tetranitroglycoluril

[VasiaPupkin]

Could you tell me about tetranitroglycoluril (TNGU, SORGYL) or dinitroglycoluril? I have some information about its VoD, density etc. but some aspects of this informaton is doubtful. And very interestly: what application of those explosives?
1) 2 OC(NH2)2 + OCHCHO => OC(NH2)2CHCH(NH2)2CO (at the room temperature)
Can I make TNGU by this reaction? -
2) OC(NH2)2CHCH(NH2)2CO + 4 HNO3 => TNGU + 4 H2O (reaction in AC2O)

Excuse me for my bad English.

[cutefix]

Hello VasiaPupkin, there is a U.S.Patent about these energetic material,You can learn or compare your information with it.It is patent # 4,487,938.check this at this site;
http://www.uspto.gov/patft use the patent number link .

[VasiaPupkin]

Thanks a lot for your help. Very interestly. If you will have more links type it.

[Microtek]

Does anyone know where to get the glycoluril? ( I've seen it mentioned as a fertilizer but I haven't seen it in any stores ).
Or maybe how to make some?

[cutefix]

There is a supplier of glycoluril,I think he supply only 100 gram basis.Check this out;
http://www.acros.be/
Glycoluril is also known as acetylenediurea or,acetylenecarbamide(MERCK).
It is made by reduction of allantoin,or by reaction of glyoxal and urea(USPatent 2,731,472).
Tetranitroglycoluril(TNGU) is a peculiar explosive.It seems to be more powerful than HMX,but its sensitivity to water I think is one cause that its not popular. There is not much literature about TNGU.For the production of DINGU(Dinitroglycoluril) check this US Patent 4,211,874.

[simply RED]

I tried the patent search but it gived this error:
Error #2406 Error: Process terminated abnormally. Document may be truncated.

[cutefix]

I also experience a problem if I search older patents in the internet,I hope anybody here could offer some remedy for it.

[nbk2000]

Where are you people looking?

Just go to the US patent office site at http://164.195.100.11/netahtml/search-bool.html and type in the patent numbers and you'll find it.

Also, you'll need a TIFF plug in to view the old files. http://www.mieweb.com/alternatiff/

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"The knowledge that they fear is a weapon to be used against them"

Go here (http://members.nbci.com/angelo_444/dload.html) to download the NBK2000 website PDF.

Go here (http://briefcase.yahoo.com/nbk2k) to download the NBK2000 videos.

[This message has been edited by nbk2000 (edited July 05, 2001).]

[cutefix]

I have been using that first address to access patent files(1975 up),but for older patents I seldom use the internet; my computer will always say download active X or other viewerfrom the listed supplier of software.Somehow I am not interested because I seldom access old patent. Anyway it is enlightening to know somebody who is knowledgeable in selecting the best source of software for this purpose,and I don,t have to worry myself where to choose from if I need it.Thanks a lot for that info NBK!

[FadeToBlackened]

I read of glyoxal while reading over a patent for making HBIW (by acid cat. rxn, glyoxal + benzylamine by HClO4, used for HNIW). Just out of curiosity, since it is actually ethenal, could it be made similarly to acetaldehyde (ethanal) but instead of using ethanol, use ethylene glycol?

[Mr Cool]

That's an interesting idea. You mean with K2Cr2O7 and H2SO4? Could be worth a try.
OK, my mind is wandering now, not really thinking anything through (too tired), but what if you then reacted glyoxal with paraformaldehyde, to make a PE-like substance? And then nitrated this, to get ???

[cutefix]

The Preparation of glycoluril is summarized as follows in that patent#2,731,472.
1)To 100 parts of 32%glyoxal solution is stirred 50 parts of urea.The temperature will rise to 35-40 C in the course of half an hour.The solution is stirred for about 12 hours and gradually cooled to 0 C at the same time.
2)The crystalline intermediate-(4,5-dihydrioxyimidazolidone-2,)thus separated.(yield about 25 parts) is filtered off.A further 15 parts of this intermediate is recovered from the mother liquor by careful vacuum evaporation at 35 C.The total yield is 61% of the theoretical.
3)This intermediate is diluted with twice the amount of water and acidified with HCl to a pH of 2-3.About 25 parts of urea are added and the whole heated to 95-97 C.
4)About 25 parts of glycoluril as a fine crystalline precipitate is filtered off.

