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Author: Subject: Amine Peroxides - the others
Axt
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[*] posted on 30-1-2005 at 20:41
Amine Peroxides - the others


Primary amines, when condensed with formaldehyde with H2O2 yield peroxidic products, most known is HMTD (from ammonia), and to a lesser extent TMDD (from urea). Heres some experiments to determine the properties of some other amine peroxides and open up some more discussion on alternative amines that could provide interesting explosive properties.

<b>Tetramethylenediperoxidedicarbamide</b>

Synthesis: 12g fertiliser grade urea was dissolved into 50ml water, then 40g 30% formaldehyde was added followed by 28g 50% peroxide and 18g 70% nitric acid. The mixture was placed into a fridge for 3 days after which the solition had turned solid with a white precipitate. This was filtered, flushed with water and dried.

<center><img src="http://www.sciencemadness.org/scipics/axt/TMDD.jpg"></center>

The precipitated TMDD must be completely dry to be ignited, and is very insensitive to impact. On ignition it deflagrated with the a soft orange flame characteristic of the peroxides, but considerably slower the HMTD. <a href="http://pulse.altlist.com/images/TMDD-german.pdf">TMDD Reference</a> (German).

<b>Ethylenetetramethylenediperoxidediamine</b>

Synthesis: 5.5g ethylenediamine was slowly injected into under the surface of 40g of 30% formaldehyde solution resulting in a very hot exotherm and the solution turning yellow. It was placed into a freezer and brought down to -10°C. Into this was slowly injected with an eyedropper 20g of 50% peroxide, temp had to be maintained <10°C or a violent runaway may result. On completion of the addition the solution had formed a slurry of crystals, this was left in the fridge overnight whereby it become solid with the precipitate. I recommend diluting the formaldehyde solution before addition of ethylenediamine.

<center><img src="http://www.sciencemadness.org/scipics/axt/HMDD.jpg"></center>

The ethylenediamine derivative is essentially HMTD minus a peroxide linkage, thus performance is lacking, although it deflagrated considerably faster then TMDD. I never tested the impact sensitivity of HMDD. <a href="http://pulse.altlist.com/images/Caged-amine-peroxides.pdf">ETDD Reference</a> (English).

<b>Trimethyleneperoxideazine</b>

Synthesis: 10g hydrazine sulphate was dissolved into 300ml of boiling water. Temperature was reduced to 50°C and a solution comprised of 40g 30% formaldehyde in 20g 50% H2O2 was added to the hydrazine sulphate. A slight exotherm resulted 50->58°C and immediate precipitation of a crystaline product. The solution was left for 30min then filtered, flushed with ether and dried.

<center><img src="http://www.sciencemadness.org/scipics/axt/TMPA.jpg"></center>

I assume trimethyeneperoxideazine takes on the dimeric structure above, thus hexamethylenediperoxidediazine. I used excess formaldehyde to try and achieve its tetraperoxide, but on ignition it flares off at a rate between that of HMDD & TMDD, accompanied by a larger more intense flame. The peroxide is not very sensitive to impact, even banging it with a hammer did not result in detonation. <a href="http://pulse.altlist.com/images/hydrazine-peroxide-german.pdf">TMPA Reference</a> (German).

The reference above was translated for me by Chemoleo, below is the translation of the "important bits".

Quote:
Anyway, regarding the trimethylazin peroxide (structure see page 496, acc. to their analyses, or I of page 492) 52 g of hydrazine sulphate is dissolved in 1.5 l of warm 3% H2O2 (about 40-50 deg C). To this one adds a mixture of 200 ml of formalin (presumably the lab reagent percentage of 38 % w/v, just checked), and 1 l 3% H2O2.
After a short while, the crystalline peroxide precipitates. This was filtered off 1/2 hour later, washed with H2O, EtOH and ether, and dried in a desiccator over P2O5 (I am sure drying at air will do).

Yield is 24.3 g. Anothe 4.7 g crystallised upon standing for 24 hours. Total yield 29 g, 71%. This compound is smell-less, slightly yellow, and somewhat soluble in Chloroform. In the flame, this deflagrates rapidly with little smoke. Melting it causes explosion. Conc H2SO4 causes explosion with the appearance of fire. It is NOT much sensitve against impact, it needs a VERY hard hammerblow to bring to explosion.

No major conclusions, except a disappointing one (and expected) which is that HMTD still surpasses the above compound in brisance, or the ethylamine derivative (for structure see first page).


The attachment shows three consecutive frames taken of the peroxides deflagrating. Which can also be seen in the movie <a href="http://www.geocities.com/roguemovies8/">here</a>. Other amines may provide interesting products, hydroxylamine for example could possibly outperform HMTD as long as the hydroxyl group is preserved. Maybe even with the correct use of solvents/temperatures and concentrations Octamethylenetetraperoxidediazine from hydrazine could be achieved ... well maybe.

[Edited on 6-1-2008 by Axt]

amine-peroxide-sequence.jpg - 94kB
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[*] posted on 31-1-2005 at 11:41


Any speculations on what sort of sensitivity/power the product of this procedure with ethylamine could produce? I've been thinking of trying it but not if it could be anything like ethyl peroxide.



