killswitch
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What is the actual mechanism for HMTD?
The mechanism for the formation of acetone peroxide (dimer and trimer) are relatively simple. From what I understand, they're just the radical
polymerization of the geminal diol hydrated form of the ketone, initiated by hydroxyl radicals from the peroxide. A first-year (though maybe not first
semester) organic chemistry student could draw a step-by-step diagram of the entire reaction.
But for hexamethylene triperoxide diamine, formation of the peroxide requires scission of amine-methylene bonds. How exactly does that occur under the
given conditions, and what limits the formation of hexamethylene chloride or citrate and the hydrolysis to formaldehyde and ammonia?
And is it true that the three-dimensional structure of HMTD resembles a continuation of the adamantane motif, but with one bond at each vertex on the
joining face replaced by a lone pair? Actually building the thing out of a MolyMod plastic kit showed me just how strained the molecule actually is,
assuming I built it correctly. The geometry is beautiful, but damn if that isn't a lot of lone pairs forced to face each other.
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AndersHoveland
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I have wondered why the nitrogens do not get oxidized to the N-oxide.
For example, H2O2 oxidizes trimethylamine to trimethylamine N-oxide.
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killswitch
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In related news, researchers have discovered that red meat causes hardened arteries due to the presence of gut flora that digest carnitine to
trimethylamine. TMA is oxidized in the liver to the N-oxide, which is a known atherosclerotic.
[Edited on 23-4-2013 by killswitch]
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Fantasma4500
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actually never thought about hexamine and hcl, why doesnt it react when mixed..?? or perhaps it does?
weird
perhaps its lacking concentration of HCl?
perhaps try in mL scale on a very sturdy glass plate or something alike to mix equal amounts of hexamine, concentrated H2O2 and HCl
perhaps in different ratios
or try to see if hexamine can react with hcl at all in low concentrations.. i think this might be what stops it from happening..
now that i think of it..
you use citric acid with hexamine, but im very sure ive seen it made with hcl aswell?
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Adas
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Quote: Originally posted by Antiswat  | actually never thought about hexamine and hcl, why doesnt it react when mixed..?? or perhaps it does?
weird
perhaps its lacking concentration of HCl?
perhaps try in mL scale on a very sturdy glass plate or something alike to mix equal amounts of hexamine, concentrated H2O2 and HCl
perhaps in different ratios
or try to see if hexamine can react with hcl at all in low concentrations.. i think this might be what stops it from happening..
now that i think of it..
you use citric acid with hexamine, but im very sure ive seen it made with hcl aswell? |
Some people make HMTD with HCl and say it works very well.
Rest In Pieces!
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chemcam
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I have tried in the past using HCl and never got the desired HE product, I tested small sample with hammer and fire to be sure. I end up with ammonium
chloride crystallizing out and a bright neon-like yellow/green colored solution of something. I would guess the H2O2 caused the color by oxidation of?
-------------------------
I have however hydrolyzed hexamine with HCl to get ammonium chloride and formaldehyde, that reaction produced a clear solution. This is a preparation
I will not do again without a strong fume hood. So yes, hexamine and HCl definitely react.
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virgilius1979
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I've tried both citric and HCl; HCl works as well, but you need to keep an eye on temperature, as it rises more than if you use citric acid.
H2SO4 should be diluted first, not to be used concentrated, as the reaction is highly exothermic.
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kratomiter
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This week I tried making some HMTD (first time) without succes.
I keep temperature under 0C, mixing 14 g pure hexamine in 50 ml 35% H202.
I tried with HCl, Acetic Acid, nitric, sulphuric... Neither give any HMTD, but there are people getting good yields with HCl.
A magnetic stirrer is a must?
I realized that hexamine and HCl reacts at higher temperatures, giving a strong formaldehyde odor.
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virgilius1979
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There are already many threads about this. UTFSE !
Your hexamine might be contaminated, or you're not controlling the temperature.
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AndersHoveland
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It does react, it simply forms the salt hexamine di-chloride. Apparently higher concentrations of acid can cause the hexamine to disproportionate into
methylamine salts and formic acid, but from what I have read, this generally requires temperatures above 90°C.
http://www.erowid.org/archive/rhodium/chemistry/methylamine....
