Any information on any of the above is greatly appreciated, especially the cyclotrimethylene trinitrosamine, in particular VoD's, sensitivity, and methods of making them (I'm thinking methylene dinitramide is hard, right?). I saw in one post that cyclotrimethylene trinitrosamine could be made by mixing C6H12N4, NaNO2 and H2SO4. Is this true?? If so, temperatures, proportions etc. would be great if anyone has them.
Also, is C6H12N4*2HNO3 made in basically the same way as MMAN (mix in the right proportions and crystalise)?

The reasons for this post are: 1) curiosity and a desire for knowledge, and 2) I have a very plentiful supply of hexamethylenetetramine, but not much to do with it! I can and do sometimes make RDX, but if I could make an explosive out of C6H12N4 that didn't need the 100% white HNO3 then that would be nice!

Also, does anyone have any info on nitrourea and dinitrourea? (Especially Philou!)

Thanks.

I'm also very interested in nitrourea. I've got one synthesys but I've never managed to accomplish it, it is from a patent. The problem is that no or very little chrystals form when I mix the solution with water. I don't know if I do it wrong or the info is wrong. Have someone made it?
Here is the synthesis:
84.ml of concentrated sulfuric acid was placed in a 200 ml three-necked flask equipped with a thermometer and a stirrer, and was cooled to -3° C. To this acid was added and dissolved 23.8 grams of urea nitrate in small portions while stirring. Having been stirred for 30 minutes, the reaction mixture was poured on 150 grams of crushed ice. The resulted crystals were filtered, were washed with a little amount of water for twice, and were dried in a desiccator under vacuum. The yield resulted in 16.2 grams of nitrourea (72.4% yield), whose melting point was measured to be 159° C. Since nitrourea dissolves easily in water, its yield is improved more by taking sufficient care when washing with cold water.

Nitrourea is slightly more powerful than TNT and has maximum detonation velocity 7000m/s.

Cyclotrimethylenetrinitrosamin expands Trauzl's lead Block 370 ccm with a DV of 7300 at 1.5 g per ccm. Slightly soluable in water, readily soluable in boiling alcohol, obtained by mixing Nitrates or nitrites of Alkalines with 6 N HCl and hexamine in the cold. pH should be around 1, at pH 2 only the dinitrosamine is formed. Mixing the trinitrosamine with H2SO4 and AN yields a dinitronitrosamine and further nitrated RDX.
Remeber that nitrosamines are CARCINOGEN!!!!

The dinitrate of Hexamine offers a Lead Block expansion of 220, being formed from diluted HNO3 and Hexamine, but the diperchlorate of Hexamine is a better choice, not very stable but comparable to Tetryl.

Nitrourea: decomposes with water, thats why pouring the solution of Nitrourea in H2SO4 into ice wouldn't work. Dinitrourea may be formed by nitrating nitrourea with acetic anhydride or so.....

Thanks.

I have also heard of reacting urea nitrate with H2SO4. Try reducing the washing water and the water that you dump the reaction mixture into at elevated temperatures (and maybe reduced pressure if possible) to see if any more nitrourea crystalises out. You could also try letting it react for longer, but I don't think this is the problem. Or, if it decomposes in water like Cipolla says, then maybe you could just cool the reaction mixture down to precipitate it, then filter it out and neutralise it with dry gaseous ammonia. This should yield a neutral product that's only contaminated with ammonium nitrate (an explosive), and it won't contact water. Then you might be able to crystalise it out of alcohol or something to purify it more. Oh, and is the formula NO2-HN-CO-NH2?

Cyclotrimethylene trinitrosamine looks easy to make, but I don't really want cancer. Do you have any information on it's reaction with H2SO4 and NH4NO3 to form RDX? I'd need the temperatures etc, I can work out the proportions.

About the dinitrosamine: is that cyclodimethylene dinitrosamine, or is it cyclotrimethylene dinitrosamine amide or something? I mean, is it the same but with an NH2 group instead of an NO2 group?

For precipitating Nitrourea from H2SO4 try puring the mixture in absolute alcohol and cooling to -30°C. The formula given is correct.

I believe the nitration of Cyclo... with H2SO4 and AN works also with HNO3 and H2SO4, or maybe the Ammonium-ions catalyze the reaction.

The dinitroso-compound, hmmm, i think there's a NH-group or a N-CH3-Group, no information is given.

I might try making the trinitrosamine and converting it into RDX, but it probably won't be soon because I'm lazy! I'll let you know if I do. If it works it might be quite a good method for making RDX, depending on the yields etc. I'll do it at low temperature, about 5*C unless anyone has any better ideas.
Thanks for your help.

I worked this out for the trinitrosamine:

3 C6H12N4 + 12 NaNO2 + 12 HCl ---> 4 C3H6N6O3 + 12 NaCl + 6 H20 + 6 CH2O

(in an aqueous solution, pH below 1)

I'm sure this is right, but if anyone else thinks otherwise please let me know before I try it.
I think you might need to warm it up, like when hydrolising hexamine to methylamine in HCl, so I'll do it at the temp needed for that reaction and see what happens. I'll mix it cold, so if anything precipitates without heating I'll know I don't need to.