Glycoluril is also known as tetrahydroimidazo[4,5-d]imidazole-2,5{1H,3H}-dione.



[This message has been edited by cutefix (edited July 07, 2001).]

[PHILOU Zrealone]

On a theorical level yes, but practically no!
Glycol could give the glyoxal only under vigorous vacuum distillation.
For acetaldehyde it works because the volatility of ethanol is less high than the acetaldehyde. Here without a strong vacuum, first of all you will form some HOCH2-CH=O but this will be oxydised by preference on the aldehyde side leading to 2 hydroxyacetic acid HOCH2-CO2H. Reaction is also non selective and amongst other compounds in the middle you will find HOCH2-CH2OH, HOCH2-CH=O, HOCH2-CO2H, O=CH-CH=O, O=CH-CO2H, HCO2-CO2H, plus reactions product of those (acetals, hemiacetals, esters,...) all with about the same boiling points- A hell to separate.

Easy to critisize one's idea! Yes, ok so I give you a solution to the problem.
Start from tetrachlorethan and boil it under reflux with NaOH conc and water:
CHCl2-CHCl2 + 4NaOH --> CH(OH)2-CH(OH)2 + 4 NaCl
and
CH(OH)2-CH(OH)2 <--> CHO-CHO + 2 H2O

------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"

[VasiaPupkin]

I fully agree with Philou. But I think there's not need to separate. I think admixtures may be separated on nitration stadium when you preparing DNGU.
And some quotation from one book (naturaly with translate) "Glyoxal may be prepared from CHCl2-CHCl2 and H2SO4 => glyoxalsulfate and then it hydrolized. Or from acetaldehyde or paraldehyde (tricyclic acetaldehyde) by oxidation by HNO3 with addition of activated charcoal or silicagel in 15-25 C. By boiling a paraldehyde in dioxane with SeO2 and addition acetic acid (50% conc.)" I will try to get a detailed lab metods of preparing glyoxal.

[cutefix]

One thing that amazes me with TNGU is the use of combination of nitrogen pentoxide, and nitric acid and the use of huge amount of this acid mixture.Imagine you will need 14 parts of acid to 1 part DNGU and 35 part acid to 1 part glycoluril to form 1 part of TNGU.Compared to nitration of hexamine, and pentaerytritol which is much lesser, it is a sheer waste of acid for such a small yield of the explosive!No wonder the U.S was not interested with this explosive.They can produce more HMX of practically similar explosive power from same amount of less concentrated acid used for TNGU!

[PHILOU Zrealone]

THat's only my point of view but I do prefer, If I have to make TNGU, to start from nearly pure glyoxal than from a poor 5% solution with 95% contaminants.

Common sense in organic chemistry: Always separate in the early stages of the synthesis; only very few examples don't follow that rule.

------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"

[Hex]

I think that the US government wre probably more interested in the hyrolysis product of TNGU (1,1,2,2-tetra(nitramino)ethane) than TNGU itself. I would guess (but have never heard of) that attempts have been made to react it with compounds such as 1,4-diformyl-2,3,5,6-piperazine to make HNIW or more probably HNW precursors (de-benzylation of precursors is currently the biggest/most expensive problem in HNIW synthesis). But that's pure speculation.

[This message has been edited by Hex (edited August 06, 2001).]

[cutefix]

