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Author: Subject: simple HMX-synth without Ac2O
Rosco Bodine
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[*] posted on 17-11-2005 at 09:04


Quote:
Originally posted by Maniak
I see there's some demand for Czechs :)
Rosco, no jokes with them! ;)
Actually I can't obtain ChemListy from 1957, but I'll try to ask in National Technical Library.
I'm also interested in HMX synth., but I'd like to use an old process with large quantity of Ac2O and then try to recover it.. The process over DAPT and SOLEX also worth trying, but there are problems with P2O5 handling :(


@ Maniak


Yes , we do need help from the Czechs ,
perhaps even a Slovak would suffice :D

That Simecek article is very interesting .
At first I thought that the reference to
H2SO4 may be a misprint in PATR , since most references say that both R-Salt and RDX decompose in H2SO4 .

But I also have a Russian abstract which refers to a different reaction where RDX is obtained from a strong solution of H2SO4 .
Here is the abstract of the Russian article :

Bibliographic Information

Unusual behavior of 1-acetoxy-2,4,6-trinitro-2,4,6-triaza-8-nitroxyoctane in the presence of sulfuric acid. Gafarov, A. N.; Punegova, L. N.; Marchenko, G. A.; Novikov, S. S. USSR. Zh. Org. Khim. (1980), 16(8), 1774-5. CODEN: ZORKAE ISSN: 0514-7492. Journal written in Russian. CAN 94:65633 AN 1981:65633 CAPLUS (Copyright 2002 ACS)

Abstract

Treatment of the title compd. with 88% H2SO4 at 0° for 30 min gave 73% trinitrotriazacyclohexane I; increasing the temp. to 5° increased the yield of I to 86%.

So it seems worth investigating the possible use of H2SO4 as an alternative for Ac2O , as Ac2O is highly restricted ,
a " watched precursor " in many areas .

The 1957 Simecek article may be key to a simplified method for both RDX and HMX from their nitroso precursors , via NH4NO3
+ H2SO4 .

Please get that article if you can get it .
For years there has been unresolved questions about this possible method for
RDX and HMX .

[Edited on 17-11-2005 by Rosco Bodine]
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Maniak
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[*] posted on 24-11-2005 at 14:05
Simecek's article


Now I've got complete proceedings of ChemListy from 1957. But...there's nothing about use of AN in the Simecek's article. TMTN was carefully dissolved in high excess of SA and then 98% NA is added. I'll try to translate the article and upload it here when I've got little more time.
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Rosco Bodine
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[*] posted on 24-11-2005 at 18:48


Excellent !

There is a second 1957 Simecek article which may provide more useful information about other conditions where H2SO4 may cause decomposition of R-salt .

J. Simecek , ChemListy , 51 , 2367-68 (1957)

Please take a look at the second article too and see what it may add .

I have reason to believe the concentration of the H2SO4 and temperature , and the time of reaction
are important . Beyond certain limited conditions , the R-salt and RDX also
will decompose . Simecek likely discovered a narrow range of conditions where the reaction would proceed .

This dissolving of nitrosamine / nitramines in sulfuric acid may follow a similar course as when polyols are dissolved in sulfuric acid , perhaps with esterfication , but without decomposition so long as the H2SO4 is of 85-93% concentration , and the temperature is mild . But at higher concentrations and temperatures , the polyol is decomposed and even charred to carbon .
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[*] posted on 26-11-2005 at 16:36


Seems good..
I've looked at the proceedings more closely and I found three articles by Simecek in 1957. I can't say everything there is interesting for you, but I'll try to translate all three (right way to improve my English :D). There's the first article...I'll add the two other soon.
Sorry for my grammar mistakes:P

Attachment: Simecek I.doc (968kB)
This file has been downloaded 1049 times

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Rosco Bodine
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[*] posted on 26-11-2005 at 19:22


It looks like the PATR abstract reversed the NA ( nitric acid ) acronym that Simecek used to AN ( ammonium nitrate ) and that
typographical error has led to a lot of what is probably false hopes :( about an easier method for RDX .

I did the math for the acid utilization efficiency for the Simecek method and it isn't superior in that regard either , in comparison to HDN + HNO3 methods .

Simecek , using .1 mole of R-salt ( 17.4 g )
would have used 80 ml of HNO3 to obtain
a near quantitative yield ~ 22 grams RDX .
On a per 100 ml of HNO3 basis that is 27.75 grams RDX maximum yield .

