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Douchermann
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That would make sense. The by products would then react producing 1/4 mole of hexamine for ever mole of hexamine used previously (ammonia as the
limiting reactant). So if 10 grams of hexamine is used initially, 2.5 grams will be produced (theoretically) from the by products.
It\'s better to be pissed off than to be pissed on.
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Rosco Bodine
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It would be nice if it went that way , but no such luck .
The acidic conditions prevent the recombination of
the byproduct ammonia and formaldehyde to reform
the original hexamine and this parallels the situation
for RDX . You see the formation of hexamine only
occurs in alkaline reaction medium where the ammonia
can be free and the formaldehyde is also reactive .
In acidic systems there is a different reaction which
leads to methylamine derivatives and di and tri-methylamine derivatives instead of the hexamethylene
cyclisation favored in alkaline systems .
Even for the case where it was once believed that
an additional yield of RDX could be gotten from the
reforming of hexamine from the decomposition products , this has been proven to be untrue , but involves some
complex intermediates of a different nature which form
in the extreme nitration mixtures for RDX , and then are converted to RDX by a series of reactions .
That is unlikely to be possible in the aqueous system
used for producing TMTN .
One thing that could be done is to use the waste filtrate
from TMTN for production of formite . Adding the proper amount of ammonium nitrate and urea would cycle the waste formaldehyde to methylamine nitrate
and the di and trimethylamine nitrates also in lesser amount . These products along with additional AN and urea ,
could be mixed to form a melt castable which would be a high energy composition nearly equivalent to TNT and probably cap sensitive . If not , the
TMTN could be used
as a booster for it .
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Douchermann
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Could just AN be used to convert the waste formaldehyde into Methylamine nitrate?
4CH2O + 5NH4NO3 = 4CH3NH2 + 6HNO3 + H2O
CH3NH3 + HNO3 ----> CH3NH2*HNO3
Or would that reaction not progress.
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Rosco Bodine
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A simultaneous reaction is not practical because the
methylamine formation is favored by high temperatures ,
while the TMTN formation requires low temperatures .
It goes something like you have it but the reaction is more complex with secondary reactions and byproducts which are reduced and involved with yet
another reaction with urea . There are a couple of patents concerning this . I can't dig them up right now as I am salvaging what I can from about
four years worth of data loss after the main drive has failed in my computer , which should keep me busy for weeks trying to get a fraction of the
data restored from what part of it was backed up . The drive failure sneaked up on me with read and write errrors that have corrupted everything
pretty badly that was a larger file . A lot of the small pdfs. I may get back but that is about it .
Everybody who has a burner should burn backups and
keep docs properly archived . I used to do it regularly , but have gotten distracted lately and didn't know that
a lot of the data I was backing up was already corrupted .
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Douchermann
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Oh okay, thanks. I'll see if I can find the patents myself.
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Rosco Bodine
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With regards to utilizing the waste solutions , it is something mainly pertinent to industrial scale production which would seem worth the trouble for
economic and environmental considerations . For lab scale syntheses it is hardly worth the trouble . This process would also be predicated on the
success of using nitric acid instead of the sulfuric or hydrochloric acid as has been described for TMTN , so that
there would only be nitrates in the final mixture . This is part of my interest in seeing if the TMTN can indeed be made
from HDN as a starting material , and using nitric acid to
achieve the pH 1 reaction condition , not only to see if the
yield of TMTN may be improved , but also because the value
of the waste solution for further reaction may be improved ....
not only for potential value in regards to formite which may or may not proceed well , but simply knowing that neutralization with ammonia and
evaporating would lead
to a useful residue of nitrates and hexamine , so that there
would be no waste output from the TMTN production .
Efficiency is everything with regards to chemical plants ,
so zero waste is an important goal for the economic and environmental concerns ......waste not , want not 
The two " formite " ( formaldehyde / AN reaction mixture ) patents that I know about are
EP0037862
GB1548827
Patent related to such mixtures value in cast melts
US1968158
Related reaction under alkaline conditions which
produces hexamine instead
US3660182
Slurry related hexamine containing AN composition
US3496040
[Edited on 12-7-2006 by Rosco Bodine]
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SAM4CH
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I prepared 150 R-salt and I tried to detonate 50g and it exploded nicly, after few months (6 month) I tried to detonate the other 100g with primer and
poster but it did not explode!! what's happen to my r-salt?