I think it was glycoluril as the starting material for TNGU;but glyoxal(32%) was the precursor for glycoluril,so if 5% glyoxal solution was used in the preparation of glycoluril it will be not cost effective in the end product,however with crystalline glyoxal you still have to make an aqueous solution for it before reacting with urea; As the preliminary step in preparing glycoluril.Philou ,maybe you had new ideas about this step.
Hex..I was excited when you say that it is pure speculation that debenzylation of HBIW is expensive.Do have some interesting ideas about it?
I thought that 2,3,4,6-tetrahydroxy-1,4-diformylpiperazine was used to make another explosive known as TEX,which has about the same power as RDX.There was also some info that some HNIW can result by the nitration of this piperazine material with mixed acid containing 90%nitric acid and oleum.
I thought that the synthesis of HNIW was already improved.In the pioneering work of Dr.Nielsen ;he used ntrosonium tetraflouroborate, and large amount of palladium catalyst and that is expensive,later it was modified by others pure using nitric acid or mixed acid combination in the nitration of an another intermediate made by hydrogenolysis of HBIW ,and even the catalyst usage was reduced so it was already and improvement.
However if compared to nitramine explosives RDX/HMX the manufacture of CL-20 is still complicated,therefore more expensive than ordinary crystalline explosives;but I think its possible for home laboratory that is well equipped,to make this caged nitramine explosive.The starting material was originally glyoxal,and a pearlmanns catalyst analog can be made in the lab from palladium chloride..You just have to procure seldom use solvents(in explosive synthesis) like sulfolane and acetonitrile, and other important precursors.Just be sure,to anybody who is interested, you are ready for complicated synthesis.


[This message has been edited by cutefix (edited August 07, 2001).]

[Hex]

Cutefix,
I'm afraid the part about HNIW/HNW synthesis from TNGU was what I was speculating about, rather than hydrogenation being the difficult/expensive part of the standard synthesis - it definitely is. My supervisor has actually done this through methods other than pearlmans catalyst, but still, unfortunately, using expensive catalysts. I can't give much detail on this, it's not published work.
One thing you might like to try is something similar to that in J.Chem. Soc., (Perkin 1),3765-3774,(2000), a paper on "Chemoselective de-benzylation of N-benzyl tertiary amines with ammonium ceric nitrate." They report good yields in aromatic and non-aromatic systems, but none of the examples are particularly similar to TBIW.
Representative Procedure:
Ceric Ammonium Nitrate (2.1eq)was added portionwise to a stirred solution of the substrate(1.0 eq) in MeCN/H2O (5/1) and stirred at room temp for (times vary depending on substrate). The reaction ws quenched by the addition of saturated NaHCO3 solution, stirred for 10 further minutes and extracted with ether. The extracts are dried over MgSO4 and concentrated under vacuum, and purified by column chromatography.

This *might* be one way of doing it at home, where hydrogen and pressure vessels are hard to come by. Not sure if anyone's tried it yet. It would, of course, have to be done in the presence of, say, acetic anhydride, as the hexahydro wurtzitane is highly unlikely to be a stable compound

TEX is indeed made from diformyltetrahydroxypiperazine. There's surprisingly little info available on this compound, considering the relatively easy synth - this could mean it's very susceptible to hydrolysis (nothing in the structure would suggest it would be particularly bad in this respect) or it's under very active military development and the results are being kept quiet. The reaction is carried out in a mixed nitrating acid, and the product density is a very high 1.99, but I haven't found much else yet. I'll keep looking and let you know if i get anything interesting.

[This message has been edited by Hex (edited August 07, 2001).]

[This message has been edited by Hex (edited August 07, 2001).]

[cutefix]

I think this TEX material belongs to the Insensitive High Explosives category,It was said to be much less sensitive than RDX.I think because of this .It is the likely candidate that can replace that TATB(triaminotrinitrobenzene) which is less powerful for warhead applications..This TEX appears to have slightly less VOD than RDX.One thing that makes this material interesting is,its root;which is also glyoxal!.This dialdehyde if reacted with formamide and neutralized with sodium carbonate and will form the basic material for its synthesis.-the diformyltetrahydroxy piperazine.If this intermediate is nitrated with urea treated mixed acid it will form this TEX as yellow solid.
About synthesis of TEX, check USPatent 6,107,483.

[Hex]

Cutefix,
Have you ever checked out the references in that patent concerning the synth of the diformylpiperazines? I would be intrigued to know what sort of yields they get, and especially what percentage of the correct (all hydroxyls equatorial) isomer is produced. I would also like to know if these compounds can be nitrated to the 1,4-nitro-2,3,5,6-tetranitratopiperazine. That would make an amazing rocket oxidant, I'm sure.
BTW, TATB, depite its low VoD, is still pretty attractive for many applications. Someone who came up with a cheap way of making it without using halo compounds would be able to earn himself a lot of cash. Purification is the big prob with TATB. It's totally insoluble in almost everything except 100%H2SO4. It's a real trial trying to get enough into DMSO to run an NMR.


