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Author: Subject: Neglected RDX Process
quicksilver
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[*] posted on 26-10-2005 at 15:51
Neglected RDX Process


The use of H2SO4 / HNO3 for the nitration of amines like RDX was explored via a patent wherein the standard nitration of potassium methyleneamidosulphonate yielded RDX. The above is synthed by condensing formaldehyde with sulphamic acid (limescale cleaner).
This would bring the synthisis of RDX to the level of a common nitration and the exploration of nitramines without the nesessity of clear white high % HNO3.
Is anyone familiar with this process and has utilized it with success?
Attached is the patent describing the method in original form.
Anyone able to shed more light on this process?
Merck lists Sulphamic acid mol weight as 97.10: my copy gave me no information on potassium methyleneamidosulphonate. If the formaldehyde is 37% what is the mechanism for synthesis?

[Edited on 27-10-2005 by quicksilver]

Attachment: RDX from sulphamic acid.pdf (204kB)
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Chris The Great
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[*] posted on 26-10-2005 at 16:19


The nitrating mixture in the patent is 80% nitric acid and 20% sulfur trioxide. I've seen the menthod mentioned before, and the 98% range nitric acid is needed, as well as pure SO3. It is actually harder than a normal nitration.

The only advantage I can see is the high yeild and smaller amount of nitric acid used.
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[*] posted on 26-10-2005 at 20:38


Quote:
Originally posted by Chris The Great

The only advantage I can see is the high yeild and smaller amount of nitric acid used.


Superficially however, that sounds like a great deal of advantages....have you or anyone you are familiar with attempted it? What are the proceedures involved?
--- A mixed nitration could be performed with a solid nitrate (yes?) thus circumventing the distilltion issue. On the surface it seems like a neat little lab.




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[*] posted on 27-10-2005 at 13:09


The problem is that the process requires absolutely anhydrous conditions ( hence the SO3 ) or the sulfuric acid destroys the RDX.
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[*] posted on 27-10-2005 at 17:37


Thus without a rather well equiped lab the process is not feasable....(?)


Should that be the case, that is a shame.

When nitrating hexamine directly occationally there is a "flash" from the addition of very small amounts of hexamine into the high grade of HNO3 freshly distilled. This material is near clear and would not contain a sizable percentage of NOx. Is this a common occurance and if so, is there a method to minimize it (like reducing the temp even further than 0 C)?
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[*] posted on 27-10-2005 at 21:06


I'd have to argue against the sulphuric acid destroying the RDX, otherwise the conversion of R-salt to RDX via AN/H2SO4 wouldn't work?!

Unless its actually been tried, I think its worth trying. SO3 may only maximise yeilds, since these are not exotic for laboratories or industry, they have no reason not to use them. Perhaps incomplete nitration is a possibility without N2O5 in solution. SO3 + 2 HNO3 <--> H2SO4 + N2O5.

See attachment for synthesis. They prefer P2O5 to SO3.

[Edited on 28-10-2005 by Axt]

Attachment: Tripotassium 1,3,5-Triazacyclohexane- 1,3,5-trisulfonate.pdf (395kB)
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[*] posted on 28-10-2005 at 00:35


I haven't tried it myself, but someone ( either here or on roguesci; perhaps it was pdb ? ) in the "community" did, and said that nitration of R-salt did work with mixed acids but that yield rapidly dropped off with increasing water content. So, I'm not saying it doesn't work, just that it probably won't work with the kind of mixed acids you can use for NG.
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[*] posted on 28-10-2005 at 10:46


H2SO4 hydrolyses RDX, so the yields cant be high...
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[*] posted on 28-10-2005 at 20:41


Quote:
<i>PATR 2700, 3, C631</i>
Simedek (Ref 12) reported the treating of R-Salt with AN & H2S04 to obtn N, N-Dinitro- N"-nitroso-cyclotrimethylenetriamine which on further treating with the nitrating mixt yielded 98% of RDX.

