Another caged energetic material: AURORA

[klasac]

Recently I was surfing on the internet looking for some new developments in the field of cage explosives and I managed to google up one interesting article by russian scientists describing cage-structured explosive with acronym AURORA. Chemical name 4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazatetracyclo[5,5,0exp3.11,0exp5.9]dodecane. If picturing the molecule is still a no-go for you, take molecule of HNIW and substitute two top nitramino moities with etheric groups, or do reverse thing with the molecule of TEX.

It is very interesting new(?) energetic material which has the advantages of both HNIW and TEX, less sensitive than HNIW and more powerful than TEX. While the synthesis of both HNIW and TEX is well known and several methods were developed to give satisfactory yields (HNIW 98%, TEX 37%), the description of process leading to AURORA molecule is somewhat vague and general.

It is mentioned that precursor for AURORA is tetrasulfo- cage compound formed by reaction of glyoxal and alkalic sulfamate in proper ratio, reaction medium, catalysis, pH, temperature, reaction time and reactant concentration. As it states further, the control of reaction conditions is crucial because various products will be obtained with slight deviation from the strict condition range. Reaction of glyoxal with K-sulfamate, depending on conditions,can lead to various products such as tetrahydroxydisulfopiperazines, N-sulfoimidazoles, desired tetrasulfonate cage product, and others. The resulting product of the concentration is always a mix of products and they are nitrated in second step withou previous division. The yield of AURORA is stated 95%, which is not bad.

The problem I think will be searching for the correct conditions during the condensation reaction. Although the article mentions the desired range, after practical experiments it did not give the desired product (nitrated in nitric and sulfuric acid). Anyone tried the synthesis of this interesting explosive?:o

[Jacks Complete]

Got some references for this stuff? Sounds interesting.

[klasac]

The article is not available online anymore since the authors published book about this synthesis in december'07 and is available online only for purchase. If anyone find something about this interesting synthesis path please let me know;-)

[Charles Owlen Picket]

I did a quick search and tetrasulfonates are extremely expensive pharmaceutical materials used in ocular medicine & surgery.
While precursors are sometimes difficult to find but can be had in technical grade (like phloroglucanol), superficially it seems tetrasulfonates are actually a pharma-grade product. [I mention phloroglucanol as it also can be a top end precursor cost-wise but can (and HAS) been found in large lots of tech-grade material.] ....But, shit, who knows....it's early & I'm probably off base on this.
I did a journal hunt an couldn't find it under either name. AURORA appears to be someone's one-night-stand unless that Russian got published in a journal I haven't seen thus far. And just for sake of comparison aren't some poly nitro benzenes like HNB & HNS on the same level of strength and sensitivity? Research is fun to look at but those guys have virtually unlimited funding when compared to a hobbyist.

[hereno]

Chemical name 4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazatetracyclo[5,5,0exp3.11,0exp5.9]dodecane. If picturing the molecule is still a no-go for you, take molecule of HNIW and substitute two top nitramino moities with etheric groups, or do reverse thing with the molecule of TEX.


You've ballzed something up there, the chemical name you have given is for TEX (http://www.sciencemadness.org/talk/viewthread.php?tid=6000). Your likely thinking of 4,8,10,12-tetranitro-2,6-dioxa-4,8,10,12-tetraazatetracyclodecane. Which has already been refered to in the HNIW thread (http://www.roguesci.org/theforum/showthread.php?t=4559&highlight=HNIW&page=3) and article given.

[Charles Owlen Picket]

hereno - you are also quite correct (as far as I know) re; the statement you made about it being very difficult to isolate HNIW. This is very professional level chemistry here. Those fellows who work with energetics commercially have a tough time of it.... I seriously doubt that hobbyists with $300 worth of glass are going to get some yields in their spare bedroom :-)

[megalomania]

How about this: What was the name and url of the article before it was removed, what is the name of the Russian scientist, and what book are they now selling? Perhaps I can get the book from the library, unless it's written in Sovietski. I don't want to search in vain based on possibly erroneous info if you have publication titles and researcher names at hand.

[klasac]

HERENO: yes, u are absolutely right, the formula I wrote was TEX, chemical name for AURORA is 4,8,10,12-tetranitro-2,6-dioxa-4,8,10,12-tetraazatetracyclodecane (as you wrote)-my bad.

The title of the article I was talking about is:
SYNTHESIS OF POLYCYCLIC NITRAMINES BY NITRATION OF CONDENSATION PRODUCTS OF GLYOXAL AND FORMALDEHYDE WITH SULFAMIC ACID SALTS
written by S.V. Sysolyatin1, G.V. Sakovich1, Y.T. Chernikova1,V.N. Surmachev1, A.A. Lobanova2
1Institute for Problems of Chemical and Energetic Technologies SB RAS
2FGUP «FR&PC»ALTAI»
1, Sozialisticheskaya, Biysk, Altai Region, 659322, Russian Federation

At first, after many unsuccessful experiments I started to think that this article and fact stated in it are not very true, but recently I found out that the authors published this (or similar, more detailed) article in a magazine, here's the link http://www3.interscience.wiley.com/cgi-bin/abstract/117857801/ABSTRACT?CRETRY=1&SRETRY=0
So there must be something true about what the russians invented- that cahed explosives can be made from (BTW cheap) starting material, namely sulphamic acid and glyoxal. They even make diamonds using cast explosives comprised of TNT and AA (aurora).
If anyone has more information, please share with us;-)

[megalomania]

The Wiley article is from ChemInform, Volume 38, Issue 52...
ChemInform just indexes interesting journal articles from other publications, in this case the original article is from Russian Chemical Reviews (English Translation).

http://www.turpion.org/php/paper.phtml?journal_id=rc&paper_id=3716
"Methods for the synthesis of polycyclic nitramines", RUSS CHEM REV, 2007, 76 (7), 673-680.
S. V. Sysolyatin, G. V. Sakovich, V. N. Surmachev
Inst. Probl. Chem. Energ. Technol., Sib. Branch Russ. Acad. Sci., Biisk 659322, Russia

Abstract
Published data on the methods of synthesis of polycyclic nitramines are analysed. The advantages, drawbacks and prospects of two main approaches to the formation of the molecular cage, namely, amine or amide condensation with carbonyl compounds and consecutive formation of the polycyclic cage with introduction of reactive terminal substituents, are discussed.

Alas, I only have access up to 2005 for this journal. I could request the article, unless anyone else has direct access to the online version. There might be some fresh info in this since the article was only published a few weeks ago, but this reads suspiciously like one of those review articles where they just reference every published journal that has ever mentioned the compound. A good one stop article to find all relevant refs, but unlikely to hold any new synth info.