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hector2000
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[*] posted on 22-3-2008 at 01:56


Ok First Rogue Science:
I think This is Easier Method but We want Anhydrid and We need Mr Sauron method For Making Anhydrid.
******
Prepare a solution of 748 mL of glacial acetic acid, 12 mL of acetic anhydride, and 17 g of paraformaldehyde, keep this solution at 44 °C while mixing. Prepare a second solution of 217.6 g of ammonium nitrate and 154.6 mL of 99% nitric acid in a 500-mL beaker. Prepare a third solution of 101 g of methenamine, 157 mL of glacial acetic acid, and 296 mL of acetic anhydride in a 1000-mL beaker. Combine the third solution with 112.5 mL of the second solution. Add this combined solution to the first solution over a 15 minute period while stirring rapidly. After the addition, continue stirring for an additional 15 minutes. Next, carefully add 296 mL of acetic anhydride, then carefully add the remainder of the second solution, then add another 148 mL of acetic anhydride, all while stirring. Continue the stirring for 1 hour more. After stirring, add 350 mL of hot water and reflux the whole works for 30 minutes. After this time, cool the liquid down to 20 °C by adding ice. Decant off as much of the liquid from the precipitate as possible and drown the remaining crystals with cold water. Filter to collect the crystals of HMX and wash them with three portions of cold water, allow to dry. The yield is about 95%. You will need a graduated cylinder for measuring liquids, a stirring rod or magnetic stirrer for mixing, and a thermometer to monitor the temperature.
****
-I Think to much Anhydrid Used in this Method.(Probably Will Work with less Anhydrid)
-I Found Patent That said You Should Reflux Final Mixture For 12 Hour but in the rogue we have 1 hour!


[Edited on 22-3-2008 by hector2000]




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[*] posted on 22-3-2008 at 02:05


Well.
A collection Of Patent About Hmx:
http://rapidshare.com/files/101436161/HMX.zip.html
New Method+Picture+.. on this




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[*] posted on 22-3-2008 at 08:26


Quote:
Originally posted by hector2000
Ok First Rogue Science:
I think This is Easier Method but We want Anhydrid and We need Mr Sauron method For Making Anhydrid.
******

[Edited on 22-3-2008 by hector2000]


Thanks for starting the ball rolling on this one- On your posted method, I would appreciate knowing the temperature parameters during the various steps?

Can you provide a link to the acetic anhydride preparation methods you mention?
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[*] posted on 22-3-2008 at 11:27


In the below topic You Will Find Interesting Methods
http://www.sciencemadness.org/talk/viewthread.php?tid=8148



[Edited on 22-3-2008 by hector2000]




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[*] posted on 28-3-2008 at 07:24


No body has Experience?



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[*] posted on 2-4-2008 at 01:50


The simplest route found in the journal literature is as follows.

<font size="4">HDN</font>

A solution of 50 g. of the tetramine in 150 cc. of water was cooled to 0°, and to it nitric acid (d. 1.42) cooled to 0° was added gradually. The nitrate was precipitated immediately in the form of small, white crystals which were separated by filtering the solution through glass wool. They were washed quickly with 50% ethyl alcohol previously cooled to 0°, and then given additional washings with alcohol and finally with ether. The mass was then dried with warm air; average yield, 78.2 g.


<font size="4">DPT</font>

One-tenth mole of hexamine dinitrate was added proportionately with 0.92 mole of 90% aqueous sulphuric acid to a stirred flask at 8° to 15° C. over a 30 min. period. After 45 min. subsequent stirring at 14° to 15° C , the mixture was poured into 400 cc. of ice and water. The solution was almost clear, but was filtered and neutralized to pH 5.6 to 6.5 with 28% ammonia to yield 0.031 mole (31% of theory) of DPT, m.p. 199° to 201° C. This yield was decreased to 23% when the addition time was 13 min., with seven minutes subsequent stirring.

