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Author: Subject: N-Nitro-N-methylhydroxyacetamide Nitrate
Rosco Bodine
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[*] posted on 14-12-2011 at 02:50
N-Nitro-N-methylhydroxyacetamide Nitrate


Here is an interesting and obscure energetic material obtainable from common precursor materials like ammonia, acetic acid and formaldehyde or paraformaldehyde.

Reportedly the material is stable and has a mp comparable to TNT but a RE of 133% TNT. Sensitivity and power are comparable to Tetryl. See PATR Vol. 8 page M-107.

Attached are relevant patents US2449843 and US2443903 and US5130328 which has an example of synthesis of the precursor for nitration which is hydroxymethylacetamide
gotten by reaction of acetamide with formaldehyde.

Attached are also some other references related to the precursor.

Attachment: Page M-107 PATR Vol. 8 M-P.pdf (94kB)
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Attachment: US2449843 N-Nitro-N-methylhydroxyacetamide Nitrate.pdf (95kB)
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Attachment: US2443903 Nitratoalkyl Amides.pdf (71kB)
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Attachment: US5130328 Preparation of Hydroxymethylacetamide Example 1.pdf (481kB)
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Attachment: Pages from hydroxymethylacetamide page 6 10_chapter3.pdf (26kB)
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Attachment: Hydroxymethylacetamide Organic Syntheses Wiley.pdf (170kB)
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Attachment: Acetamide Organic Syntheses Wiley.pdf (112kB)
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AndersHoveland
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[*] posted on 15-12-2011 at 20:38


The structure of N-Nitro-N-methylhydroxyacetamide Nitrate appears to be,

CH3-C(=O)-N(-NO2)-CH2-ONO2

I am surpised that a nitrate group can be so stable on a methylene group also attached to a nitramine group.
I am also surprised that the nitramine group can form in the presence of concentrated sulfuric acid.

This indeed appears to be a unique explosive with ideal properties, easily accessible to the amateur hobbyist.
Great find Rosco Bodine!

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AndersHoveland
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[*] posted on 16-12-2011 at 02:09


Is it possible those patents could be inaccurate?
Perhaps the compound that is actually forming is:
Ac-N(-NO2)-CH2-N(-NO2)-Ac,
where Ac = acetyl group

This seems to me a more likely possibility.

These types of methylene-N-acetylnitramine compounds are typical byproducts from the synthesis of RDX, for example.

[Edited on 16-12-2011 by AndersHoveland]
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Rosco Bodine
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[*] posted on 16-12-2011 at 02:53


Quote: Originally posted by AndersHoveland  
Is it possible those patents could be inaccurate?
Perhaps the compound that is actually forming is:
Ac-N(-NO2)-CH2-N(-NO2)-Ac,
where Ac = acetyl group

This seems to me a more likely possibility.


I don't see how on earth you come up with that.

So...do you think Filbert is a nut ? :D

CH3CONHCH2OH + 2 HNO3 ----> CH3CON(NO2)CH2ONO2 + 2 H2O

It is both a nitroamide and a nitroester

A similar case occurs with the Glucose Nitroureide Tetranitrate

But here we have an acetamidomethanol nitrated to yield
an acetylnitroamidomethyl nitrate

[Edited on 16-12-2011 by Rosco Bodine]
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nitro-genes
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[*] posted on 16-12-2011 at 06:17


Nice find! Meltcastable, low sensitivity to heat, more brisant than TNT as a binder, fairly straightforward synthesis and low ciritical diameter according to its use as basecharge in compound detonators... Where is the catch?! ;-)
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Rosco Bodine
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[*] posted on 16-12-2011 at 12:49


No experiments have been done by me with this material, so there isn't much I can add. One thing of interest that I did note is the evolution of gas reported at 50C which has a parallel with regards to the synthesis of RDX where there evidently occurs formation of unstable intermediates or byproducts that are decomposed by mild heating. That reaction aspect of gas evolution involving the nitrolysis is something which should probably be compared, studied to see if there exists a similarity involving an intermediate or byproduct in the nitration / nitrolysis, because some of the experiments towards optimizing yields and strategies for acid recovery or salvaging useful products by making use of the spent acid from RDX synthesis could possibly also be useful and applicable here.
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AndersHoveland
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[*] posted on 19-12-2011 at 15:23


I strongly suspect that the compound they obtained was actually N,N'-diacetyl-methylenedinitramine. Consider that the patent is from 1948, and the researchers probably did not have any convenient method of determining the molecular structure available to them. One impotant measurement the researchers made on their compound was that it contained a 15.52% nitrogen content by weight.