Does anyone know if the equation above is correct?

The equation would need:

420 grams of hexamine,
4380 grams of 10% HCl, and
828 grams of sodium nitrite.

This would make 696 grams of the trinitrosamine. Due to it's low solubility in water the yields should be quite high I think. In theory, this could then be reacted with H2SO4 and NH4NO3 to make 888 grams of RDX!

I think to make the trinitrosamine, I'll divide the HCl sol. into two parts, dissolve the hexamine in one and the sodium nitrite in the other, and mix them. Then, if neccessary, I'll heat the solution to about 70*C or so for about 30 mins, let it cool, and see what happens! Or I might do the same thing, but dissolve the NaNO2 in all of the HCl (hot), and then add solid hexamine in small portions, stirring between additions to dissolve it.
Any thoughts on this? I haven't calculated anything about the reaction to RDX yet.

HAHAHA!!
It's easier than HMTD, and a hundred times faster!
I dissolved 10 grams of NH4NO3 (it was damp, so I used more than is necessary) in 60ml of 15% HCl (so it was in excess), and added, in four portions, 4 grams of powdered hexamine. The hexamine dissolved, and immediately formed fairly large amounts of a fine, colourless crystaline precipitate, which I think can only be the trinitrosamine. No heating or cooling was required. Due to the fact that I used a nitrate, not a nitrite, it will I think have formed NH4ClO, not NH4Cl. Is that dangerous? I think I've read it might be, like the chlorate. I didn't think of that until now http://theforum.virtualave.net/ubb/smilies/frown.gif.
I'll filter, wash, dry and test it later, and I'll tell you the results as well as the yield. I'm hoping for 5 or 6 grams, which would be a good yield.

[This message has been edited by Mr Cool (edited June 05, 2001).]

No hypochlorite could exist in a solution containing HCl.

What is the molecular formula of the trinitrosamine? The formula is written: "trinitrosamine" doesn't it mean trinitro ester { (NO2)3 }.C3H6N6O3? where are these 3 nitro groups. And how such substance with negative oxigen balance can give 7,3 km/s and 370cc?


[This message has been edited by simply RED (edited June 05, 2001).]

The structure is like RDX but with NO instead of NO2. The detonation velocity depends much more on the desity but on the power, and the cyclic stucture of this explosive and the large amount of gas evolved on explosion (remember the not oxidized Hydrogen and the little molecular weight of CO)makes it very strong....

No hypochlorite possible? Well, I've just realised that the extra oxygen is enough to perfectly oxidise all of the CH2O into CO2 and H2O, so maybe this has happened.
Unfortunately, after standing in the HCl solution in which it was made for about 7 hours (I've been too busy to filter and wash it), it has almost all dissolved and/or decomposed. There was a thin layer of crystals at the bottom of the beaker, and when I stirred it it was clear that the bottom portion of liquid had dissolved a lot of it because I could see the differences in density because of refraction (the lower portion was much denser). I'll make up another identical batch now and filter it immediately. If it works well then it is an incredibly easy to make, fairly powerful explosive, and possibly a good route to RDX.

Has anyone else tried this? I'd like to hear other people's experiences if you have.
And does anyone have any ideas on the conditions needed to oxidise it to RDX? I need temperatures, times etc.

When You did this, what was the temperature of the solution? ( initially and during the process ).
Also, if the product dissolved wouldn't You say that maybe it isn't cyclo.... after all ( since that had a low solubility in water )?
Did the hexamine dissolve completely before the precipitate formed ?
Just one more question: Does anyone know the sensitivity of hexamine dinitrate ?

It started at room temperature, and didn't rise a noticable amount. However, when I did it in a larger quantity (20 grams of hexamine), a very thin mist was produced. This could just be HCl, but 15% doesn't normally fume.
I was thinking that it could actually be hexamine dinitrate (2NH4NO3 + C6H12N4 + 2HCl --> 2NH4Cl + C6H12N4*2HNO3), but I don't think this would have precipitated out at all.
I added the hex to the clear solution of NH4NO3 in HCl. It sank to the bottom. I then vigorously stirred the solution, and after a few seconds (a lot of the hex. had dissolved), the solution started to turn milky with precipitate. The crystals grew and sank, and didn't dissolve noticably after half a minute of quite rapid stirring.
It should be dry now, so I'll go and do a few tests.

For something different: I've tried preparing Methylenedinitramine following the instructions given on Megalomanias Site....I refluxed Formamide with Hexamine for a few hours, and yes, on cooling a precipitate appeard which is mentioned to be Methylenediformamide. I worked out an equation for this rection assuming that the formula of methylenediformamide is H-C(=O)-NH-CH2-NH-C(=O)-H and ir works, evolving ammonia (and it smelled like much of this). Then I've tried to nitrate this stuff using HNO3 and acetic anhydride, but that doesn't work, don't know why but I will try until it works. The rest should be done with the greatest of ease....