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[*] posted on 31-1-2005 at 12:09


You can expect ethylamine derivative to be pretty poor, nothing like ethyl peroxide. Check the hydrazine reference for the peroxide of methylamine. Nitrating ethanolamine -> ethanolamine dinitrate, find a solvent (maybe ethanol/ether) and try to condense with formaldehyde/peroxide could provide something better. O2NO-CH2-CH2-N(CH2-O-O-CH2)2N-CH2-CH2-ONO2.
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[*] posted on 31-1-2005 at 12:37


Why was there no citric acid needed for HMDD to form?
Does HMDD form easier than HMTD?

Ethyl peroxide- was this discussed?
What's this substance?

Still interesting, Axt, even though no high-power explosives are made this time.
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[*] posted on 31-1-2005 at 13:06


If you pour ethylenediamine/formaldehyde/peroxide together you get pops, bangs and peroxide crystals everywhere, sadly I know this as fact :( I made the mistake of assuming an acid would be needed as well. Acetic acid is used in the reference provided, but with the concentrated solution its not needed.

Ethyl (hydro)peroxide is in equalibrium in a mixture of peroxide/ethanol but being soluble and only present in small concentrations, its not easily isolated.
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[*] posted on 13-2-2005 at 11:45


When I looked up the synth. of urea, I stumbled across the Woehler type synthesis of semicarbazide, H2N-CO-NHNH2. It seems easy enough, if one has hydrazine and cyanate. Equally, the semicarbazide can be reacted on to the bis-urea, (H2N-CO-NH)2.
I imagine both should make more interesting peroxides with CH2O and H2O2 than urea itself?!

[Edited on 13-2-2005 by chemoleo]




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[*] posted on 19-2-2005 at 08:37


<b>Tetramethylenediperoxidebis(nitroaniline)</b>

No references for this one, but nitroaniline isn't very flammable, but the product of the synth below is, so I assume its taking on the structure below. I dont think aniline itsef will work as it precips immediately as the aniline/formaldehyde resin.

Synthesis: 5g nitroanilne was dissolved into 200ml ethanol, into this was added 10g 30% formaldehyde and 15g 50% peroxide. A bright yellow precipitate formed overnight which was filtered and dried.

<center><img src="http://www.sciencemadness.org/scipics/axt/tetramethylenediperoxidebis(nitroaniline).jpg"></center>

The yellow precipitate deflagrates slowly, and not very energetically with the distinct smell of burning hexamine. I also formed a precipitate from acetaldehyde/nitroaniline/peroxide, thus probably forming a tetraethylidene derivative which hasnt been ignited, though it isn't going to do much. Trying the higher nitroanilines would be interesting, even if they arn't going to be a practical explosive. The movie of the above was tagged onto the end of the other <a href="http://geocities.com/roguemovies8/">amine peroxide</a> movie, though its not worth the extra 3MB download.

<center><img src="http://www.sciencemadness.org/scipics/axt/tmdpbna.jpg"></center>

Anyway, <a href="http://v3.espacenet.com/origdoc?DB=EPODOC&IDX=FR893942&F=0&QPN=FR893942">french patent 893942</a> gives some discussion on explosive amine peroxides, focused on the derivative of tricrotonoylidenetetramine, mentions its suitable for detonators, though I'm a sceptical considering the structure they give which is probably wrong (didn't get HMTD right either). Others are mentioned, such as derivatives of Schiff's bases.

[Edited on 9-12-2005 by Axt]
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[*] posted on 6-1-2008 at 04:11


What would ethyl amine + formaldhyde yield ?



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[*] posted on 6-1-2008 at 08:49


Below is the structures assigned to the amine peroxides according to the given references. Note that a lot of these are wrong but demonstrate the difficulty in determining the correct structure in the early years, when most of the study was done. The empirical formulas are correct however the MW and structure vary considerably.

Ethylamine is there, however I'd think that it would form a dimeric structure due to the peroxide moiety's preference for a larger ring, thus being an analogue to the known ammonia derivative, HMTD.

[Edited on 7-1-2008 by Axt]

structures.jpg - 56kB
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[*] posted on 6-1-2008 at 09:12


CH2-O-O-CH2
/ iiiiiiiiiiiiiiiiiiiiiiii \
N-C2H5 C2H5-N
\ iiiiiiiiiiiiiiiiiiiiiiii /
CH2-O-O-CH2

Would be something like that?


[Izmenjeno 6-1-2008 Bromine]




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[*] posted on 19-1-2008 at 21:34
HMTD from ammonium sulfate and formaldehyde


From https://sciencemadness.org/talk/viewthread.php?action=attach... (German)

Here they use a one-pot direction straight from ammonium sulfate and formaldehyde, perhaps someone is interested in testing this.

Quote:
HMTD:

50 g of ammmonium sulfate (or hydrogen sulfate, it doesn't say) is dissolved in an equal mass amount of 3% commercial H2O2, brought to 55 *C and filtered. To the warm solution 5 g of 40% formaldehyde is added. After a few moments a large amount of precipitation occurs, which is separated by filtration after 30 minutes in the cold.