12) J. Simecek, ChemListy (Czech) 51, 1323-26 (1957) & CA 51, 17942 (1957).
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[*] posted on 29-10-2005 at 06:38


Quote:
Originally posted by Axt
Quote:
<i>PATR 2700, 3, C631</i>
Simedek (Ref 12) reported the treating of R-Salt with AN & H2S04 to obtn N, N-Dinitro- N"-nitroso-cyclotrimethylenetriamine which on further treating with the nitrating mixt yielded 98% of RDX.

12) J. Simecek, ChemListy (Czech) 51, 1323-26 (1957) & CA 51, 17942 (1957).



EXACTLY... There is no question it can be done.
I will have most of the materials when I can finally get some phosphorus pentoxide this weekend.
The article was a real help. -=Thank you=- I have found some other material by Bockmann as well.

The concept of "All Liquid Feed" interests me as I have a 3 neck flask but not a "five neck flask" as mentoned in the article that further detailed this issue. (Frankly, I have not even seen one). What was mention was the introduction of heximine in solution with glacial acidic acid for this "all liquid feed"....would that funtion equally well in all instances; such as streight nitration...?
My reason for asking is that powder feed has resulted in tiny "flashes" that are dangerous and annoying. This problem had been mentioned in a patent (US2798870) and was one of the chief reasons for a "all liquid feed" in industry to this day. Werner Bachmann copied the liquid feed from Canadian, George Wright (US2434879).
There is such a weath of knowlege on this subject but it's tough to get at....and few people have worked with nitramines in the "hobbiest community", it seems. All help here is DEEPLY apprieciated.
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[*] posted on 29-10-2005 at 07:37


Have you tried using hexamine dinitrate instead of plain hexamine to see if the problem with " flashes " on contact with the acid is eliminated ?

Preforming the dinitrate of hexamine eliminates a lot of the exotherm which occurs simply upon neutralizing the hexamine when it hits the acid and it also eliminates 2 moles of the fuming nitric acid requirement for the nitrolysis , since ordinary concentrated acid or less , can be used for the neutralization in advance of hexamine .

Also , and this would need to be verified , it seems like I remember something in the literature about the presence of NH4NO3 in certain percentages premixed with the fuming nitric acid is beneficial to the stability and safety of the nitrolysis , and I believe this was a patent method which applied to all the usual nitrolysis schemes with some variation for each . Does that sound familiar to anyone ? I would have to review the literature to be certain of this . And IIRC it was not a universally accepted method or theory , having some argument in the literature similar to the
" K " process for increased yields which others never seemed to get , but the use of NH4NO3 was for stability and safety and not claiming any increase yield from dubious secondary reactions .

[Edited on 29-10-2005 by Rosco Bodine]
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[*] posted on 29-10-2005 at 10:46


Quote:

I remember something in the literature about the presence of NH4NO3 in certain percentages premixed with the fuming nitric acid is beneficial to the stability and safety of the nitrolysis , and I believe this was a patent method which applied to all the usual nitrolysis schemes with some variation for each . Does that sound familiar to anyone ?


It seems that the ammonium nitrate added to the fuming nitric was a commonly known fact in the past, or at least in several old organic chem books from around the 50's that I have read. However, the use of the NH4NO3 in all these books is to "increase yield by allowing the utilization of all the hexamine or HDN's methyl groups". As for the use of NH4NO3 being added for stability, I have not heard that mentioned, not saying I do not believe you, just saying I have not heard it mentioned elsewhere.

[Edited on 29-10-2005 by rogue chemist]




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[*] posted on 29-10-2005 at 11:54


I have mixed concentrated HNO3 and NH4NO3 before. It was a while ago but what I do remember is after dissolving the NH4NO3 in the nitric acid an unstirrable crystal sludge resulted. I was lead to believe it was ammonium dinitrate that was formed.

Regarding the link given by Quicksilver (very interesting, thanks). I would just like to clear up weather there is a difference between 'aminosulfonate' and 'amidosulfonate' (sulfamate). Over the ages I'm assuming it may be possible that the names ultimately refer to the same thing. If so..
Just to point out that it states that the methylene 'amino'sulfonate is prepared by reacting ammonium 'amino'sulfonate with formaldehyde, not sulfamic acid with formaldehyde. I would then assume that ammonium 'amino'sulfonate is prepared by a simple acid/base reaction involving ammonium hydroxide and sulfamic acid. Or would there be such a thing as sulfaminic acid?