Actually, this could potentially explain why the nitrogen do not get oxidized. They are protonated. By the time the solution is neutralized, the H2O2
is also gone. I wonder if it is possible to oxidize HMTD to the N-oxide with H2O2 at neutral pH, or whether that would cause the product to be
destructively oxidized/hydrolyzed.
[Edited on 25-4-2013 by AndersHoveland]
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chemcam
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| Quote: Originally posted by kratomiter | This week I tried making some HMTD (first time) without succes.
I keep temperature under 0C, mixing 14 g pure hexamine in 50 ml 35% H202.
I tried with HCl, Acetic Acid, nitric, sulphuric... Neither give any HMTD, but there are people getting good yields with HCl.
A magnetic stirrer is a must?
I realized that hexamine and HCl reacts at higher temperatures, giving a strong formaldehyde odor.
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I know these threads on HMTD are everywhere so I'm only going to say a few necessary things.
If you like your fingers, hands, arms, upper torso, your life then I would not make so much, 14g, that is a hell of a lot. It is so much safer and
smarter to make a maximum of couple grams each time. What will happen is you will have a HUGE pile, then you will take a small sample to test
friction/shock, it will surprise you how sensitive it is, then you will be scared to go near your pile, and have a hard time disposing it. Maybe you
have a death with, I don't know. HMTD and TATP are very similar in stability and safety. Just be aware, I'll stop being a wet towel now. If this is
your very first HE you may want to reconsider and find one which is a little more stable and forgiving.
I see one flaw to your synthesis you wrote in addition to not having the preferred acid. If you really want help post the ENTIRE procedure
step-by-step exactly what you did.
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Adas
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| Quote: Originally posted by AndersHoveland | Actually, this could potentially explain why the nitrogen do not get oxidized. They are protonated. By the time the solution is neutralized, the H2O2
is also gone. I wonder if it is possible to oxidize HMTD to the N-oxide with H2O2 at neutral pH, or whether that would cause the product to be
destructively oxidized/hydrolyzed.
[Edited on 25-4-2013 by AndersHoveland] |
Remember that not every nitrogen in organic compounds can be oxidized. And I would assume that HMTD is too resistant towards oxidation + it is
insoluble.
Rest In Pieces!
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kratomiter
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Thank you everyone, I got a good yield with just 5 mL HCl 20% more.
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chemcam
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Can you post your whole process, I'd like to see it since I have never gotten it to work without citric acid and are you sure what you got is HMTD
have you tested it yet?
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killswitch
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What solvents dissolve HMTD?
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Adas
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There are no solvent that can dissolve HMTD easily, AFAIK.
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killswitch
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Looking at it, it seems like a weak base with a band of high electron density at the center, surrounding the peroxide bonds. It seems like it would be
only weakly polar, if at all.
So, an aprotic, mildly electrophilic, weakly polar liquid? Maybe nitromethane, or something similar?
Of course, another route would be to form a quaternary salt, but... Jesus Christ. I wouldn't be surprised if such a thing matched lead azide crystals
in sensitivity.
Though I guess if you're in it for the chemistry, you could try something crazy like HMTD nitrate or HMTD picrate, but I wouldn't want to make much
more than is necessary to be seen with the naked eye.
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killswitch
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Now, when I said I wanted the mechanism, I meant a step-by-step. Something like this, which I assume is the TATP reaction. I drew it in ChemDoodle:
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kratomiter
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| Quote: Originally posted by chemcam |
Can you post your whole process, I'd like to see it since I have never gotten it to work without citric acid and are you sure what you got is HMTD
have you tested it yet? |
First I cooled down to -10ºC 50 mL H2O2 35%, then added 14 grams Hexamine.
After stirring and keeping the solution in an ice bath, I drop 10 mL HCl 20%.
No precipitated was formed after 6 hors, so I took out the solution form the ice bath.
After around 8 hours at room temperature, no precipitated was formed.
I tried adding 5 mL HCl 20% more... I just 20 min I had a lot of cristals, so I didn't wait long and filtered them.
Yes, it seems to be very pure HMTD and deflagates without no residues left.
I detonated with it MHN, even p-mononitrotoluene and commercial MEK peroxide.
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chemcam
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Thanks, even when I use citric acid I don't get any crystals until I remove the flask from the ice bath and the temp rises to room temp. That's when
they always fall out I guess.
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killswitch
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So does anybody know the reaction mechanism or is this thread going to be synthesis questions by third parties?
I had this same problem trying to get the equilibrium constant for the nitration of glycerin.
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