If anyone has an idea about this procedure or if my formulas are incorrect i would like to know. I think it should be carried out to prepare this stuff, Methylenedinitramine, according to it's DV of about 8500 and the Lead Block expansion that must be around 660!!!

Sorry, I don't know anything about methylenedinitramine (although your formula looks correct to me). It's reactants are a bit too exotic for me actually, I like being able to walk into a supermarket and buy them http://theforum.virtualave.net/ubb/smilies/smile.gif

However, I have the results of the first test I did on my mystery precipitate: behaviour to flame.
A pea sized amount was lit with a match. It melted, started to turn golden brown, and caught fire more or less at the same time, very shortly after the match flame was applied (it caught fire easily). When burning, it all melted and turned brown, and appeared to boil. It burnt rather vigorously with a slightly luminous flame (purple/blue with a slightly yellow tip), and the whole lot was gone in a few seconds, leaving a small amount of carbon. It "hissed" slightly while burning.
Does anynone know how this compares to hexamine dinitrate or c. trinitrosamine burning?
I don't understand this. Why does it precipitate and then re-dissolve?
If it's not the trinitrosamine, why isn't it? And what is it? Does the reaction need heating? Does it not work with nitrates? Is the ammonium ion causing problems?
I have so many questions but I can't find anything on the net to answer them!! http://theforum.virtualave.net/ubb/smilies/frown.gif
Please, if you have any info I'd greatly appreciate it!
Even if the overall yield of hexamine to RDX was 50%, 420 grams of hexamine would still make just under a pound of RDX (444 grams). In my opinion, this is worth persuing, since all the reactants are very easy to find.

Oh, and how about this for the trinitrosamine to RDX reaction:

2 C3H6N6O3 + 6 NH4NO3 + 3 H2SO4 ---> 2 C3H6N6O6 + 3 (NH4)2SO4 + 3 H2O + 3 NO + 3 NO2

???

Shit, I've realised my trinitrosamine ---> RDX rxn is wrong if Cipolla is right about a dinitrosamine being formed as well. I really should have read the earlier posts more carefully, since it also says it should be done in the cold and I was just about to try heating it. I might try it anyway though, to see what happens.
Just checking: is 6 N HCl the same as 6 mol/dm3?? 219 grams of HCl per litre of solution? If this conc is necessary then mine is too weak. I'll concentrate it and try again.

Did you try to make methylenedinitramine? What happened?

To make cyclotrimethylenetrinitrOSamine, you need nitrite and no nitrate! Nitrous acid is unstable in solution and if you heat, first you will volatise a portion of your HCl, but you will lose the not so cheap nitrite in fumes!
2HNO2 -->H2O + NO + NO2!

There is no way the HCl will trun in HClO3 nor the nitrate to turn into nitrite!

The compound you have formed is HMdinitrate..a soluble compound but HMdichloride can compete in the mix since HCl is a more powerful acid than HNO3-but a more volatile one too!Better then do HNO3 + HM and cristallise!

HNO2 has a very good hability to react with secondary amines to give nitrosamine only with sec amines!
R-NH-R + HO-NO --> R-N(NO)-R + H2O

------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"

I agree that nitrites are needed, this fits better into this reaction, but I wonder that Köhler and Meyer ("Explosives") give the information that nitrate is used....

I tried it with nitrate, a day ago, no precipitate, no nothing, it only started to smell like methanal. But my HCl was not clear, the hexamine wasn't clear also....
Hexamine diperchlorate is compared to tetryl, great, can you tell me some more on it, what is the detonation velocity, is it water soluble, hygroscopic. What about urea perchlorate?
by the way: I won't try hexaminediperchlorate soon, i just told my chem suplier to find isopropanol, and he said it will come after some weeks(i wish so!).

[This message has been edited by simply RED (edited June 08, 2001).]

Right, I've bubbled loads of HCl into my HCl solution. It is now fuming strongly, so it should be concentrated enough! I got the HCl using NaCl and H2SO4, as if making HNO3.
And I think my local garden centre has NaNO2. I'll check.
Or can I make it by heating NaNO3, maybe with something not too reactive (e.g. tin, lead etc to react with the excess oxygen?) to form NaNO2?

The only information given about hexamine diperchlorate is that it's an explosive having 125 % of the power of TNT. Impact sensitivity is comparable to Tetryl. The stability must be unsatisfying.

I'd expect the diperchlorate to have a low storage stability, but it might be interesting to make. I think it'd also be a bit hygroscopic.

Have you succeeded in making methylene dinitramine yet?

Any ideas on making NaNO2? My garden centre didn't have it http://theforum.virtualave.net/ubb/smilies/frown.gifhttp://theforum.virtualave.net/ubb/smilies/frown.gifhttp://theforum.virtualave.net/ubb/smilies/frown.gif I think I read that you can heat NaNO3 with Pb, and then seperate it from the insoluble lead oxide formed. Would this also work with KNO3 (can't see why it wouldn't since they're so similar, but you can't really tell)? I've got more KNO3, but I could convert it with NaCl.

I'll go and do some experimenting now. I'll let you know if I get any positive results.

