Sciencemadness Discussion Board

Sorguyl

Nitrojet - 24-10-2006 at 12:53

I have prepared 15gr of glycolurile through direct condensation of glyoxal and Carbamide. This is the primary step to synthesizing Sorguyl (Tetranitroglycolurile) which is a very interesting explosive because of its very high detonation velocity (9150m/s @ d=1.95gr/cc). The nitrating agent is somehow troublesome to be prepared because it has to be a mixture of HNO3-N2O5 to yield the tetranitro product. does anybody have any experience with such a nitration agent? is it possible to prepare Sorguyl with strong Nitric acid (d=1.523)?

Axt - 24-10-2006 at 15:09

Can you get P2O5? N2O5 doesnt need to be isolated as such. HNO3/P2O5 will suffice and should be as readily available as say, glyoxal. I couldnt find the detailed procedure in the literature but-

"Nitroureas II. Synthesis of Bicyclic Mono- and Dinitrourea Compounds" PEP, Vol. 21, Issue 1 , pg. 14 - 18 (1996)

I believe should have it, pitty people with access to the old PEP's are few and far between.

[Edited on 24-10-2006 by Axt]

Nitrojet - 25-10-2006 at 00:31

There are certain problems associated with P2O5 but ofcourse from legal standpoints rather than chemistry points of view! The material is a precursor to home manufacture of Acetic Anhydrid which is itself absolutely necessary for manufacture of drugs. Aside from this, i could not find "Nitroureas II. Synthesis of Bicyclic Mono- and Dinitrourea Compounds" PEP, Vol. 21, Issue 1 , pg. 14 - 18 (1996), even through an extensive search.
Does PEP stand for " Pharmacology Education Partnership"?

Axt - 25-10-2006 at 01:53

Propellants, Explosives, Pyrotechnics

Paste "Nitroureas II. Synthesis of Bicyclic Mono- and Dinitrourea Compounds" into google.

P2O5 isnt regulated here, and rather cheap.

[Edited on 25-10-2006 by Axt]

Nitrojet - 25-10-2006 at 11:03

I already have a 1kg pack of reagent grade P2O5. So legal issues can not be an obstacle for proceeding into nitration of the glycolurile. but the problem is that i don't have the least idea of how to carry out the nitration process, i have no experince with such nitrating agents. does any body have a detailed synthetic procedure of Sorguyl using HNO3/P2O5?

vulture - 25-10-2006 at 14:05

You might want to try nitration with DCM/HNO3 first before going the anhydride route. If you go the anhydride route, I would suggest nitrating in acetic acid anhydride. Direct addition of P2O5 to the nitration mixture is going to cause a mess.

Acetylnitrate is a very good nitrating agent but explosive in high concentration so use caution.

garage chemist - 25-10-2006 at 14:19

P2O5 dissolves cleanly and rapidly in anhydrous HNO3, the resulting solution is as mobile as the HNO3 before and the mix makes the most powerful nitrocellulose I've ever seen.

I'd suggest to just dissolve the P2O5 in the HNO3 and using this as the nitration mix.

A nitration mix with acetic anhydride and HNO3 is explosive in itself (homogenous mix of oxidiser and flammable liquid) and also unstable, slowly generating tetranitromethane and also capable of self- accelerating runaway nitration of the acetic anhydride.

chemoleo - 25-10-2006 at 18:20

Nitrojet, and others:

A suggestion for the future - please post chemical structures, and reaction equations in the future (Use attach function or FTP for graphics). This will make it much easier for the uninitiated reader to follow the nomenclatures you use. I don't think it can be expected for everyone to immediately know what Tetranitroglycolurile (or Fox-7, see below) would look like.

I am also pretty sure it will attain more attention that way.

Much appreciated. Thanks!

Edit: I think the same goes for this thread:
https://sciencemadness.org/talk/viewthread.php?tid=5346

Many readers will be thanking you!

[Edited on 26-10-2006 by chemoleo]

solo - 1-11-2006 at 08:13

Reference Information


Nitroureas II. Synthesis of Bicyclic Mono- and Dinitrourea Compounds
Philip F. Pagoria, Alexander R. Mitchell, Edward S. Jessop
Propellants, Explosives, Pyrotechnics Volume 21, Issue 1, Date: February 1996, Pages: 14-18



Summary
We report the synthesis and characterization of several bicyclic
mono- and dinitrourea compounds as energetic materials and discuss
their use as precursors to other energetic compounds. The
new nitrolyzing reagent, trifluoromethanesulfonic acid anhydride/
20% NzOs/nitric acid, will also be described.