Molecular formula for
N,N'-diacetyl-methylenedinitramine: C5O8H8N4
N-Nitro-N-methylhydroxyacetamide Nitrate: C3O7H5N3

I cannot find any information about N,N'-diacetyl-methylenedinitramine, but N,N'-dimethyl-methylenedinitramine has been researched as an energetic plasticizer.

If my suspicions are correct, that this compound is indeed N,N'-diacetyl-methylenedinitramine, the acetyl groups should hydrolyze off in NH4OH, leaving methylene dinitramine (MEDNA). (actually it would leave the ammonium salt of MEDNA, which would then have to be acidified and the ammonium salt separated out). MEDNA melts at 105-106deg C (it begins to decompose with the evolution of gas just a few degrees higher, at 110degC ), so it would not be very difficult to verify this.

The procedure in the patent uses 98.5% conc. HNO3 and 96% H2SO4, which is remarkable in that it shows that nitramines can be formed, at least under some conditions, in the presence of concentrated sulfuric acid. (no doubt 60-70% HNO3 could be used instead, which would be compensated for by simply using a larger portion of the concentrated H2SO4).

As MEDNA can easily condense with CH2O to form HMX, this could be part of a route to obtain pure HMX using only plain mixed acids for the nitration step.
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Rosco Bodine
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[*] posted on 19-12-2011 at 19:12


Quote: Originally posted by AndersHoveland  
I strongly suspect that the compound they obtained was actually N,N'-diacetyl-methylenedinitramine. Consider that the patent is from 1948, and the researchers probably did not have any convenient method of determining the molecular structure available to them. One impotant measurement the researchers made on their compound was that it contained a 15.52% nitrogen content by weight.


Some of the old chemists and other scientists have done reasonably accurate work circa 1948 was well along into the time of reasonably accurate analytical work so I trust those figures are close enough for DuPont and close enough for government work :D Only two of the three nitrogens would be set free in the nitrometer, so the 15.63% corresponds with an actual Nitrogen content of 23.4634% for C3O6H5N3
N-Nitro-N-methylhydroxyacetamide Nitrate or my other more trivial name for the compound acetylnitroamidomethyl nitrate molecular weight 179.0881

Quote:

Molecular formula for
N,N'-diacetyl-methylenedinitramine: C5O8H8N4
N-Nitro-N-methylhydroxyacetamide Nitrate: C3O7H5N3


Count your Oxygens again Anders .....
you have an interloper:D

Quote:

I cannot find any information about N,N'-diacetyl-methylenedinitramine, but N,N'-dimethyl-methylenedinitramine has been researched as an energetic plasticizer.

If my suspicions are correct, that this compound is indeed N,N'-diacetyl-methylenedinitramine, the acetyl groups should hydrolyze off in NH4OH, leaving methylene dinitramine (MEDNA). (actually it would leave the ammonium salt of MEDNA, which would then have to be acidified and the ammonium salt separated out). MEDNA melts at 105-106deg C (it begins to decompose with the evolution of gas just a few degrees higher, at 110degC ), so it would not be very difficult to verify this.


Okay you volunteered to confirm "If" your suspicions are correct .....it would not be difficult.
Quote:

The procedure in the patent uses 98.5% conc. HNO3 and 96% H2SO4, which is remarkable in that it shows that nitramines can be formed, at least under some conditions, in the presence of concentrated sulfuric acid.

So can RDX be formed in the presence of sulfuric acid, this is not unprecedented.....it just makes things difficult with regards to RDX. Other nitramines like acetylnitroamidomethyl nitrate aren't necessarily going to encounter the same difficulty.
Quote:

(no doubt 60-70% HNO3 could be used instead, which would be compensated for by simply using a larger portion of the concentrated H2SO4).

That could be overreaching because moisture even in the presence of H2SO4 could still be a sensitivity issue with regards to oxidation. It's a huge "maybe" there instead of a "no doubt".

Quote:

As MEDNA can easily condense with CH2O to form HMX, this could be part of a route to obtain pure HMX using only plain mixed acids for the nitration step.


There is still a lot of "if" involved in your suspicion which is the premise.

The low melting point of this compound could be reduced further in binary or ternary or quaternary melts / possible eutectics. Candidate materials which would probably be chemically compatible are Glucose Nitroureide Tetranitrate,
RDX, HMX, and R-Salt, Pentryl, and Tetryl. Another curiosity is what may happen in a melt or solvated system with Urea Perchlorate .....would transesterfication occur and a possible perchlorate variant result ....acetylnitroamidomethyl perchlorate :D Such an experiment does not fill me with enthusiasm for reason of the safety issue unknowns. But it would seem to be a compound having interesting potential as an energetic if it exists.

[Edited on 20-12-2011 by Rosco Bodine]
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