I've tried preparing methylene dinitramine following the instructions megalomania gave, the formation of methylene diformamide from formamide and hexamine occured easily but the nitration of this substance failed. Urbanski mentions a way of preparing from methylene diacetamide, so this is what I'll try next. Further is the information given that methylene dinitramine is only stable at pH 1 and pH 10. So it could be obtained by hydrolizing the nitrated methylene diformamide or diacetamide with Ba(OH)2 to form its barium salt and then get pure methylene dinitramine through acidifying this salt with a strong acid.

[This message has been edited by Cipolla (edited June 10, 2001).]

Methylenedinitroamine has a lead block expansion ranging from 565 to 630 ccm/10g
(188% to 210% explosive power of TNT). Plus, it has perfect O.B.:

NHN(=O)O
|
CH2 ---> CO2 + 2 H2O + 2 N2
|
NHN(=O)O

Gas volume= 823L/kg (at STP)

[This message has been edited by fightclub (edited June 10, 2001).]

Would you please post more info about Hexamine nitrate.
I tried the method in KIE for making it, but dont know why it didnt work.

I have this method:
1. Dissolve the hexamine in water(make as concentrated solution as possible).
2.Cool the hexamine solution and some 40-60% nitric acid to 1-2 degrees celsius(calculate 1mol hexamine 2 mols acid)
3. Add the hexamine to the acid. It will react and the temperature will rise.
4. Evaporate the water to left the hexamine dinitrate(this is soluble in water as I know).

Cippola:
nitrate-nitrite...just a typo error amongst some others I have seen in Rudolph Meyer's!
Excellent ideas to make Medina from
H-CO-NH-CH2-NH-CO-H or from CH3-CO-NH-CH2-NH-CO-CH3 (CH2(NH-CO-H)2 and CH2(NH-CO-CH3)2 ) with a subsequent hydrolysis and isolation of an unsoluble salt!
What about an urea-formol derivative?
...-CH2-NH-CO-NH-CH2-NH-... with a subsequent hydrolysis!

------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"

As a nitrite is needed to make the cyclo...,
it would seem that a good method for producing this chemical is desirable.
In "improvised explosives" a method is mentioned where You heat XNO3 and lead together for an hour. then You are supposed to dissolve the XNO2 in methanol and filter the PbO. My question is: does ethanol work as well as methanol for this, and if not, what can You do instead?

@ Philou you mean polymerizing urea with formaldehyde and nitrating the resulting amino plastic? That's a good idea, we should carry out this. I would prefer nitration using acetic anhydride because I feel like sulphuric acid would decompose the mixture.
The yield shouldn't be so good due to the linked stucture of the polymerisate but little MEDINA should be obtainable.

I have nothing to support this (except the slight chemical similarity between the polymer you describe and hexamine), but I also feel that H2SO4 would decompose it.

I beleive that if you heat KNO3 with lead it'll decompose to make NO2 due to the lesser thermodynamic stability of KNO3 compared to NaNO3, but I think it does work with NaNO3. I've also heard that you can just heat NaNO3 alone to make NaNO2, but if it's too hot it will also make NO2 and no NaNO2.

DNU's (dinitrourea) chemistry:
Stable in H2SO4!!!
Out of a patented process:
urea is made to react with HNO3 conc (99%)and H2SO4 conc (95%) at -10C; after 1/2h the cristalls of O2N-NH-CO-NH-NO2 are forming (yield near 100% based on the urea)! The resulting cristalls must be filtered under vaccuum fitration under -10C (otherwise they redissolve) and washed with a little very cold H2O!
The remaining cristalls must be dryed; the final compound is not stable in the time due to an hydrolysis to NO, CO2 and H2O!
A stable salt can be acheived via the ammonium or potassium salt (NH4OH or KOH) but during the process 1/2 of the DNU is lost (hydrolisis)!

Now the interesting part is that when the DNU is alkylated...you get nitramines upon hydrolysis!
Thus from urea-formol polymer or from the previously mentionned methylendiacetamide or methylene diformamide...you would get the medina by simple boiling in water!
(-CO-N(NO2)-CH2-N(NO2)-)n + nH2O --> nCH2(NHNO2)2 + n CO2

------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"

Interesting...
Can you think of any reasons why the H2SO4/NH4NO3 method might not work?
If it does then I might give this a try.


[This message has been edited by Mr Cool (edited June 19, 2001).]

There ist little similarity between dinitrourea and the mentioned polymere. The reactions which took place by hydrolysis are comparable, but the desired product MEDINA could only be obtains out of the polymer for sure. And when only find the time I'll try.

..... argh I've no Ba(OH)2 !?!

Since were on the subject of dinitrates what about dinitronaphthalene?The first 2 nitrations seem fairly easy but the last one requires 100% Nitric Acid(Hard to come by)
I believe the dinitronaphthalene would be explosive but it probably would have a negative oxygen balance like Hexamine dinitrate.Any ideas?VOD,ect....
Demolition

VERY negative oxygen balance - 4 oxygen atoms, 19 more needed to make a zero balance!
Although it probably is explosive, just very insensitive and not very powerful. DNToluene, DNPhenol and DNBenzene are just as easy, but much better.
Incidentally, some suppliers (www.nbsbio.co.uk for example) sell DNPhenol as a narrow range pH indicator. 100g for £12.30. They also sell DNToluene, £8.50 for 1kg (97% 2,4-DNT). Lots of other useful things like acetic anhydride, pentaerythrite etc., but I haven't dared to try and order anything from them yet.