Attachment: Nitroureas II. Synthesis of Bicyclic Mono- and Dinitrourea Compounds.pdf (542kB)
This file has been downloaded 2166 times


Axt - 1-11-2006 at 08:31

Thanks solo, nice info. Well it only referred to P2O5/HNO3 but didnt detail it. It referenced to PATR2700, gave the wrong page but the info sought is under the entry for glycoluril G117 [attached]. Yield isnt so great, maybe better to isolate the dinitroglycoluril first instead of going it in one step.

[Edited on 1-11-2006 by Axt]

TNGU-HNO3-P2O5.jpg - 41kB

chemoleo - 1-11-2006 at 16:52

Ah, finally looked this up:
Glycoluril - wonderful, makes totally sense, the structure, obtained from urea and glyoxal.

What is the procedure for making it? Heat until any water vapors are driven off?
I wonder whether similar products are possible, i.e. with guanidine, semicarbazide, thiourea (from , photography supplies), biurea
etc. There should be some interesting possibilities.

Slightly off topic - does anyone know the name of the condensation product of oxalic acid and urea? It should theoretically yield a circular amide [CO2]2[NH]2CO, which in turn could be nitrated similar to what Axt described in one of his threads (forgot which one it was).

Axt - 1-11-2006 at 22:04

Glycoluril is relatively insoluble so the condensation is very easy in acidic aqueous solution.

Guanidine if analogous to urea forming a bicyclic product would likely only be nitrated at the imine nitrogens, so not that attractive as an energetic material.

Quote:
Originally posted by chemoleo
Slightly off topic - does anyone know the name of the condensation product of oxalic acid and urea? It should theoretically yield a circular amide [CO2]2[NH]2CO, which in turn could be nitrated similar to what Axt described in one of his threads (forgot which one it was).


Parabanic acid, Its nitration product (if possible) would likely be very susceptable to hydrolysis. J. Phys. Chem. 1991, 95, 844-848 [attached]

Its closest relevant thread would be PETN-based Cast Explosives with the nitration of dimethyloxamide. You were probably thinking of Nitrated Organic Acids & Salts where you brought up the condensation of tartaric acid with ethanolamine. Also maybe thinking about nitration of imidazolidone as intermediate to ethylenedinitramine.

[Edited on 2-11-2006 by Axt]

Attachment: hydrolysis of nitroureas.pdf (1.4MB)
This file has been downloaded 695 times


chemoleo - 2-11-2006 at 18:13

Thanks for the info. Parabanic acid it is. Given that it is an acid, I imagine it'd be very difficult to form some sort of nitramide.


Yes, cheers, it was the Nitrated Organic Acids thread. I'll have to look up the methodology for the condensation of i.e. tartraric acid with ethanolamine. Although it's off topic - please remind me where I can find such information, by U2U if need be. Sorry for my laziness... but it seems you keep a much better mental trackrecord as to where things have been discussed!

Axt - 3-11-2006 at 11:21

Quote:
Originally posted by chemoleo
Given that it is an acid, I imagine it'd be very difficult to form some sort of nitramide.

Not saying its likely but its not unheard of, glycoluril is a feeble acid. Maybe accessable through a different route such as chlorination of the sodium salt, then reacting with AgNO2 like brought up with dichloro-EDNA thread.

Quote:
I'll have to look up the methodology for the condensation of i.e. tartraric acid with ethanolamine. Although it's off topic - please remind me where I can find such information, by U2U if need be.


I actually dont know, Nitrojet seems to be saying that he condensed methylamine with oxalic acid here so I guess one should hit him up in that thread about the methodology, without resorting to the ethyl ester (or maybe he did?).

Nitrojet - 4-11-2006 at 05:05

In my attempts to synthesize Dimethyloxamide, I condensed Methylamine with both Methyl and Ethyl esters of Oxalic acid. Direct combination of the acid itself with Methylamine gives entirely different results. The product of neutralizing Oxalic acid with Methylamine which is an organic base is known as Methylamine Oxalate.
Based on the availability of the raw materials, Ethyl Oxalate and Methyl amine, synthesis of Dimethyloxamide is a simple straightforward route:

In a 500ml beaker, put 55gr Ethyl Oxalate and Add 90gr of 40% Methylamine solution (Equal to 36gr of pure reagent) from a separatory funnel in a dropwise fashion. Hold vigorous agitation inside the beaker by means of a magnetic stirrer and adjust the rate of addition so that all the contents of the funnel get discharged into the beaker in 20 minutes. Continue stirring for an additional time of 1hr after addition is completed. No special care for temperature control is needed whole during the synthesis. Filter out the white crystals out of the solution and dry them at 30’C. The yield is 26gr or almost 50% based on Ethyl Oxalate.