Given the essential nature of extreme cold and the sulfuric acid requirement beyond the HNO3 , with the added danger if conditions were not closely controlled , the Simecek method is not superior in safety nor economy to the nitrolysis of HDN by HNO3 . The volume of the mixed acid reaction mixture is more than 3 times the volume for a similar straight HNO3 nitrolysis mixture for producing a similar amount of RDX .

It might be interesting to see if instead of HNO3 , if solid urea nitrate added to the cold mixture would effect the nitration instead of simply being converted to nitrourea . I have often wondered if urea nitrate could substitute for an inorganic nitrate salt in various nitration schemes where a sulfuric acid solution of some organic substance awaits the addition of nitric acid or the provision of nascent nitric acid . Nitroguanidine is reported to work in this manner for some nitrations ,
so perhaps guanidine nitrate , its precursor , would work as well in the cold , and the same for nitrourea or urea nitrate .

The idea of a possible route to HMX by the Simecek method applied to DNPT remains interesting since the difficulty for HMX synthesis is acetic anhydride .
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[*] posted on 19-12-2011 at 15:24


From what I have read, it appears that the nitration for di-keto HMX could probably be done with only mixed HNO3/H2SO4 acids, without the need for acetic anhydride or >90%conc HNO2.

N,N'-dimethyl urea can be nitrated with conc. H2SO4/HNO3.
Quote:

adding N,N'-dimethylurea in an organic solvent (for example, methylene chloride) to mixed acid which is maintained at a temperature which is above the freezing point of mixed acid up to 5° C. to produce N,N'-dimethyl-N,N'-dinitrourea and then drowning the mixed acid solution in ice water

US 4476322

In another thread on this forum, "N-Nitro-N-methylhydroxyacetamide Nitrate", http://www.sciencemadness.org/talk/viewthread.php?tid=18243
There is a procedure which describes the mixed acid (HNO3, conc. H2SO4) nitration of hydroxymethylacetamide. Although the patent claims the compound thus formed is "N-Nitro-N-methylhydroxyacetamide Nitrate", I strongly suspect that the compound they obtained was actually N,N'-diacetyl-methylenedinitramine.

Simply condense urea and CH2O, then use a normal mixed acid nitration.







[Edited on 19-12-2011 by AndersHoveland]
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[*] posted on 26-9-2012 at 23:56


Here is described, which IL (Ion Liquid ) has to be added to reaction mixture to increase yield of HMX www.wydawnictwa.ipo.waw.pl/cejem/Cejem-8-2-2011/Zhi.pdf



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[*] posted on 27-9-2012 at 02:58


Quote: Originally posted by quicksilver  
There is some interesting stuff there.
Unfortunatly the patent is 10 pages long and Rosco mentioned that the board has a one Mb limit on posts so I can't post the patent as a PDF (or even a zip with all the .TIFF's)


The posts got me interested. It does look like a keeper. I'm trying to upload the file. It is 676k and the limit is 2mb, so I think it should work.



Attachment: US2678927.pdf (657kB)
This file has been downloaded 946 times
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[*] posted on 5-2-2014 at 22:14


Methods for obtaining HMX

www.chemikinternational.com/pdf/2012/01_2012/CHEMIK_2012_p58-63.pdf

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[*] posted on 6-2-2014 at 07:16


Quote: Originally posted by Rosco Bodine  
This is somewhat getting off topic but
if you are looking for HMX performance
with * perhaps * less extreme conditions for synthesis , maybe take a look at keto-RDX , having a slight power edge over HMX .

Dinitrourea and HDN are precursors and the process is fairly efficient . The attached file relates to dinitrourea , but includes a reference to keto-RDX . There was some discussion at E&W a year ago , and also there has been general mention of keto-RDX here , but the discussion never really went far .


Try compressing it to a DejaVu file *.djvu. I have seen 20 megs go down to around 2 megs.




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[*] posted on 7-2-2014 at 03:38


Quote: Originally posted by SM2  

Try compressing it to a DejaVu file *.djvu. I have seen 20 megs go down to around 2 megs.


It is not necessary

Attachment: dinitrourea.pdf (85kB)
This file has been downloaded 427 times

Attachment: phpSuTAZI (85kB)
This file has been downloaded 507 times

Attachment: Synthesis, characterization and thermal studies of keto-RDX or k-6-1.pdf (113kB)
This file has been downloaded 1002 times

Attachment: phpLSLKI5 (276kB)
This file has been downloaded 754 times

Attachment: Synthesis+of+Keto-RDX+and+its+Characterizations+Calculation.pdf (1.1MB)
This file has been downloaded 508 times

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