No reasons it wouldn't work. NH4NO3/H2SO4 conc should work fine.

------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"

Excellent, that will definately end up on my site.
Philou, or anyone else, I have a question:
Can monomethylamine nitrate be dehydrated with H2SO4 to make methylene nitramide, in a similar way to that in which urea nitrate can be made into nitrourea? It'd be like an RDX monomer I suppose.

I dare to doubt that this'll work. Acetic anhydride should be taken. When I heated methylamine nitrate in acetic anhydride it dissolved. The probaly yielded methyl nitramine is a strong explosive, stronger than Tetryl, wich melts around 38 °C. Soluable in water and alcohol and a strong acid which foms salts. When brought in cotact with concentrated sulfuric acid it explodes!

OK, thanks for the input. I thought it was worth inquiring about, but sadly I can't get hold of acetic anhydride so I won't be making this http://theforum.virtualave.net/ubb/smilies/frown.gif
I tried to make the cyclo..., using home-made KNO2 and the proportions that I worked out, adjusted for using KNO2 not NaNO2 obviously. I dissolved the KNO2 in the HCl (I used 15%) at room temperature, and then slowly added the crushed hexamine. There was a very slight bubbling, but no precipitate. Cipolla, when you said the reaction was done in the cold, did you mean cold as in -10*C or something like that, or just not externally heated?

[This message has been edited by Mr Cool (edited June 24, 2001).]

It looks like you found out why Trimethylenetrinitrosamine ist not comercially used: The preparation yields too little of the desired product. At first, as I said, it's essential that the pH is kept at 1. The most investiagtors used 6 N HCl and diluted that, then dissolved NaNO2 and finally added the mixture to a solution of hexamine in ice and water. So the temperature should be kept at 0°C for 30 min. The maximum yield is around 50 %.

Primary nitramines are unstable towards H2SO4!But secondary are OK!
Thus with H2SO4
dimethylamine nitrate --> dimethylnitramine
guanidine nitrate --> nitroguanidine
urea nitrate --> nitrourea
urea nitrate + HNO3 --> dinitrourea

Methylnitramine is only reachable from dimethylurea dinitramide hydrolysis or from methylamine nitrate in Ac2O!


------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"

Right, I'll try again at 0*C and see what happens.

No I made a mistake! Secondary nitramines are not OK with H2SO4- otherwise there wouldn't be any problem to do RDX from HNO3/H2SO4 what is not the case!!!But ...they can be made from pure HNO3 or from the nitrate salt + acetic anhydride while primary nitramines are hardly done from pure HNO3!!!
Only guanidine and ureas resist the H2SO4 dehydration!

------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"

A complete synth for the trinitroso compound may be found in WE Bachmann and NC Deno, JACS, 73, 2777-2779 (1951).
The pH is critical - above 2 and the dinitroso bridged [3.3.1] compound forms. I haven't got time to type out the prep at the moment, if enough people want and don't have access to journals I'll do it tomorrow. Let me know.
MEDINA may be made from methylene-bis-acetamide, which is simple to do (heat acetamide and paraform overnight) Again, I'll post details if required.
Also, dinitrourea is reasonably stable if the last traces of the nitrating acid are removed. You can do this with trifluoroacetic acid. I've actually prepared this stuff as part of a nitramide preparation - extremely vigourous mechanical stirring is required! If the urea sits on the surface for any time the whole reaction goes tits-up.

Hope this helps.
Hex

Shady said in one of the past topics:
Foss,Hirst,Jones,Springall,A.T Thomas and T.Urbanski have established that boiling an aqueous solution of hexamine dinitate causes the substance to transform into methylhexamethylene mononitrate.

Now when you add the hexamine+h2o solution to the 70% or less NA you will get heat thats all!! nothing precipitate.
Does it needs to be boild or what?

If you want the dinitrate, the temp must stay below 15 °C. No boiling!

------------------
for best catfood visit:
kangaroooo.cjb.net (http://kangaroooo.cjb.net)

Ive made hexamindinitrate but i have tried to wash it with sodium carbonate solution and i think the sodium carbonate has decompused the
dinitrate =(
how do i clean it without this problem ?

Nitro, how did your brain decided to treat such compound with carbonate solution?

I m not an chemist.And in the manuals for RDX
they use na2co3 to neutralize the acid so i thought i can use it for dinitrate too.And how do you clean this products if you cant use alkalis to neutralize the remaining acid
in the product.

I've got a tub of hexamine dinitrate which was washed with water only that's sat quite happily on my bench for 4 months without any apparent decomposition.
BTW, the conversion of HDN to methylhexamminium nitrate as described by Jones, Springall et al requires a 2.5 hour reflux.