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quicksilver
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What conditions was it stored under? And what were the specifics of the attempt at detonation? - In other words, if something funtions at one time and
then at another time the SAME thing does not funtion, the question one asks is "what changed?" This is the way computer code is debugged & the
same methodolgy works for a variety of issues.
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SAM4CH
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it kept in empty aerosol can "semi tight", and about detonation there is no sign for explosion of r-salt and I am sure because I could see the traces
of powder and the explosion sound was weak!!?
Note: I kept it as a block "I melt it before"...
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Kray
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How I know need make all reaction by all rules if you want to make r-salt.Whats was the temperature when you was making it?
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DeAdFX
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| Quote: | Originally posted by Mumbles
I've tried it and gotten shit for results. I keep the temp low, but it started bubbling. It's definatly not ammonia, or formaldehyde or HCl. It's
hard to explain. It smells kinda like warm bread if that makes any sense.
After maybe 45 minutes this foamy stuff on top forms. I think this is the R-salt. I let it react for the time recomended by Mr. Cool, and by morning
the foam was all but just about gone. I don't like it. I would be willing to try if I found a better method. |
Hmm I got the same results[shit] as you but I only let my stuff settle for 6 hours instead.
Probable reasons for shit yeild. I was only able to keep the temp between 10-15C through most of the synthesis[getting as high as 17-20C. The
thermometer was difficult to read as the foam was blocking the #'s. I also waited to damn long to purify the "product". As mentioned in this .pdf http://www.sciencemadness.org/talk/viewthread.php?action=att... it says that you should only let the product react for 20 minutes to get the
greatest yeild. Does this mean the moment you add the acid or the moment you are done adding the acid?
Hmm its a little difficult to maintain the temperature @0C than I though. I guess I could use more ice, cool down the Nitrous acid before addition,
or slow down the acid addition[nitrous to hex/hcl]. I guess these are the only easy ways to maintain the temperature?. .
Stupid question but since I failed in the synthesis.... Are the CTMTNA crystals suppose to perciptate[95% of them] within the first 10 minutes with
the other 5% in the next 10 minutes? Or is your product the foam shit because looking at Axt's pictures my foam is yellow and his product is yellow?
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SAM4CH
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I need a perfect procedure for oxidation of r-salt to RDX using AN/H2SO4 or H2O2 or hypochlorite!!!
Sam
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quicksilver
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In an attempt to re-energize discussions on energetic materials here I was wondering anyone continued any of the experiments dealing with R-SALT and
reached any conclusions outside of the quoted material re:
*R-SALT as a "gateway" to RDX synth,
*R-SALT yields (influences) and conclusive stats on R-SALT - it's VoD & uses in industry or the military......anyone(?)
[Edited on 1-10-2007 by quicksilver]
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The WiZard is In
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I have eye-balled this in the obvious books. The Book sez —
It do be/can be made from formaldehyde, ammonium hydroxide, and sodium nitrate.
Köhler and Meyer note that ... although easily prepared and
powerful, the explosive has not been used in practice owing
to its limited chemical and thermal stability.
They note the hexa. / alkali metal nitrite / dilute acid method
of synthesis.
PATR2700 C630-31
It was Bachman & Deno who discovered that the chief factor
that determines the nature of the product is the pH of the soln.
WE Bachmann & NC Deno, The Nitrosation of Hexamethylenetetamine
and Related Compounds, JACS 73, 2777-79 (1951).
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quicksilver
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Wooo... you hit an old thread; cool.
I hit the PATR first thing.
I did find some material from a text written in German (don't have it near this station) at or around the time of the War.
They experimented with it but dropped it as it had a low shelf life (needed seriously strict conditions to maintain itself) & reacted poorly to
compaction & or a eutectic w/ what little TNT was available at the time of writing. The idea was to stretch the TNT supply as well as heighten
it's brisency. It made more sense to adulterate the TNT with ammonium nitrate rather than R-Salt and most likely the heat (even as low as 80 C)
disagreed with it's (R-Salt's) longevity.
Back some years ago when I really did look into this; mostly it was European material that had any info. The important elements to the synthesis are
temperature control (cold) and maintaining ph. It's a easy lab but it's a curiosity as a practical expls. it's not really appropriate.
edit:
Bachman was a real RDX fan. Much of his professional published stuff was RDX this and that. Most likely, the REALLY interesting stuff he did is still
tough to get due to the nature of government patent disclosures.