[This message has been edited by Hex (edited August 09, 2001).]

[cutefix]

Please check these files.USPatent 6,069,277;5,569.783; and 4,248,798 where they made TATB without Halo compounds.
Regarding ketopiperazines check this files -old US Patent 3,365,454-titled Diformyltetrahydroxypiperazine and derivatives.They mentioned this nitrated product only-Diformyl-tetranitratopiperazine through reaction of the diformyl-tetrachloropiperazine(made previously by refluxing the diformyl tetrahydroxypiperazine in thionyl chloride and pyridine) with silvernitrate dissolved in acetonitrile.A nother way they mentioned of getting this nitrated piperazine was through acetyl nitrate(the reaction of 10 parts of diformyltetrahydroxypiperazine with 376 parts of 100%nitric acid and 81 parts of acetic anhydride) to form 14.4 parts of the same nitrated product.


[This message has been edited by cutefix (edited August 09, 2001).]

[Hex]

Cheers Cutefix,
The stuff on the formyl piperazines was very interesting...I'd love to know if anyone has tried to react this compound with 1,1,2,2-tetra(nitramino)ethane.
I've seen some of the stuff on TATB before, as a guy who's just left here did his PhD on TATB synthesis. Vicarious nucleophilic methods have quite a lot of drawbacks (mainly partially aminated products and the yields are decreased if the alkylammonium salts aren't halides). The UK (and probably most of NATO) have set time limits to go over to using insensitive fillings, so I guess TATB will be around for a while, simply because they haven't got anything better that's been tested properly. Although we're looking for someone to do a PhD in HNS chemistry at the moment....

[cutefix]

HNS,you mean Hexanitrostilbene another thermally stable explosive?.I hear it is also insensitive but not similar to TATB,but still it has low detonation speed.What so interesting with this material anyway?.I only know it was added in TNT based melt cast explosives to prevent cracking during cooling of the cast explosive.It tends to improve grain structure of the finished explosive also.I think there are already a lot of information about its synthesis.As far as I remember it was originally made from oxidation of TNT then hexanitrobibenzyl,then later from dipicrylethane.Some of these materials are not as available as TNT.So this standard explosive become the raw material of interest for this and the yields were also satisfactory).Therefore instead of looking for microbes to digest trotyl from obsolete weapons,there is a good use for it.Some years ago Lawrence Livermore laboratory was doing some study also on how to recycle Explosive D,and they found out that it can be converted to picramide where it can be converted to TATB through vicarious nucleuphilic substitution..So, even if the yield of TATB is lesser compared from chlorinated aromatic materials it was still worth the effort instead of throwing those old explosives to the dump or landfill(it is toxic and took time to decompose).
The later synthesis from TNT is pretty straightforward,just by reacting it in almost 1:1 ratio TNT/cupric chloride/ and in the presence of sodium benzoate in DMSO,then precipitated in water and then washed with water and methanol.Therefore I think the the graduate student who will be interested in HNS for his thesis will have an easier time for further study....




[This message has been edited by cutefix (edited August 11, 2001).]

[PHILOU Zrealone]

Hex, could you send me more info's about the phD you talk about on LOUISPHZ@hotmail.com, thanks!

In my lab we were doing some research on polyazaaromatics and one of the key intermediary was hexaaminobenzene!THe process surely pass trough TATNB since they have isolated it many times
Process:
Sym trichlorobenzene + HNO3 + H2SO4 -->TNTCB
TNTCB + excess NH3(l)+ Na(s) --> HAB
(aminolyse of Cl and concomitant reduction of NO2 via Na-NH2/NaH)!

TCB is C6H3Cl3
TNTCB is C6Cl3(NO2)3
HAB is C6(NH2)6

One thing I will try for sure in a near future is a process to TATNB from nitroacetamide NH2-CO-CH2NO2
3NH2-CO-CH2NO2 --> TATNB + 3 H2O

------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"