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[*] posted on 29-10-2005 at 15:46


For the NH4NO3 + HNO3 related patent see US2395773 .

There seems to be conflicting information in the patents regarding the usefulness of NH4NO3 and under what conditions it may participate in the reaction .

See US2798870

Among my notes for a suggested but not yet done experiment using HDN as the precursor is nitrolysis by addition of the dry HDN to 97% HNO3 , using 2.2 ml of the 97% HNO3 per gram of HDN , and premixing dry urea nitrate in small amount
with the dry HDN , 5 or 6 milligrams of urea nitrate for each 1 gram of HDN .

I had not yet decided whether or not to use any NH4NO3 mixed with the HNO3 in advance , or perhaps also mixed in small amount with the HDN . These are experiments which I have not yet done .
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[*] posted on 30-10-2005 at 04:53


The attached file should be of interest .

In regards to the use of NH4 salts with HNO3 in the patent US2395773 , a 91% yield of RDX is reported in example 5 .

Even though the ratio of HNO3 used in all the examples is so high as to negate any economy , it is the comparative nature of the examples which is interesting , showing that the ammonium sulfate really increases yields .

There is another thread which is related to Ammonium Pyrosulfate , and one potential usefulness may be found in in RDX synthesis if the pyrosulfate is found to have the same or perhaps even better effect as a nitrolysis catalyst as the normal sulfate . Since the pyrosulfate has the ability to take up water and convert to the acid sulfate , it should be tested to see if it has value even beyond ordinary ammonium sulfate .

Attachment: US2395773 RDX via HNO3 and NH4 salts.pdf (237kB)
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[*] posted on 30-10-2005 at 07:20


Quote:
Originally posted by Rosco Bodine

Also , and this would need to be verified , it seems like I remember something in the literature about the presence of NH4NO3 in certain percentages premixed with the fuming nitric acid is beneficial to the stability and safety of the nitrolysis , and I believe this was a patent method which applied to all the usual nitrolysis schemes with some variation for each . Does that sound familiar to anyone ? I would have to review the literature to be certain of this . And IIRC it was not a universally accepted method or theory , having some argument in the literature similar to the
" K " process for increased yields which others never seemed to get , but the use of NH4NO3 was for stability and safety and not claiming any increase yield from dubious secondary reactions .

[Edited on 29-10-2005 by Rosco Bodine]


This is an excellent idea. I just took a look at the patent...GOOD STUFF!
The "flashes" are something I had hoped to address with an "all liquid feed" mixing the hexamine w/ Glacial Acidic Acid but the NH4NO3 idea is a good one. The flash is anoying and potentially dangerous. I thought it had to do with temp, the hex or HDN "splashing" into the acid; but to no effect. It would happen once in a nitration....I simply don't understand it. But now I hear that it has happened elsewhere...
I really want to try my hand at alternative methods of working with hexamine ever since I saw the beautiful needle crystals I got from my HDN.

Thanks again.
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[*] posted on 30-10-2005 at 07:29


Quote:
Originally posted by froot
Or would there be such a thing as sulfaminic acid?


I have a large PDF Merck (11th ed.) and could not find any "sulfaminic" acid. But that doesn't mean it doen't exist of course. I just could not find any info....and the search engines continue to correct the name....:P




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[*] posted on 8-11-2005 at 06:21


Quote:
Originally posted by Rosco Bodine
The attached file should be of interest .

In regards to the use of NH4 salts with HNO3 in the patent US2395773 , a 91% yield of RDX is reported in example 5 .

Even though the ratio of HNO3 used in all the examples is so high as to negate any economy , it is the comparative nature of the examples which is interesting , showing that the ammonium sulfate really increases yields .
.