[Edited on 1-5-2010 by quicksilver]
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The WiZard is In
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Quote: Originally posted by quicksilver  |
They experimented with it but dropped it as it had a low shelf life (needed seriously strict conditions to maintain itself) & reacted poorly to
compaction & or a eutectic w/ what little TNT was available at the time of writing. The idea was to stretch the TNT supply as well as heighten
it's brisency. It made more sense to adulterate the TNT with ammonium nitrate rather than R-Salt and most likely the heat (even as low as 80 C)
disagreed with it's (R-Salt's) longevity.
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The Book sez
Eutectic Composition With TNT
42% Cyclo....
58% TNT
Rate of detonation 7 000 m/sec
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hiperion42
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necromantic 
.....ejuu....................................................................Ffg..............................g.............
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gnitseretni
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Just re-read the whole thread and noticed there was no mention of recrystallization. Is it just not necessary or is there a different reason?
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quicksilver
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| Quote: Originally posted by gnitseretni | | Just re-read the whole thread and noticed there was no mention of recrystallization. Is it just not necessary or is there a different reason?
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I think that's a very good question. In literature (especially from Germany) there had been no specific mention of re-crystallization. It may be that
R-Salt is a delicate material & recrystallization may not be the best idea from a stability stand-point. It apparently does not have a great
shelf-life in any event (narrow temp sensitivity). The solvent may be too expensive to make that an industrialist effort worth the money (Ethel
Acetate was mentioned). But I see no reason why a less expensive material couldn't be used. Lab-grade acetone is NOT what is bought at hardware stores
and the impurities associated with less expensive materials may be the real reason. R-Salt was an effort to save money.
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gnitseretni
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I can't find any useful information on R-salt, let alone anything on recrystallization
I suspect the low yield is to blame.
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gnitseretni
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Made some R-salt. Used the same amounts Axt did but yield was (as usual) crappy. Only a measly 5 grams
I took a teaspoon R-salt and dissolved it in 10ml denatured alcohol. It dissolved easily. Then I added it to an ounce of cold water. Nothing happened.
I thought maybe I didn't have enough water so I doubled the amount of water... still nothing. Then 250ml water... STILL NOTHING!! What the hell!
I thought adding more water would probably be a waste of time so I flushed it down the drain. Then I tried it with methanol(HEET). Same thing..
nothing!!
Then before I got a chance to try it with MEK, a windgust came and blew the rest of my R-salt all over the lawn  And I was like.. F U then.. I don't like R-salt anyway  No really.. I won't make this shit again, I had enough of the crappy yields.
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Anders2
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RDX easy synthesis
I wonder if H2O2 can oxidize this nitrosamine to the nitramine, potentially forming RDX?
I read in the literature that nitrosobenzene can be oxidized to the nitro by bubbling in NO2, so presumablym adding a small ammount of nitrate salt to
the nitrite used in the reaction for making CTMTNA, would allow formation of RDX, not CTMTNA. Since HNO2 + HNO3 <--> 2NO2 + H2O
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Rosco Bodine
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No, there won't be any "RDX easy synthesis" via the method you are proposing.
IIRC there is a conversion of R-salt to RDX possible using H2O2 and high concentration HNO3, but the overall yield is inferior from the same starting
materials to the conventional nitrolysis of hexamine dinitrate using highly concentrated HNO3, so the economics are unfavorable for the R-salt route.
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quicksilver
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Absolutely. One of the simplest direct nitration is in use in a plant in the mid-west US (the USA's largest) & in fact does use hexamine
di-nitrate. It's a straight nitration and has been in operation for decades. So the likelihood of another technique superseding it is very unlikely.
This has been demonstrated as an entrenched production method in industry magazines and even television shows like Discovery because in the final
analysis the cost factor is really only the higher percentage acid.
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AndersHoveland
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| Quote: Originally posted by Anders2 | I wonder if H2O2 can oxidize this nitrosamine to the nitramine, potentially forming RDX?
I read in the literature that nitrosobenzene can be oxidized to the nitro by bubbling in NO2 |
Although nitroso groups can usually be easily oxidized, oxidizing nitrosamines (where the -NO group is connected to a nitrogen atom) is much more
difficult. Plain H2O2 is unable to oxidize nitrosamines, such as CTMTNA.