The yield could be increased to 35% by adding the two ingredients proportionately to 0.2 mole of 98 to 99% nitric acid; but in this case a 14.5% yield of impure Cyclonite (m.p. 188° to 198° C.) had to be filtered off before neutralization.


<font size="4">HMX</font>

When 2.18 gm. (0.01 mole) of DPT was added to 12.7 gm. (0.2 mole) of 99.6% nitric acid at 0° to 10° C. over five minutes, a slurry formed, After 25 min. this mixture, drowned in ice, yielded a precipitate melting at 232° to 260° C. This was heated with 70% nitric acid until nitrogen oxides were evolved, then cooled, chilled-, and filtered. The washed, dried material weighed 1.01 gm. or 34% of theoretical and melted at 278.5° to 279.5° C.

Recrystallization from acetone, 70% nitric acid, dioxane (10% solution hot, 9% solution cold) or nitromethane, (solution 7.5% hot, 2.2% cold) raised this to 280.0° C. (decomp.). These solubilities refer to crystallization over a few hours; the acetone solution precipitates more HMX over several days.

LLNL handbook gives mp. for HMX as 285°C, and RDX 205°C.

[Edited on 3-4-2008 by Axt]
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[*] posted on 2-4-2008 at 06:11


Cool, I don't think I've seen that one before.

But HMX is so last millenium ;).
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[*] posted on 3-4-2008 at 13:05


I have used the Lukasavage patents with great results. I started out from DADN (the diacetyldinitro analog to HMX) which is prepared quantitatively from hexamine and acetic anhydride (and other more easily accessible materials). The nitrolysis of DADN to SOLEX (the acetyltrinitro analog) and subsequently to HMX gives essentially 100 % yield but requires P2O5 and anhydrous nitric acid.

I suppose that if you have access to Ac2O, you might as well use the conventional method giving something like 95% yield of 95% purity without the hassle of P2O5. However, I wanted to start from a substrate that would reduce the likelyhood of any product being just RDX (I didn't have access to any analytical methods that would reliably distinguish between RDX, HMX and any linear nitramines in the product).
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[*] posted on 4-4-2008 at 00:23


Mr Microtek Please say your Ratio and instruction of your reaction.
Before i made hmx using rogue science method but in the final product you will have Rdx and Hmx.and also you should use lot of anhydrid i dont advise rogue method(bachmann)




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[*] posted on 21-8-2008 at 03:34


I've successfully made HMX by method from US Patent №3926953, desctription of experiment and my notes and pictures are shown below:



7g (0.05 mol) of hexamine and 3.1g ammonium acetate (0.04 mol) are added to 3.6 ml of water (0.2 mol) cooled to 5-10°С. 15.3g (0.15 mol) of acetic anhydride is added with stiring in period of 60 minutes. Resulted colerless solution of DAPT is stirred for 30 minutes and then slowly, with stirring added drop by drop to mixture of 31.5g nitric acid (21 ml, 0.5 mol, density 1.495) and 110.5g sulphuric acid (60 ml, 1.13 mol, density 1.835) placed in ice bath in period of 120 minutes. Temperature is not allowed to rise above 15°С, solution is added by 6-7 drops at one time and then thoroughly mixed before adding new portion of solution (Note #1). After addition is completed, mixture is removed from ice bath and allowed to stand at room temperature for 2 hours. Mixture is poured on 0.5 kg of ice and 500 ml of water is added, resulting solution is thoroughly mixed and allowed to stand overnight (Note #2). Precipitated solid is filtered off, washed with cold water and dried at dessicator with P2O5. Yield is 10.6g (73%) of pure 1,5-diacetyloctahydro-3,7-dinitro-1,3,5,7-tetrazine (DADN).

