New HMTD synthesis?

[DBSP]

Today I was browsing through the Swedish infomania files. I was looking at the info about TMDD and at the same time I read the HMTD info while I was at it. Then I noticed a second procedure for HMTD that I hadn't noticed before, that one involved glacial acetic acid, hydrogen peroxide and hexamethylenetetramine.
<img src="http://w1.478.telia.com/~u47804009/E&W/HMTD_chems_by_DBSP.JPG" alt=" - " />
The synthesis goes like this: 10g of HMTA is dissolved in 50ml of glacial acetic acid and when the HMTD has completely dissolved 25ml of 35% H2O2 is added to the mixture and the whole thing is swirled around for a minute or two to ensure that the chemicals are properly mixed. This liquid it then allowed to stand at room temperature for about 4-5 hours. After that it's just to wash and nutrolise the usual way.
<img src="http://w1.478.telia.com/~u47804009/E&W/HMTD_by_DBSP.JPG" alt=" - " />
The good thing about this synthesis is that it's extremely fast and has a good yield compared to the usual synthesis. The yield is stated to be 75-80% of the theoretically value, the normal method has only got a yield of about 60% of the theoretically value. And it is much easier since you don't need to cool the reactants since the temperature only rises 5-10 degrees, if you would need to coll it simply dipping the vessel into some cool water would suffice.

At first I didn't belive this method to be as good as it was stated to be so I decided to have a try. I simply crushed one tablet of esbit and added it to 15ml of glacial acetic acid and swirled it untill all hex had dissolved, note that I didn't purify it first but it allmost seemes like the additives dissolves as well because there wasn't much left after a while. Then I added 8ml of 35% H2O2. I didn't experiense any temperature rise at all but that might depend on that fact that there wasn't any great volumes invlolved in the experiment. In the pics below you can see the formed HMTD one hour into the reaction, I was very supprised when I first had a look at it. All that HMTD in only one hour. I'm not used to make HMTD but the times I have done it the reaction allways have been very slow and the yields haven't excactly been very satisfying either.
This off course the first experiment but if it workes as good as this in greater volumes as well I will definately abandon AP as my primary primary. The reason to why I haven't been using HMTD has been that it's to much work and has low yields. This definately changes that.
<img src="http://w1.478.telia.com/~u47804009/E&W/HMTD2_by_DBSP.JPG" alt=" - " />
If this has been discussed here previously I appologise, if it hasn't which I think I hope this can help others. Has anyone heard of this method before? And if someone has acces to the chems needed please try this and see if you can confirm my (probable) succes.

[Mr Cool]

Seems like a good method, although essentially similar to the usual one.
Hmmm... this reminds me. Has anyone tried to make HMTD from ammonium sulphate, H2O2 and formaldehyde? It's in KIBC.

[DBSP]

It's filtered and is drying now. The washing is what takes most of the "work" time it took several liters to get all the acid out of the HMTD but this isn't a very big problem, it's just to set the tap running at the same speed as the water leaves the filter and have it running for 15 mins or so and then nutrulise and rinse with acetone to make it dry a bit faster. I belive that you might be able to go from seperate chems to finnished explosive ready to use in less than 7 hours maby even 6.

The major advantage I see with this method is that it takes very little effort to get it running. I find it very boring and tíme consuming to set up an ice bath and keep the temp where it shuld be. This method saves a lot of time and if the yields are better at that it's great.

[Madog555]

hmmm, looks good. too bad vinegar isnt concentrated, if i do this i will have to concentrate some vinegar via mega's method. i cant get citric acid so i have never made HMTD. i tried with HCl twice but i didnt get anything <img border="0" title="" alt="[Frown]" src="frown.gif" />

[Einstein]

You have to have organic acid to make HMTD or it won't work.

Not true, I used to use HCl when I made it.

<small>[ June 23, 2002, 02:16 PM: Message edited by: Mr Cool ]</small>

[xoo1246]

I have read about this method too, never got around trying it. I have a couple of liters of acetic acid (60 %), maybe I should try it.
DBSP, have you checked your mail?
Only problem with this reaction is that it stinks. :p

[Madog555]

it will work einstein, but not reliably

[DBSP]

In the text I found this synthesis it says that using 24% acid(special brand availible in sweden) might cause the reaction to get to hot, I don't see why but never the less. Using megas method for acetic acid will work very well.

A possible reason to why you didn't succed with HCl might be becuse the HMTA got decomposed by the HCl. In the text they state that: "HCl is incompatible with HMTA" and further thay say that mineral acids doesn't work very well either. And that ascorbic acid might cause allmost explosive reactions.