C6H12N4.2HNO3 is an acidic salt not a nitro derivative like nitrate esters, nitrocarbons or nitramines/nitrosamines. This explains why it can't be washed with a medium strenght base like Na2CO3 you simply make sodium nitrate and free some H2CO3 (H2O+CO2) reducing your efforts to zero http://theforum.virtualave.net/ubb/smilies/frown.gif

------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"

I've found the synthesis of the trinitrosamine and a similar nitrosamine. Both use only C6H12N4, NaNO2 and HCl. They're in Swedish, but you can understand what they're saying OK. If anyone wants them ask and I'll copy them here. There's a link to them in this section, it also has many other useful reactions, but if you don't want to search through it then I'll give you the relevant section.
It says that the yield of the trinitrosamine is 50%, and it can be oxidised to RDX using H2SO4/HNO3 (or H2SO4/metal nitrate) with a 74% yield. That means that 140 grams of C6H12N4 (1 mole) could make around 110 grams of RDX, without concnentrated nitric acid!!

But Cipolla, you said that reacting the trinitrosamine with AN/H2SO4 produced RDX and a dinitrosamine. Is that just what happens to the rest of the trinitrosamine that isn't converted to RDX, or is there a mistake in the text? I'll paste it here so you can see:

1,3,5-triaza-1,3,5-trinitrosocyklohexan


Fysikaliska egenskaper

Densiteten på TMTN är 1,59 g/cm³, och det är svårlösligt i vatten (vid 20 °C löser
sig 0.2 g TMTN i 100 g vatten). Det lösningsmedel som bäst lämpar sig är aceton.
Vid 60 °C löser sig 255 g i 100 g aceton. Ämnet har en smältpunkt runt 106 °C.

Kemiska egenskaper

Vid rumstemperatur reagerar TMTN explosivt i kontakt med konc. svavelsyra, men
vid lägre temperaturer bildas istället trimetylentriaminsulfat. TMTN bryts ned
av natriumhydroxid under bildandet av formaldehyd, kväve och ammoniak. Även
vatten bryter ned ämnet, något som kanske förklarar utbytet. Oxidering av TMTN
med antingen svavelsyra och salpetersyra (99%) eller väteperoxid (30%) och
salpetersyra (99%) ger RDX med ett utbyte kring 74%.

Explosiva egenskaper

Tabellen nedan visar sambandet mellan presstryck och densitet för TMTN.

+--------------+----------+
|Tryck (kg/cm²)| Densitet |
+--------------+----------+
| 170 | 1,10 |
| 340 | 1,23 |
| 680 | 1,37 |
| 1020 | 1,44 |
| 1700 | 1,53 |
| 2380 | 1,57 |
| 3000 | 1,59 |
+--------------+----------+

Vid densiteten 0,85 g/cm³ krävs det 0.3 g kvicksilverfulminat för fullständig
detonation. Samma förhållanden men med en densitet på 1,57 g/cm³ kräver hela 2.5 g
för samma resultat. Stötkänsligheten är samma som för TNT. Vid en densitet på
1,57 g/cm³ har TMTN en detonationshastighet på 7800 m/s då laddningsdiametern var
30 mm. Blyblocksexpansionsvärdet är 125,5 (TNP satt som 100). Tabellen nedan
visar sambandet mellan densitet och detonationshastighet.

+----------+---------------------------+
| Densitet | Detonationshastighet (m/s)|
+----------+---------------------------+
| 0,85 | 5180 |
| 1,00 | 5760 |
| 1,20 | 6600 |
| 1,40 | 7330 |
| 1,50 | 7600 |
| 1,57 | 7800 |
+----------+---------------------------+

Tester som genomförts angående ämnets lagringsstabilitet visade att TMTN var
helt oförändrat efter 6 år i rumstemperatur. Vid 150 °C började ett markant
sönderfall, och runt 300 °C sönderföll det helt. Blandas TMTN med TNP
(pikrinSYRA) reagerade blandningen våldsamt efter 2 timmar. Temperaturen var
60 °C. Vid 100 °C reagerade det på 10-15 minuter. Smält TMTN reagerar med järn,
koppar och aluminium.

Tillverkning av TMTN

TMTN bildas när man reagerar HNO2 med HMTA vid pH=1. Utbytet blir under 50%
med denna metod. Man kan få högre utbyte (50%) men då tycks det krävas en
riktig pH-mätare.

1. Lös upp 7 g HMTA i 50 ml vatten. I denna lösning hälls 26 ml konc. saltsyra.
Blanda detta med 400 g is i en bägare.

2. Lös upp 10.4 g natriumnitrit (NaNO2) i 50 ml vatten och häll detta i en
portion ned i isbadet. Låt lösningen stå i en timme vid 0 °C.

3. Filtrera ut de bildade kristallerna och tvätta dem med vatten. Lös upp dem i
varm aceton och häll ut det i 100 ml 5% natriumbikarbonatlösning. Filtrera
igen och torka i rumstemperatur. Produkten bör väga cirka 3.6 g.