Notes:

1. Patent literature mentiones possibility of violent exoterm, after aproximately 20 minutes from addition start, witch can cause heating to 85C. Exoterm is result of oxidation of formaldehyde byproduct with nitric acid. In order to eliminate this exoterm addition time is increased to 120 minutes (from 80 original) and portions of added solution is reduced to level at witch oxidation is not have time to start before next stirring. If added portions are larger, if stirring is not preformed propertly or if mixture have no time to cool before addition of new portion, violent exoterm is started, followed by foaming and evolution of large ammounts of nitrogen oxides.

2. Netherless very low solubility of DADN in water, crystallization of product can not start imidately (supersaturation) and should be aided by friction of glass rod on side wall of reaction wessel (below level of liquid). Crystallization is started after several hours and is completed in about 12 hours.



Solution of N2O5 in nitric acid is prepared by adding 50g phosphorous pentoxide to 100 ml of nitric acid (2.38 mol, density 1.495 g/cm3). Temperature is not allowed to rise above 30C, resulted solution is gently stirred and allowed to stand for 30 minutes at room temperature (Note #1). N2O5 solution is heated to 30C, 6g of DADN is added and mixture is stirred until DADN is fully dissolved (~10 minutes). Reaction mixture is heated to 50C and kept at this temperature for 1 hour (Note #2). After nitration is complete mixture is poured on to ice (300g) and 200 ml of cold water is added, poorly soluble HMX precipitates from solution as white solid (Note #3). HMX precipitate is filtered, washed with small ammount of ice cold water, placed to 100 ml of 3% solution of NaHCO3
and allowed to sit for 1 hour. Washed HMX is filtered and dried in dessicator with P2O5. Yield is 5.82g (95%) of HMX with ~100% purity.

Notes:

1. Formation of N2O5 takes some time, after mentioned period clear yellow solution is formed. Addition of P2O5 to nitric acid generates large ammounts of heat (especialy if acid contains water) and solution can heat to boiling, generating many nitrogen oxides, resulting from decomposition of N2O5 and partial decomposition of HNO3. That's why keeping temperature below 30C is essential during adition, towards end of P2O5 additon heat evolution ceases. It should be remembered that solution of N2O5 in anhydrous nitric acid is extemely corrosive and will cause severe burns and deep painfull long healing ulceration if spilled on skin.

2. Cover of reaction vesel should not be screved tightly, process generates nitrogen oxides witch can blow reaction vesel. Process should be carried out with effective ventilation or under the fume hood. Part of nitrogen pentoxide decomposes, generation NO2 and oxygen, however not affecting reaction yield.

3. Then mixture is poured on ice, large ammount of heat and nitrogen oxides is generated. Nitrogen oxides are relatively badly soluble in cold water and part of them escape, without ability to fully react with water. Resulted solution has sky blue color due the large concentration of HNO2 is present (it is formed by reaction of NO2 with water). Solubility of HMX in water is very limited (0.003% at 20°С;), however large ammounts of water should not be used because it will lead to some losses of reaction product.





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[*] posted on 17-8-2010 at 08:58


I've just found another method, which seems damn interesting because it is so easy to prepare!
But I don't know if it will work.
Here it is:
http://www.pyrotube.com/read_blog/2/hmx-%28octogen%29-from-u...

Maybe this is an unusual synthesis. Every anrachy crap book you read around and terrorist handbooks have the usual "urea nitrate from piss". How about "HMX from piss" ?!?!? this procedure may be so.... altough only a careful chemist may succed in these synthesis.

- First step: The first step is rather easy. It consist of preparation of urea nitrate by simply adding nitric acid in excess to a solution of urea. Must be plain fertilizer grade urea and not a salt (urea sulphate). The nitrate ion bonds to urea at the OXYGEN ATOM !!! weird, isnt it ?? the polarity of oxygen binding to the carbon causes it to have the negative charge that atracts NO3+. It doesnt in any way bonds to the ammonia part of the urea. This is important to know because it will give a 1:1 nitrate to urea and not a dinitrate.