For oxidizing CTMTNA into RDX:
Peroxytrifluoroacetic Acid. I. The Oxidation of Nitrosamines to Nitramines
William D. Emmons. J. Am. Chem. Soc., 1954, 76 (13), pp 3468–3470 (1954)
Peroxytrifluoroacetic does not seem to oxidize organic chlorides,
"Anhydrous solutions of peroxytrifluoroacetic acid in methylene chloride can be prepared..."
however, peroxytrifluoroacetic has been shown to oxidize off tert-butyl groups, but not methyl or ethyl groups,
"The trifluoroacetic acid-mediated removal of t-butyl groups in protected amino acids leads to the formation of t-butyl trifluoroacetate"
Peroxytrifluoroacetic acid can be prepared by reacting 90% H2O2 with pure trifluoroacetic acid.
Other possible methods of oxidation
Peroxytrifluoroacetic acid is also mentioned in the literature as being used to oxidize pyridine to pyridine N-oxide. Oxidizing pyridine in this way
must be very difficult, otherwise such an obscure regent would not have to be used. Any other regent that is capable of oxidizing pyridine to its
N-oxide also probably has a high likelihood of being able to oxidise nitrosamines to nitramines.
So here is a list of the other methods that can be used to selectively oxidize pyridine:
Titanium "zeolite" catalyst
Selective mono N-oxidation of substituted pyrazines in good yields using 30% dilute H2O2 as an oxidant with a specially prepared titanium silicate
catalyst is possible.
Preparation of the Catalyst:
Add a solution of titanium peroxide to ethyl silicate (with or without an organic solvent) to obtain a gel. Hydrolyze the homogeneous gel previously
obtained, by adding an organic base to the gel. The ammount of organic base should be only 6-15% of the ammount of silica gel. Next, add deionised
water after the yellowish-white color of the gel begins to turn into a greenish-white color. Stir the greenish-white gel for about 1 hour, then heat
the gel in a pressure cooker at 100 -110 C. The gel must be constantly heated in this way for at least 20 hours. Further heating, up to 2 days, is
preferable. This will result in a solid composite product. Separate out the resultant solid composite material, dry, and bake at a 350-500C
temperature to obtain the final product. This is a catalyst and so only a small quantity need be prepared. The organic base should be an organic amine
with lots of bulky organic groups on it, either a tri- or tetra-alkyl amine, such as tetrapropyl ammonium hydroxide. Alternatively positively charged
coated silica particles can be used instead of the ethyl silicate. These can be prepared by mixing an aqueous colloidal silica with stabilized basic
aluminum acetate. The aluminum composition is stabilized with a small quantity of boric acid, which controls the hydrolysis of the aqueous solution of
basic aluminum acetate.
The catalyst produced above is known as TS-1 and is basically a porous titanium silicate crystal with a structure analogous to zeolite. TS-1 is not
yet commercially available. It can also catalyze the oxidation by H2O2 of imines R2C=NH into oximes R2C=NOH.
Methyl Cyanide Activation
Methyl cyanide, also known as acetonitrile, can activate the H2O2 so that it can oxidize the cyclic nitrogen atom in pyridine.
At a pH of 8 , H2O2 reacts with CH3CN to form a peroxycarboximidic acid intermediate, with the structure,
CH3C(=NH)O--OH. This is unstable and immediately oxidizes whatever reducing agent is in solution. If no reducing agent is present, acetamide will
result and oxygen gas will escape from solution. Other nitriles beside methylcyanide also will work, possibly even addition of threads of acrylic
fabric (synthetic wool) will work. An alkaline solution of a nitrile and H2O2 can also oxidize an alkene to an epoxide.
Using H2O2 and Acetic Acid
This method initially sounds too easy to be true. But it may be possible that this simple method has been overlooked by researchers, in favor of the
much more obscure/uncommon peroxytrifluoroacetic acid.
"Oxidation of 2,6-diamino-3,5-dinitropyridine by refluxing with a 30% solution of H2O2 in acetic acid produced
2,6-diamino,3,5-dinitropyridine-N-oxide in 80% yield."
R. Hollins, L. Merwin, R Nissan, Journal of Heterocyclic Chemistry 33, p895 (1996)
H. Ritter, H. Licht. Journal of Heterocyclic Chemistry, 32, p585 (1995)
So there you have it, three different methods that are likely to be able to oxidize CTMTNA into RDX, using readily available precursors.
[Edited on 22-9-2011 by AndersHoveland]
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