BTW I just weighted the HMTD, 3 grams. Is it correct that one mole of HMTA is equal to one mole of HMTD? In that case 3g HMTA is 0,021 moles that would in turn mean that the ammount of HMTD shuld be 208*0,021=4,368g 3/4,368=0,68. not to bad. The only flaw is that my scale only is sensitive to one gram, thus a 46-92% yield. I need a better scale. I'll try a larger ammount soon to lower the percentage errors.

Xoo time to check your mail. Good night folks.

<small>[ June 22, 2002, 06:51 PM: Message edited by: DBSP ]</small>

[xoo1246]

Maybe if it's cooled, anyhow you should get a more accurate scale, I bough one a few weeks ago, it's accurate down to .1 grams, can measure up to 225 grams and weren't that expensive.
Look here if you are interested:
<a href="http://www.sagitta.se/humatutr.html" target="_blank">http://www.sagitta.se/humatutr.html</a>

I quoted that text(well, almost :) ) in another post, remember?
</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica">HCl and HTMD is imcopatible, ascorbic
acid too and mineral acids.... stick to citric or concentrated acetic acid. </font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">

[Polverone]

This method seems to work very nicely! I used 10 g hexamine, 50 ml glacial acetic acid, and 40 ml H2O2 (since I know my H2O2 is pretty high concentration but I'm not positive how high). I let it react for about 5 hours. It took only about 40 minutes to start seeing HMTD precipitate out. I've filtered it and washed it with potassium carbonate solution and about 2 liters of water. When it dries I will post my yield. In any case it seems much nicer than the citric route, which always gave me trouble. It's faster too. Thanks for drawing my attention to this method.

(edit)
Okay, it's dry now. I got 4.0 g of HMTD from 10 g of hexamine. The temperature rose very little during the process. Some time in the future I'll try a batch twice as large.

<small>[ June 24, 2002, 12:33 PM: Message edited by: Polverone ]</small>

[inferno]

Citric acid is sold at any supermarket, grocery or milk bar even here. Its just a food additive, no restrictions here. Madogg, are you sure you dont have access to it? Im pretty sure if you can get sulfuric (needed to purify vinegar to glacial acetic acid) you could get citric?

THis method sounds better than the citric acid one, however my only source for glacial acetic is bloody expensive chemical supply places, so its better for me to use citric, which is like 2 dollars for 300 grams. I have 0 access to sulfuric (again, without paying exorbitant prices or opening up car batteries, something that for me is a bit hard) so i cant purify vinegar.

[DBSP]

I've aalso made a larger batch now. I used 9g of hexamine and 50ml of GAA and 25ml H2O2. I got 14g(+/-1g) from that batch.
Pulverone, something must have gone wrong with your batch, what kind of scale do you use?

<a href="http://w1.478.telia.com/~u47804009/E&W/HMTD_yield.JPG" target="_blank">http://w1.478.telia.com/~u47804009/E&W/HMTD_yield.JPG</a>
<a href="http://w1.478.telia.com/~u47804009/E&W/goran_persson_and_14g_of_HMTD_by_DBSP.JPG" target="_blank">http://w1.478.telia.com/~u47804009/E&W/goran_persson_and_14g_of_HMTD_by_DBSP.JPG</a>

[Polverone]

Something gone wrong? I was actually pleased with my results, given that I got only 3.7 g of HMTD from 14 grams of hexamine using the citric acid method from Megalomania's site. I see that there is great room for improvement, though :) It's interesting (to me) that the acetic acid HMTD came out like fine sand, whereas the citric acid HMTD is superfine, like powdered sugar.

Part of the problem may be that I don't precisely know what percentage H2O2 I have on hand. It seems quite potent - it's sold as part of a 2-part wood bleach - but I'm not sure just how much H2O2 is in there. It seems to behave very similarly to 35% peroxide that I had before (also obtained as wood bleach), but I can't find a good MSDS for this brand. Perhaps I should ask for one at the place I buy it, next time I restock. I will try another batch, I guess, and not add an extra 15 ml of H2O2 "just for safety's sake." Maybe the dilution actually lowered my yields.

I use an electronic balance with 400 g capacity and 0.1 g resolution.

I will try once more and see if experience improves my yields.

[DBSP]

I suspected that it was the H2O2 that was the problem. I hope that you find somehing about your conc, since that would greately improve your yields. This method has actually made me go from AP to HMTD as my primary explosive.

[Rat Bastard]

Im pretty sure that the wood bleach is 30% or higher. I made a batch of AP with it, and the whole solution was crystals (nice!). Wood bleach comes in 2 250ml bottles part A is H202 and part B is caustic soda.