- Second step is the synthesis of nitrourea. It is important to create mono-nitrourea and not n,n-dinitrourea. Dinitrourea WONT WORK because mono-nitrourea haves a NH complex that can still react. This is important for the next step. If you decide to do a nitrolysis on site of a mixture of nitric and sulohuric acid and then adding the urea, you will gent dinitrourea, so its important to start from urea nitrate, and adding it to sulphuric acid to generate mono-nitrourea. Nitrourea at this step is also a very good explosive, but chemicale unstable, meaning that altough insensitive, will decompose quickly on time specially if moist. it must be dried quickly !!!!!!!

- The most difficult step is the third: synthesis of DPT. This is done by carefully mixing nitrourea with a concentrated (37%) formaldehyde solution. If you mix plain urea with formaldehyde in a acid media, it will form a polymer beacuase it haves th both NH2 radicals free to join to the urea. Mononitrourea only haves "one", so it will form a dimer of urea-formaldehyde. I dont know if it may form a cage structure at this time, but the addition of 5% NaOH will produce the solution of DPT relasing CO2 and a "cyclooctane" cage-like structure, known as DPT. It is precipitated by simply adding ammonia to the solution and filtering it off. More ammonia can be addedd to the solution to make sure all is filtered.

- Final step: An usual nytrolisis of DPT yields HMX. This is best done through nitrogen pentoxide, maded by mixing nitric acid and phosphorous pentoxide. To make things easier for a home made pyro, high concentratoon nitric acid with ammonium nitrate may do. I dont suggest dehydratation with sulphuric acid because it will hydrolize DPT !!! The stronger your nitric acid, the best it will do, but low concentration nitric acid may work if a lot of ammonium nitrate is disolved first. Then an usual precipitation with water will yield a mixture of DPT and HMX, with a predominant of HMX (about 70%) Sorry, i still dont know how to separate DPT from HMX, but DPT is a high explosive by itself so it will work also very good!!

Is this just nonsende or perfect?
I'd jsut have to now some more details, masses, volumes, etc.


EDIT: I've just found another PATENT! which claims to get cheap DPT from Nitrourea but they don't exactly know how it works, BUT IT WORKS!

I think, my next batch of HMX won't be far away and it will be BIG :D

Just going to use my CHEAP Urea fertzilizer and my CHEAP 53% HNO3 to make some UREA NITRATE and then make some CHEAP NITROUREA with cheap H2SO4 and then add some CHEAP Formaldehyd solution and some Cheap sodium hydroxide and some cheap ammonia solution and get some CHEAP DTP and make some HMX with 100% HNO3 and AN (or I may build an ozon generator to make some nice Nitrogenpentoxide.


Yes, I'm crazy and I'm sure there is somewhere another thread about it and you already discussed this stuff, but I could'nt find it by using the search engine, so I thought: Be so kind and post some very interesting and helpful.

[Edited on 17-8-2010 by maxidastier]
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[*] posted on 26-8-2010 at 13:16


Anybody tried the method (HDN-->DPT) that posted by Axt? On this weekend i will try it, and if somebody interested in i will post the results.

--------

Today i tried to synth. DPT from HDN. I added the HDN to the sulfuric acid at 12-13° C and got a white dense mixture. I stirred it for 40-45min, after i poured it to ice and neutralized it with NH3 solution to pH 6.5 (when i neutralized the mixture, the temperature was 15-20° C), but i didn't get a precipitate. :/

Anyway i found a US patent about this synth and i read this: "HDN may be converted to DPT by treatment with sulfuric acid... " So may be not :D



[Edited on 27-8-2010 by Peroxid]
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[*] posted on 27-8-2010 at 10:42


Anyone tried or knew the method I mentioned.
Is it cheaper/easier than HDN-->DPT) route?
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[*] posted on 27-8-2010 at 12:04


Quote: Originally posted by maxidastier  
Anyone tried or knew the method I mentioned.
Is it cheaper/easier than HDN-->DPT) route?