Here's the other nitrosamine from hexamine, yields look better:

DNTP

Mycket lite nämns i litteraturen om DNTP. Smältpunkten är cirka 207 °C.
Ämnet har tydligen använts vid tillverkning av porös plast och gummi.
Tillverkningen av DNTP går i stort sätt till på samma sätt som för TMTN,
men det går åt mer NaNO2. Å andra sidan går det åt mindre saltsyra.

1. Lös upp 7 g HMTA i 50 ml vatten. Denna lösning hälls i 13 ml konc. saltsyra.
Blanda detta med 400 g is i en bägare.

2. Lös upp 20,8 g natriumnitrit i 50 ml vatten och häll detta i en portion
ned i isbadet. Låt lösningen stå i en timme.

3. Filtrera ut de bildade kristallerna och tvätta dem med vatten. Lös upp
dem i varm aceton och häll ut det i 100 ml 5% natriumbikarbonatlösning.
Filtrera igen och torka i rumstemperatur. Produkten bör väga cirka 7,1 g.

What about C₆H₁₂N₄·2(H?)ClO₃? Is this possible? Would it be too unstable? Someone said no OCl can exist in a HCl solution... I assume this also means no NaClO₃ either, so could Mr Cool's HMDN process be used but with a lot of weak organic acid such as citric and NaClO₃? If I weren't such a bastard, I'd try it myself.

Mr cool do you want me to translate that?
And could you give me a link to that swedish archive.

------------------
¤monte¤

[This message has been edited by DBSP (edited September 07, 2001).]

The file can be found here: http://swi.1av10.nu/dist/pyrok2k.zip

Would you mind terribly translating the whole archive? It has a bunch of great info in it, it would be AWESOME to have a full trans of it. http://theforum.virtualave.net/ubb/smilies/smile.gif

Well it's possible to roughly guess what it's saying, but any translations you could do would be great because a rough guess isn't good in this subject...

I allmost thought it was from that archive.

I'll do the translation as soon as I can,
possible later tonight, it's 8 a clock in the evening here in sweden.

I will have a look at the archive and see what could be useful to the Forum, and I will
try to translate as much as I can/and have time for. What would you think about me putting up the translations in new post, if it is enaugh to be worth it?

------------------
¤monte¤

Here is the trans.
I'm very interested in this explosive as a
way to RDX without strong NA.
Does anyone have any info/ideas about the conversion to RDX. And spicific info about how to get KNO2 from KNO3, temperatures, should the lead be a powder or lumbs etc.??

1,3,5-triaza-1,3,5-trinitrosocyklohexan

Fysicalic properties
Density of TMTN is 1,59 g/cm³, and it has a low solubility in water (at 20 °C .2g
of TMTN disolves in 100 g of water). The best solvent is is acetone.
At 60 °C 255 g disolves in 100 g acetone. The pruduct has a meltingpoint around 106 °C.

Chemical properties
At roomtemperature TMTN rects explosively in contact with conc. H2SO4, but
at lower temperatures trimetylentriaminsulfat is instead formed. TMTN decomposes
by NaOH during the formation of formaldehyde, nitrogen and ammonia. Also
water breaks down the pruduct, something that maybe explains yield. Oxidation of TMTN
with either H2SO4 and nitric acid (99%) or H2O2 (30%) and
nitric acid (99%) gives RDX with a yield about 74%.

Explosive properties
The table below displays conection between loading presure and density for TMTN.
+--------------+----------+
|Press (kg/cm²)| Density |
+--------------+----------+
| 170 | 1,10 |
| 340 | 1,23 |
| 680 | 1,37 |
| 1020 | 1,44 |
| 1700 | 1,53 |
| 2380 | 1,57 |
| 3000 | 1,59 |
+--------------+----------+

At the density of 0,85 g/cm³ 0.3 g mercury fulminate is needed a for complete
detonation, but with a density of 1,57 g/cm³ 2.5 g mercury fulminate is neded for the same results. the shock sensitivity is the same as for TNT. At a density of
1,57 g/cm³ TMTN has a detonationvelosity of 7800 m/s at a 30 mm diameter . The leadblocktest value is 125,5 (TNP 100).

The table below
displays the connection between density and detvel.
+----------+---------------------------+
| Density | detvel. (m/s)|
+----------+---------------------------+
| 0,85 | 5180 |
| 1,00 | 5760 |
| 1,20 | 6600 |
| 1,40 | 7330 |
| 1,50 | 7600 |
| 1,57 | 7800 |
+----------+---------------------------+
Tests concerning the storage stability showed that TMTN was
entirely unaltered after 6 years at room temperature. At 150 °C it begins to decompose and around 300 °C it entirely collapses. TMTN mixed with TNP
(picric acid) reacts violently after 2 hours. the temperature was
60 °C. At 100 °C it reacts after 10-15 minutes. Melted TMTN reacts with iron,
copper and aluminum.
the manufacture of TMTN