Just after I bought the bleach kit, I opened the box and, one of the bottle lids wasn't screwed on properly (it was leaking a bit). I didn't notice untill I had small bleach white spots on my fingers. :mad:

<small>[ June 24, 2002, 01:13 PM: Message edited by: Rat Bastard ]</small>

[Zambosan]

Hmm, yield is certainly an issue!

<small>[ July 18, 2002, 12:49 AM: Message edited by: Zambosan ]</small>

[BrAiNFeVeR]

That's what I like about it too, that and it makes great putty with most kinds of binder. (Ap leaves crystals visible sometimes on the edges)

Since glacial acetic acid is not too simple for me to aquire, and if I get it, it will be far more expensive then the citric acid. Altough the shorter reaction time is good, I kind of dislike the larger crystals ...

Maybe you can alter crystal size by dissolving and making it precipate out very fast ?

[DBSP]

What solvents are HMTD suluble in? Not these at least.


grams suluble in 100g of solvent at 20 centigrades:
H2O--0,1
C2H5OH--0,01
diethylether--0,017
carbondisulfide--0,01
carbontetrachloride--0,013
anhydrus acetic acid--0,14
chloroform--0,64
C2H6O--0,33
glycoldiacetate--0,9
(info taken from the Swedish infomania files)

[Madog555]

does anyone have any idea if ASA (asprin) will work as a catylist?

that would be interesting if it did

[Zambosan]

Anything's possible; it's a weak acid.

<small>[ July 18, 2002, 12:51 AM: Message edited by: Zambosan ]</small>

[Kekule]

I assume that almost every dilute acid would work in order to create HMTD from Hexamine. This is shown by the reaction process of the fromation of HMTD.

The direct method to synthesize HMTD would be the acid catalyzed peroxidation of two mol Formaldehyde-Hydrate to Dihydroxymethyleneperoxide and the subsequent condensation of three mol of Dihydroxymethyleneperoxide with two mol of NH4+ Ions to HMTD followed by the catalyst restoring protolysis of two mol H+

Equtations:

1. Formation of Formaldeyde-Hydrate


H2CO + H20 -----&gt; H2C(OH)2

2. Peroxidation of Formaldehyde-Hydrate

2 H2C(OH)2 + H202 ---(H3O(+))----&gt; H-O-CH2-O-O-CH2-O-H + 2H2O


3. Condensation of Dihydroxymethylperoxide with Ammonium Ion

2 NH4(+) 3 H-O-CH2-O-O-CH2-O-H ----&gt;(+)H-N-(CH-O-O-CH2)3-N-H(+) + 6H20

4. Protolysis

(+)H-N-(CH-O-O-CH2)3-N-H(+) ----&gt; HMTD +2 H(+)

If you synthesize HMTD with Hexamine in an acidic solution, the Formaldehyde-Hydrate and the Ammoniumions are produced by the hydrolysis of HMTD:


C6H12N4 + 12 H20 --(H3O+)--&gt; 6 H2C(OH)2 + 4 NH4(+)

Therefore, every diluted acid could be used, because there are the neccessaty H2O molecules and the H3O(+) ions needed by the hydrolysis of HMTA and by the peroxidation-reaction. One question is, how high the concentration of the Hydroniumions has to be in order to achieve the fastest reaction velociety and which concentration of H3O(+)-ions leads to the decomposition of the O-O link in the peroxy-group

I use sulfuric acid with c(w)= 38 %( meaning ordinary battery acid). The reaction is completed in approx. 20 min(!) when using this acid.
An other question is, wich acids should be used in order to get a stable product, meaning that the very small percentage of irremoveable traces of the acid or of the salt formed by the neutralisation of the acid have no negative effect on the stability.

[kingspaz]

madog555, i think that may work but not the way i think you think <img border="0" title="" alt="[Wink]" src="wink.gif" />
the acetyl salycylic acid will by hydrolised by water to form salycylic acid and acetic (ethanoic) acid. the phenol group left on the SA will donate H+ to catylise the reaction as will the CH3COOH.

[Madog555]

ok, i doubt it will work then. it was just a thought.

[Zambosan]

Hmm, not entirely sure I follow, but hey... :)

<small>[ July 18, 2002, 12:53 AM: Message edited by: Zambosan ]</small>

[andreas]

Whell you could add more water as I think this will cause it not to detonate and then crush them but I dodn't know for shure

[VX]

Well a few times I have found a solid bed of AP or HMTD at the bottom of a flask. However for me it has always consisted of tiny crystals that have fallen on top of each other, and somehow just meshed together.