There is no question now; HN4NO3 addition DOES increase yields. EVEN with a 5:1 ratio. Out of context of the patent's original intentions (12:1) a simple experiment showed this to be a continious 70%+, which is good with a 5:1 HNO3. The addition should follow the patent which is a very small amount of the HN4 salt measured to the HNO3. The safety issue was paramount in my concerns and indeed the HN4 addition plays a unique role, of which I do not understand (the patent did not explain why either)......but it is the method of choice if direct nitration of HDN or hexamine is utilized.
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[*] posted on 8-11-2005 at 07:00


Quote:
Originally posted by quicksilver
HN4 salt


Dyslexia :P

Quote:
Originally posted by quicksilvera simple experiment showed this to be a continious 70%+,


Does that mean you just followed the patent recieving 70+% yeilds? which example?

See attachment for NH4 salt + hexamine + acetic anhydride -> 2 RDX. Not as useful as the patent which dismisses acetic anhydride, but it adds to the discussion.

[Edited on 8-11-2005 by Axt]

Attachment: A New Method of Preparing the High Explosive RDX.pdf (528kB)
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Rosco Bodine
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[*] posted on 8-11-2005 at 12:59


With regards to the usefulness of NH4 salts in the nitrolysis reaction producing
RDX , the sulfate salts are even more interesting than is ammonium nitrate ,
since the yield is increased even beyond
what is gotten using the nitrate . The sulfate is more interesting also because there are a series of sulfate salts , not only the normal sulfate , but the acid sulfate , and the pyrosulfate , which have
untested potential .

It is not clear if the NH4 salts will have as much value in increasing yields in nitrolysis
mixtures where a lower excess of HNO3 is
being used , and HDN is the precursor instead of hexamine . Neither is it clear if
the stoichiometric ratio of NH4 salt which is optimum should be calculated on the basis of the amount of HNO3 , or on the basis of the hexamine or hexamine contained in HDN . So there are some unknowns with regards to adapting the patents ratios to a more economical nitrolysis using from 2 to 2.5 ml of 1.5 HNO3 per gram of HDN . Also it is known that urea nitrate in .5 - 1% added to the
hexamine by itself can give a 4 or 5% yield increase in the nitrolysis using low amount of HNO3 , like 2 ml HNO3 per gram of HDN . Dicyandiamide ( and probably even better its nitrate ) produces a similar increase when used the same way . The one thing in common about these two substances and ammonium salts is that they tend to act as anti-oxidants in nitric acid , reducing the oxidizing decomposition products of nitric acid to nitrogen and water , while themselves being decomposed . Another
variable is whether it is better to add the NH4 salt to the acid , or premix it with the HDN or hexamine , or apply both strategies .

It is this property of ammonium salts which accounts for a more pure form of nitric acid being obtained by distillation
of H2SO4 + NH4NO3 mixtures than is gotten from use of alkali nitrates .

Since nitrolysis mixtures are heavily polluted with the very sorts of unstable decomposition products which behave similarly as an accellerated decomposition
of HNO3 itself , this is probably why is
realized the usefulness of NH4 salts and
urea and dicyandiamide in the nitrolysis
mixtures , as they stabilize the deteriorating acid and oppose the autocatalytic decomposition from accumulating byproducts , maintaining a higher nitration quality for the acid while the nitrolysis is in progress by slowing its
deterioration to a more oxidizing and contaminated acid . This is even more important when the lessser amounts of acid are being used for economy .