TMTN is formed when you react HNO2 with HMTA at PH=1. yield is under 50%
with this method. you can get a higher yield (50%) but then it seems to demand a
real pH-meter
.
1. dissolve 7 g HMTA in 50 ml of water. In this solution 26 ml konc. HCL is poured in.
Mix this with 400 g ice in a beaker.
2. dissolve 10.4 g of (NaNO2) in 50 ml of water and pour this into
the beaker with ice. Let the solution stand a hour at 0 °C.
3. Filter the crystals and wash them with water. dissolve them in
warm acetone and pour it in 100 ml a 5% sodiumbicarbonate solutin. Filter
again and dry at room temperature. The product should weigh about 3.6 g.
Here's the other nitrosamine from hexamine, yields look better:

DNTP
Very little is mentioned about DNTP in the litterature. the meltin point is about 207 °C.
DNTP has apparently been used for processing porous plastic and rubber.
the manufacture of DNTP is about the same as for TMTN,
but it uses more NaNO2. but on the other hand less HCl is used.
1.dissolve 7 g HMTA in 50 ml of water. This solution is poured in 13 ml of konc. HCL.
Mix this with 400 g ice in a beaker.
2. dissolve 20,8 g of NaNO2 in 50 ml of water and and pour this into the
the icebath. Let the solution stand for one hour.
3. Filter the crystals and wash them with water. dissolve them in warm acetone and pour it in 100 ml of a 5% sodiumbicarbonate-solution.
Filter again and dry at room temperature . The product should weigh about 7,1 g.


------------------
¤monte¤

Thanks for the translation!

The temperature I always remember hearing for the NO3 --> NO2 reduction is 400*C. At this temperature, the lead will melt and sink so it doesn't matter what form it's in.

If it reacts explosively with sulfuric at room temperature, perhaps there is the possibility for a purely chemical detonator? For instance creating a device wherein the sulfuric is confined in a seperate compartment to the TMTN, only to be released at a desired time. If it reacts this way to H₂SO₄, what about to HNO₃? Surely that would be more violent...

PS. Thanks for the trans, it's a great help! http://theforum.virtualave.net/ubb/smilies/smile.gif

Almost all of the files in the infomania archive are excellent, for instance there is an alternative method for producing MHN which is quite superior to the one I posted some time ago ( of course we should have thought of it our selves; it basically involves using ordinary 70% HNO3 and then just adding a bit more H2SO4 to absorb the water - so no thick NH4SO4 sludge ). The yield seems to be better as well.
So if you have the time ( unfortunately I don't ) go ahead and translate them all.

Microtek,could you please post that information on MHN using 70% nitric acid in the MHN topic.Thanks.


------------------
http://www.angelfire.com/retro/mafsexplosives/
Demolition

"Nitro"... Just rinse it with some pure acetone. I rinsed mine(48g) with 4 portions 0.5dl each...

I got quite nice yields with it. 28g hexamine in some 95ml of warm water.
I let it cool to near 0 deg.C
Then i slowly added 45ml 60% HNO3.
Quickly stirred a little and poured everything into a big coffee filter then I rinsed it with the acetone...
I got 48,5g yield 90%+:)

Ive noticed that HMD will detonate very mildly when not confined. I detonated 9g with 1g of Pb-adize in a small plastic cup.
I heard a weak bang and went to see. The largest piece of the cup left was about 1x1mm and the light concrete brick it was standing on had a pit in it (maybe 1-2cm deep). I don't think I can call this complete detonation, but something obviously happened:)

I did a couple searches on the forum and web about this explosive, never really coming up with many valuble results. When I first started out with explosives - goes all the way back to the K3wl days when we took the "explosive" out of fireworks. I wanted to make my own, started researching and so on. For many years the only thing I knew were organic peroxides that would go off any time they felt like it. I have been looking for a website that details the synth of a high exploive that isnt so costly but is less sensitive than stuff like AP or HMTD.

I found somthing that may work:

Hexamethylenetetramine Dinitrate

5g of hexamethylenetetramine,
65mL of 15% hydrochloric acid,
10g of ammonium nitrate,
A 150mL beaker,
A filter funnel,
A filter paper,
A glass rod,
A fridge.

1) Pour the hydrochloric acid into the beaker and add the ammonium nitrate.
2) Stir the solution with the glass rod until all the ammonium nitrate has dissolved.
3) Cool the solution to 5*C in the fridge.
4) Add the hexamethylenetetramine. Stir it with the glass rod until it has all dissolved. A white crystalline precipitate should form.
5) Quickly filter out the precipitate.
6) Leave it in a warm, dry place to dry fully.


Has anyone done this synth?

It's from Mr. Cools website, I have done a couple from his instructions and they have all worked fine, but there is little info on this explosive. If you have any warnings, ideas or have done this please let me know!

Try using the word 'dinitrate' in the search engine to find one of a dozen existing threads to post this in, such as this one by Mr. Cool.

Sorry for bringing up this old thread but HDN (Hexamethylenetetramine Dinitrate) looks like a decent explosive that I can easily make. I am wondering about the storability of this explosive. Have any of you attempted to store it for extended periods of time? Maybe up to a few months? If the synth on Mr. Cools website is accurate (im sure it is :)) Then I should be able to make it in large amounts and throw some AP togeather for a quick detonater. Does anyone have any info on this explosive??

It's unstable in storage.