Don't worry about it too much as long as they are wet. If I were you I would simply get as much of the acidic mix out of the flask as possible, then use a glass rod or whatever to gently break the lump apart. (Sometimes this can actually be quite hard!). After removing them from the flask you can descide whether you want to keep the it :) , or if the crystals are too big, and need to be disposed of :( .

If you really don’t want to do this you could dissolve the HMTD in a solvent, and then just pour the mix away.

[DBSP]

What solvent? HMTD seemes insuluble in most common things. just fill the flask with cold water and gently break up the crystaline mass. I you would like to protect yourself put the flask in a wodden box and wear the usual protection. Use a long L-shaped stick to break the mass up.

[Zambosan]

Wouldn't a water solution would just increase the mechanical coupling between voids in the mass?

<small>[ July 18, 2002, 12:53 AM: Message edited by: Zambosan ]</small>

[Zambosan]

Oops, sorry for the double-post...

<small>[ July 18, 2002, 12:54 AM: Message edited by: Zambosan ]</small>

[viemane]

DBSP: where did you buy your 35% H2o2. i haven´t fin it just 19,5, for some reason they have removed it in every shops I have checked.

Iam also thinking about if my 19,5% lower the yields in both ATCP and HMTD syntheses, especially in HMTD. I have to let the mixture stand in 24hour(in the proceduer i use(citricacid)the suggest 3hour for 30-35%H2O2)
The last time i tried this I got, cant remember exactly, but I think 10g out of 16g hexamine and correctly ammounts of the other chemicals (45g citricacid) Is this normal? (is my penis normal :) )

An other problem may be that if use acetic acid 99% or 100%, I think, it may be a greater risk for a run away reaction as I have more water in my H202 and that is the same thing that if I had used weaker acid and 35% H2O2.

[DBSP]

I don't think that I can buy the 35% anymore since the highest canc allowed by law is 20% now in sweden. I bought the H2O2 in a small paint shop. Are you from sweden?

[xoo1246]

Hmm, I bought 35 or 30% H2O2 at the pharmacy some time ago, then I bought 19.5% from a paint shop, they said that it was the highest concentration allowed. DBSP, check your mail.

[Helos]

I had the same thoughts about H2O2, in paint shops they said that they weren´t able to sell higer than 19,5% any longer, what can be the reasons of this news, I have heard that it was because bottles of H20" exploded or broked (pressure from released oxygen), or could it be too stop people from making the dangerous ACTP, maybee.
If it is a law that more than 19,5 can´t be sold longer, it is just to forget to obtain 30-35%.
This is a problem when you synthezize HMTD, I have only used the citricacid method, and there the additional water makes the reaction slower, and I also think you get a lower yeild even if you wait for a greet time? When you use aceticacid as catalyst the problem is even greeter or at least you have to add more acid if the reaction is not going to be violent, still I don´t know why this can happen (to little or to weak acetic acid in the synthesis), anyone who knows

When I checked, this forum I was chocked about how many Swedes that was here, beacause sweden is not a wery big country.
Anyway, it may be boring for many others to discuss swedish matters, as this or how N-28 is going to be used, but for me this is wery useful information ofcourse

[Helos]

BTW, I also used esbit for my HMTD, but now I have find a commercial source for HMTA, it is both cheaper and better HMTA.
DBSP, check your mail, it is about N-28 mm.
Okay, now it´s luckily sent and I have luckily followed Kingpaz advice!

<small>[ June 30, 2002, 06:28 PM: Message edited by: Helos ]</small>

[DBSP]

I'll check my source of the 35% this week to see if they still sell it or if they've got the 20% now.

Helos, send me a mail with your questions about N28 and I'll try to help you. We aren't to many swedes here only 3 active posters at this time.

[kingspaz]

Helos, don't be offended the following it is constructive critisism.
1. don't double post but use the edit function if you forget to add somthing.
2. the correct abbreviation is CTAP - cyclo triacetone peroxide.

[Helos]

1.Okay Kingpaz, if I grew old on this forum I will learn, I hadn´t noticed that you could edit sent messages.

2. I can´t agree that CTAP is the correct name, it is (acording to IUPAC 3,3,6,6,9,9-hexamethyle-1,2,4,5,7,8-
hexaoxocyklononan) It´s on to hard to write so we use letter combinations for this peroxide I have seen many: ACTP, TCAP, AP TATP and others Acetoneperoxide is a bad name because it can be misstaken for other substance but if you choose ACTP, TCAP or CTAP, what the hell the are all good, but ofcourse other people have to now what it´s.
I don´t want to mess about names, it´s boring...

[kingspaz]

like i said, constructive critisism. i was trying to help <img border="0" title="" alt="[Wink]" src="wink.gif" />

[Helos]

okay, forgive me if I sounded agressive or something like that...