Much less time consuming than the method suggested in COPAE.
They state that the product is soluble in hot glacial acetic acid, benzene (toluene?), chloroform, and ethylacetate, where it can be recrystallised as rhombic plates.


In the paper they also describe peroxides of acetaldehyde, benzaldehyde and chloraldehyde.


[Edited on 20-1-2008 by chemoleo]




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[*] posted on 14-2-2008 at 06:58


The preparation of acetaldehyde peroxide was done in accordance to the link chemoleo gave above, the quantities used were 17g H2SO4, 12g H2O and 2g 50% H2O2. This was cooled to -10°C then 1g acetaldehyde was added where temperature rose to +5°C. It was left sit in the freezer for 2 hr then at room temperature for two days. The milky emulsion that had formed in the freezer seperated at a clear upper layer. The solution was diluted with water whereby the oil fell to the bottom as globules, see attachment. in standing a number of days a few crystals did apperar in solution though immediately disappeared when it was swirled.

The actual constitution of the oil isnt well given in the literature, they assigned it CH3-CH(OH)-O-O-CH(OH)-CH3 which turns into the crystalline CH3-CH=(O-O)2=CH-CH3 on heating, though one would expect this diol derivative to undergo simular reactions to dimethylol peroxide with amines and at least be somewhat soluble, the oil does neither. Its possibly a polymeric diperoxide? its a thin liquid at room temperature though gets quite viscous at 0°C. Its an exceptionaly violent explosive and very sensitive, a slight tap steel on steel will result in detonation and if a small drop if touched by the flame of a match it detonates removing the end of the said match.

Anyways to bring that back on topic the same was tried in the presence of ethylenediamine, with the same oily product as a result. This suggests that it cant be used in analogous reactions to formaldehye, and is supported by the fact that I have never come across an amine-acetaldehyde peroxide in the literature yet those of formaldehyde are many.

So, its probably best to ignore my claim of a a nitroaniline-acetaldehyde peroxide a few posts up as it was never tested for explosive props. I've also since come across literature attemps at peroxides with aniline and nitroaniline with formaldehyde, though they yielded no peroxidic product (no product was mentioned at all). So Tetramethylenediperoxidebis(nitroaniline) a few posts up looks wrong as well, which gives some explanation to the weakly explosive product I achieved. It should be tested without the H2O2 to see if the same products are obtained.

[Edited on 15-2-2008 by Axt]

acetaldehyde peroxide.jpg - 18kB
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[*] posted on 19-2-2010 at 16:34


I think that is not a good idea to use Nitric acid as a catalyst for the sinthesis of TMDD. What about urea nitrate ?
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[*] posted on 26-10-2011 at 10:33


It would be interesting to try to use formamide instead of formaldehyde.
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[*] posted on 26-10-2011 at 10:47


Quote: Originally posted by Axt  
acetaldehyde peroxide: The actual constitution of the oil isnt well given in the literature, they assigned it CH3-CH(OH)-O-O-CH(OH)-CH3 which turns into the crystalline CH3-CH=(O-O)2=CH-CH3 on heating, Its possibly a polymeric diperoxide? its a thin liquid at room temperature though gets quite viscous at 0°C. Its an exceptionaly violent explosive and very sensitive, a slight tap steel on steel will result in detonation and if a small drop if touched by the flame of a match it detonates removing the end of the said match.


One would think it is probably structurally similar to diethyl ether peroxides. http://en.wikipedia.org/wiki/Diethyl_ether_peroxide
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[*] posted on 29-12-2011 at 06:35


What about this one made of acetamide?






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[*] posted on 29-12-2011 at 15:40


Organic peroxides made from formaldehyde tend to be less chemically stable than those made from ketones. The reaction of H2O2 with CH2O can apparently result in oxidation at ambient temperatures under some conditions. See the thread, "Producing Hydrogen by partial oxidation", http://www.sciencemadness.org/talk/viewthread.php?tid=18169


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[*] posted on 4-1-2012 at 11:01


I have a new idea. So many ideas in my head :D

TetramethyleneDiperoxideDiamine and DimethylenePeroxideAmine can be produced by hydrolysis of compounds on the left side. However, this can be done for research of those compounds only, because it is impractical. They are probably very unstable, maybe more than HMTD.

And the materials on the left side are very interesting EM (energetic materials) themselves, I think.






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[*] posted on 4-1-2012 at 22:30


I do not think this would work, because the methylene groups, -CH2-, that result from the condensation of formaldehyde with ammonia have some hydrolysis equilibrium. Those compounds you imagined would likely transiently form, but they would hydrolyse into other compounds, with the likely expulsion of some proportion of ammonia. One of the resulting products may likely be HMTD.

The peroxide of acetamide-formaldehyde only exists because the nitrogen atoms do not have any hydrogen atoms bonded to them (which can ionize off, precipitating hydrolysis).

[Edited on 5-1-2012 by AndersHoveland]
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