Sydnone itself is not isolatable on its own, similar to the free Azasydnone - both are more stable as the acids (diazoacetic and azidoacetic
respectively). They say the rings can exist though, if a suitably bulky donating group is thrown on the side. The issue I looked at a while ago
related to these was essentially if functionalization of the 5-position can suitably stabilize the ring in either Azasydnone or Sydnone instead of
messing with the 1-position, since that’d obviously hinder nitration ability. Although I have my suspicions that any e-withdrawing groups like a NO2
on that 1-N or even the 5-C would tear the rings apart.
Ethyldiazoacete is handled commonly in industry, so maybe the ester of diazopropionate (from nitrosoalanine) could show promise?
The 3-nitroaminomethylamine you spoke of is interesting. I tried to make methylenediamine a while ago, as it is able to be prepared (in low yield) and
extracted as its salt. I can’t find the prep method I followed at the moment thought. I wanted to see if Methylenedinitramine was even stable, as
that’d be obviously powerful. I don’t think it is though, and I don’t know how stable 3-nitroaminomethylamine would be either.
[Edited on 17-4-2025 by dettoo456]
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Axt
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Quote: Originally posted by dettoo456  | | I wanted to see if Methylenedinitramine was even stable, as that’d be obviously powerful. I don’t think it is though, and I don’t know how
stable 3-nitroaminomethylamine would be either. |
Methylenedinitramine (MEDINA) is well known though? and stable, even taken to pilot production. PATR2700 M49 has a large entry. 4% better performance
than RDX in shaped charges. 71.9g sand crushed compared to 61g RDX. Methylenedioxyamine is known too (H2NOCH2ONH2), isolatable but unstable. I made
the mono-oxyamine nitrate which seemed to be stable enough although sensitive.
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MineMan
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| Quote: Originally posted by Axt | | Quote: Originally posted by dettoo456 | | I wanted to see if Methylenedinitramine was even stable, as that’d be obviously powerful. I don’t think it is though, and I don’t know how
stable 3-nitroaminomethylamine would be either. |
Methylenedinitramine (MEDINA) is well known though? and stable, even taken to pilot production. PATR2700 M49 has a large entry. 4% better performance
than RDX in shaped charges. 71.9g sand crushed compared to 61g RDX. Methylenedioxyamine is known too (H2NOCH2ONH2), isolatable but unstable. I made
the mono-oxyamine nitrate which seemed to be stable enough although sensitive. |
Do you have the VOD of MEDINA and its detonation pressure and density? For those sand crushing test I would expect far more improvement than 4 percent
in shape charges as HMX should provide more than that… and CL-20 provides 40 percent more penetration than HMX in shape charges according to
articles by the US Army.
It seems it is higher performance than HMX. I fact it was investigated 65 years ago. What is old is new again. Makes me wonder what the army research
laboratories and national labs are cooking up.
https://scholar.google.com/scholar?hl=en&as_sdt=0%2C3&am...
[Edited on 18-4-2025 by MineMan]
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Axt
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MEDINA has lower crystal density than RDX, thus lower maximum brisance, but more significantly outperforms it at similar densities. It performs best
in the "power" category due to its perfect OB.
MEDINA 8500m/s @ 1.68g/cm3. power 188-210% TNT
RDX 8270m/s @ 1.675g/cm3. Power 170% TNT
These are tabled PATR2700 2 B67.
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MineMan
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| Quote: Originally posted by Axt | MEDINA has lower crystal density than RDX, thus lower maximum brisance, but more significantly outperforms it at similar densities. It performs best
in the "power" category due to its perfect OB.
MEDINA 8500m/s @ 1.68g/cm3. power 188-210% TNT
RDX 8270m/s @ 1.675g/cm3. Power 170% TNT
These are tabled PATR2700 2 B67. |
That makes sense. However the power of an explosive is the heat of detonation x the volume of gases. RDX has perfect oxygen balance of 0 for CO which
would mean a higher volume of gas but less heat of detonation. Anyways, this is off hand without calculating the heat of detonation and volume of
gases per gram. I am a bit surprised at the difference as the sand crushing test is substantial percentage. But of course the perfect OB lends to
higher Vdets at the same density 
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