That's my theory concerning the usefulness of NH4 salts under conditions
which are much different from the K-process parameters , and involve no
" recombinant formaldehyde " reactions
which seem unlikely to me . As I see it ,
no free fromaldehyde would long survive in a nitrolysis mixture , to be reacting with anything except the nitric acid itself and
quickly converted to formic acid as a stable
end product and byproduct in the mixture .
I just can't visualize any Knoffler style scheme for the utilization of the formaldehyde , maybe in reaction with nitroamide which could be present , but
not according to the classical textbook
comments on the Knoffler reaction ....IMHO those theories just have it wrong whatever is occuring to explain some anomalous utilization of byproduct formaldehyde . It may be that formaldehyde is somehow being returned to the reaction , just not by the mechanism they are suggesting , which is doubtlessly an oversimplification of what is actually occurring . A nice way of saying they have an idea of what has occurred but little clue as to the mechanism :D Anyway , there are
many complex reactions occurring in a nitrolysis , and there is probably a different explanation for the reactions which are most likely at different temperatures and concentrations of
acids and NH4 salts . Only in certain
reaction conditions which are specific to
the particular temperatures and ratios of reactants , will an increase be produced
beyond a plain HNO3 nitrolysis . If the
correct proportions are not used , then
a negative effect is the result , and that
is something of an enigma itself to explain .
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[*] posted on 9-11-2005 at 06:56


Originally posted by Axt
Quote:

<i>PATR 2700, 3, C631</i>
Simedek (Ref 12) reported the treating of R-Salt with AN & H2S04 to obtn N, N-Dinitro- N"-nitroso-cyclotrimethylenetriamine which on further treating with the nitrating mixt yielded 98% of RDX.

12) J. Simecek, ChemListy (Czech) 51, 1323-26 (1957) & CA 51, 17942 (1957).


It would not be any surprise at all to me if the PATR abstract concerning this route to RDX is a typographical error or a misinterpretation , and that this route to
RDX is not possible .

It would seem more logical to me if the
further nitrolysis of R-Salt was accomplished by AN + HNO3 , rather than
AN + H2SO4 as PATR is saying .
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[*] posted on 9-11-2005 at 07:04


Quote:

Does that mean you just followed the patent recieving 70+% yeilds? which example?



Mean Dyslexia you? Happens me to never.

Actually, I wanted to avoid working with the older methods and try something new like an R-salt process or the titled method using sulfamic acid but I just couldn't afford the chems and I just hate distilling acid... But Roscoe posted that patent re: higher yields via ammounium nitrate....Hell, I had to try it.
But mind you I am not THAT wasteful of acids. So I used a 5:1 ratio with DNH and simple hex w/ the addition of NH4NO3. I need to be looking at the patent and I dont have it in front of me but I believe I used Example 2 so that is one part by weight ammonium salt to fifty parts acid (tiny bit) but my extrapolation from that varied from the example which used a 1:12 ratio of acid to hexamine. I used a 1:5. I received 23.5 grams totally dry product from 25 grams hexamine - That's close to 70 when I looked at the DNH yield which was better and averaged so I would say I was about at 70 via the process. I don't have my notes here so I can't show the math but it's close...(I just got taught a lesson about drying my product and made sure that stuff was BONE dry this time) :D My DNH nitration was much better but I don't want to post the figures as that was a smaller one and I don't have the figures in front of me (but all the other factors were the same, temp, time in each bath, etc).
The major issue was that when I used a simple nitration previously I has a "flash" when I added the hex (it would actaully fire!) even in amounts that were tiny. It was dangerous and time consuming. By the use of the patent proceedure I received no flash and I believe my yields improved by worthwhile percentage. Previously I believe that from a ratio of 25gr to 125 gr of HNO3 I would get about 19gr and it would take all damn day (using un-nitrated hex). I am extremely careful and wear the appropriate protective gear but that flash seemed unavoidable. I didn't enjoy nitarting hex as it seemed that it in-and-of-itself was wasteful of material. My purpose was not to make RDX per se' but to learn more about the niration process. Thus if I had x amount of starting material and received y amount via an intermediate nitration (DNH) in a sence I was receiving close to the same final product. If I could improve the final yield even if it was a few perrcent and not have to waste hex through a di-nitration, that was useful information, plus eliminating the flash....it seems like I got just what I had hoped for in that info. Example 2 claimed 85% yields as I remember but they used a lot of acid. 12 to 1 ratio I believe.