I found this patent about this method...maybe i will try it.
http://www.freepatentsonline.com/4338442.pdf

The yield that is discribed by this patent (52%) is better than hexamine + acetic anhydride + cc.HNO3 route(48% - I done this procedure and i got 44-45% yield. ) - W. E. BACHMANWN,. J. HORTONE, . L. JENNER, N. W. MACNAUGHTAONND L. B. SCOTT, J. Org. Chem., vol73,p.:2769-2773,(1951).


[Edited on 27-8-2010 by Peroxid]
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[*] posted on 4-9-2010 at 08:33


Yeah, that's the patent...
But I won't be able to get formaldeyhde solution of that STRENGTH! Only 20%..
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[*] posted on 15-9-2010 at 19:09


An alternative is just to condense MEDINA with CH2O, guaranteeing absolutely no RDX will contaminate your product.
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[*] posted on 2-4-2011 at 04:07


http://www.e-journals.in/PDF/V8N1/97-100.pdf

What about that? May be hard to get that "ionic liquid", especially because it described very detailed.
But maybe someone knows something :D
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[*] posted on 26-8-2011 at 07:28


Quote: Originally posted by Peroxid  

I found this patent about this method...maybe i will try it.
http://www.freepatentsonline.com/4338442.pdf



pretty cool synth.

anyone already testet it?

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[*] posted on 5-3-2012 at 12:51


Some notes about separating RDX from HMX,

The solubility of RDX in water at room temperature is 45.9 mg/L.
The solubility of HMX in water is 3.49 mg/L.

By dissolving a mixture of RDX and HMX is another solvent that these compounds are both more soluble in, and then adding a quantity of water, in specific proportions, it is possible to selectively precipitate out the RDX.

For example, with 2 grams of crude RDX (which contained 8.6 percent HMX content) dissolved in 50 mL acetonitrile, if 25mL of water were added a precipitate of pure RDX could be separated out, giving 42.4 percent yield. Whereas if 50mL of water were added, the purity of the RDX in the precipitate was 99.2 percent, with a higher yield of 72.7 percent.
"Preparation Of Insensitive Rdx From Crude Rdx Using An Antisolvent. Phase Separation Process", Veera Boddu, Abburi Krishnaiah

[Edited on 5-3-2012 by AndersHoveland]
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[*] posted on 5-3-2012 at 19:38


I've found couple of words about HMX. Treatment of DTP (1 mole) by 3.2 mole of HNO3 + 1.6 mole of NH4NO3 at 60-65 C. I rather doubt about it- at the end of reaction HNO3 will be diluted. But who knows... Nice method of preparation of DPT has been evolved by an amateur- read my article at this forum.



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[*] posted on 9-3-2012 at 03:17


I heard somewhere that using urea and CH2O to form di-keto HMX can use concentrated H2SO4 (and NaNO3) in the synthesis with acceptable yields. Of course, normal mixed acids do not work when making normal HMX, or RDX.

[Edited on 9-3-2012 by AndersHoveland]
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[*] posted on 9-3-2012 at 04:43


After the 1000 posts AndersHoveland should be "Giver of the worst advice" ...



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[*] posted on 10-3-2012 at 22:38


Why so? I do not remember something really stupid in articles, written by Anders Hoveland. Or you lost finger or eye following his tips?



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[*] posted on 10-3-2012 at 22:44


"I heard somewhere that using urea and CH2O to form di-keto HMX can use concentrated H2SO4 (and NaNO3) in the synthesis with acceptable yields. Of course, normal mixed acids do not work when making normal HMX, or RDX."

Isn't this enough?




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[*] posted on 11-3-2012 at 14:44


Well, it is not obviously the best ant clearest explanation. But it is only a tip- look in a literature for some additional info. It is not the detailed manual how to prepare keto-HMX (BTW, what is it? I've never heard about such compound, only about keto-RDX). I think, that really bad advice is to make silver fulminate- it is well-known benchmark of very sensitive explosives.



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