Jeez, I just re-read this post, it's early out here and I'm at work - I am babbeling.....forgive me; you get the idea of what I was trying to get accross.
:o

[Edited on 9-11-2005 by quicksilver]
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[*] posted on 9-11-2005 at 07:44


Quote:
Originally posted by Rosco Bodine
With regards to the usefulness of NH4 salts in the nitrolysis reaction producing
RDX , the sulfate salts are even more interesting than is ammonium nitrate ,
since the yield is increased even beyond
what is gotten using the nitrate . The sulfate is more interesting also because there are a series of sulfate salts , not only the normal sulfate , but the acid sulfate , and the pyrosulfate , which have
untested potential .

It is not clear if the NH4 salts will have as much value in increasing yields in nitrolysis
mixtures where a lower excess of HNO3 is
being used , and HDN is the precursor instead of hexamine . Neither is it clear if
the stoichiometric ratio of NH4 salt which is optimum should be calculated on the basis of the amount of HNO3 , or on the basis of the hexamine or hexamine contained in HDN .



Your thoughts on accellerated decomposition are well taken. I wonder were these processes to take place in industrial settings if some decomposition could be avoided..... However from what little I worked with I would say that the quality of the HNO3 has an impact in a small-scale experiment. - It DID indeed work out the way the patent pointed to. But I would hasen to add that this was not preformed repeatedly and that on other occations I have gotten some variences for no explainable reason I could find. But not this time.
When variences have occured in times past I noted everything I did. But I can find no yardstick for them.
In this instance I took the leap that the stoichiometric ratio of NH4 salt which is optimum would be calculated on the basis of the amount of HNO3. But you say Dicyandiamide [& urea nitrate] may also be of value....and point to them acting as anti-oxidants in nitric acid. This rings a bell as acid quality has been a big thing with me. If it's REALLY clear white fuming; I get results.

I had thought about the sulfate and it's potential. Since for no other reason than it's unbelievable availablity I would enjoy testing it as well. - Could you please elaborate on the pyrosulfate? :P




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[*] posted on 9-11-2005 at 09:03


There is a thread I started in General about Ammonium Pyrosulfate . See the details there . It really seems to me that there is little published about the material which is so easily made and may have value in many different possible syntheses , including RDX .

I have in mind an RDX experiment for which I have not completed my best guesses about the temperatures and times , but here is what I am thinking :

6.4 grams of Ammonium Bisulfate are
melted and dehydrated by strong heating to a clear melt endpoint at ~400C , which
should produce a weight loss of .4 grams .
The beaker is stoppered when cooled somewhat , and when solidification begins
the material is stirred with a glass rod to
prevent it forming a solid monolith .
100 ml of cold d. 1.5 HNO3 is added and
( hopefully ) the ammonium pyrosulfate will be dissolved .

45 grams of Hexamine Dinitrate is mixed in advance with .3 grams of Urea Nitrate ,
and is gradually added at 20-25C to the
HNO3 and ammonium pyrosulfate solution , reacted for 20 minutes past
the end of the addition and the mixture
dumped onto 750 ml of crushed ice and water .

100% of theoretical yield of RDX would be 37.53 grams

80% of theoretical would be 30 grams RDX
which is about the amount which would make me happy if the reaction proceeds
according to plan .
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[*] posted on 9-11-2005 at 16:45


Quote:

See attachment for NH4 salt + hexamine + acetic anhydride -> 2 RDX. Not as useful as the patent which dismisses acetic anhydride, but it adds to the discussion.



You know I just realized something that I did that should be pointed out.....the PDF file you posted made me think about it.....
When I said about 70% yield I should have used the term "solid precipitate" as the amount of HMX (or Heaven knows what) is unknown since I did no melting point test! Re-reading the text you posted I just realized that Bachmann was invested in the synth of RDX not simply a solid precipitate.
However the CONCEPT of the use of ammounium salts is certainly a viable one IMO.
Of casual interest may be that I raised the temp of the 2nd bath to 60 C for 15 minutes after which I used cracked ice (approx 1 liter). Total nitration time being the hour it took to add the material to the acid which was maintained @ 15 C and the 15 minutes of elinimation of liniar nitramine elimination via raised temp (hot water bath). So that there was very rapid cooling. That has proven itself to be a good foundation in the past.
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