In case of unavailability of Ethyl oxalate one may use more conveniently, the Methyl ester which is far less troublesome in synthesis. Methyl oxalate is a low melting point solid which can be easily synthesized from Oxalic acid and methanol. Also for those who might not have an easy access to Methylamine, a very good alternative is Hexamine-HCl. Treating this material with alkaline solutions give Methylamine solutions of different concentrations.

Engager - 17-9-2008 at 07:21

Reciently i've successfully prepared TNGU by nitration of glycouryl. TNGU - colorless or slightly yellowish crystaline compound, insoluble in water and is slowly hydrolized by it to tetranitraminoethane, fast decomposed in alkaline solution. Decomposes by hot ethanol. Very powerfull, and dense explosive, easily pressed, density is 2.02 g/cm3 (from nitromethane), density of technical grade product is 1.98 g/cm3. Slightly more sensitive then PETN, soluble in nitromethane. Decomposition starts slightly above 100C, flash point 200C. Detonation velocity is 9150 m/sec at 1.95 g/cm3. Brisance by sand test is 61.9g of crushed sand (TNT - 48g, PETN - 62.7g). Practitial use is not widespread because of unsufficent hydrolitic stability, partialy decomposed on melt with TNT. Can be used in flegmatized state or with thermoplastic polymeres.


Here is synth procedure i've used:



Production of glycouryl. 5.84g of glyoxal (0.1 mol, 12.3 ml 40%, density 1.19 g/cm3) is mixed with 15g of powdered urea, solution is mixed until urea is completely dissolved and then acidified by sulphuric acid to pH~0 and placed on water bath under reflux condenser. Rection mixture is heated on water bath for 1 hour, cooled and filtered to get glycouryl. Crude product is mixed with 100 ml of boiling water, well stirred and mixture is left to cool to room temperature. Pure glycouryl is filtered and dried at room temperature. Yield is 9.9g (71%).


Synthesis of TNGU. 15 ml of ice cold concentrated nitric acid (density 1.51 ~100%) is slowly added drop by drop with stirring to 45 ml of cold acetic anhydride, not allowing temperature to rise above 15C, mixture is left to stand for 30 minutes at room temperature (Note#1). 6g of finely powdered glycouryl is added by portion with stirring, mixture is stirred at 20C for 30 minutes and then heated to 30C for 2 hours (Note#2). Precipitate of TNGU is filtered on glass filter, washed with 75 ml of ice cold water, 50 ml if ice cold ethanol and dried at dessicator over P2O5. Yield is 7.1g (52%).


Notes:

1. Addition of nitric acid causes slight heating, acid should be added drop by drop with gentle stirring, not allowing temperature to rise above 15C. Acetic anhydride reacts with nitric acid forming acetyl nitrate and N2O5, witch are in equilibrium with each other. Accumulation of this products takes some time. At 20C conversion of acetic anhydride to acetyl nitrate reaches 70%.


2. Additon of glycouryl to acid mixture, produces no or very low heat, but glycouryl must be added by portions to ensure efficient mixing. Glycouryl and product of it's nitration are insoluble in nitrating mixture, so nitration proceeds on the surface of glycouryl particles and precipitate is slowly covered by solid layer of nitration product, blocking acess of acid to inner layers witch can be low nitrated. Because of that all nitration must be carried out with efficent stirring, to ensure complete nitration, not allowing solid layer to settle.





OregonTrail - 18-9-2008 at 22:20

If you can get your hands on an ozone generator (commonly used in the aquarium industry or relatively easily built), you can easily make N2O5.

Engager - 4-7-2009 at 02:40

Photo of Sorgyul made from microscope:


[Edited on 4-7-2009 by Engager]

Microtek - 7-7-2009 at 13:56

Engager:
Is that a nitration method from litterature ? I have only ever seen TeNGU produced with the use of P2O5/HNO3.
Also, what methods do you use to check that your product is in fact TeNGU and not the di- or tri-nitro derivatives?

Recently, I have been preparing some TeNGU (for use in my HNIW experiments) and checked the product via Raman spectroscopy. The absense of N-H stretching bands were then taken to mean a fully nitrated product. The thing is however, that some experiments which were supposed to give TeNGU (P2O5/HNO3 method) only produced lower nitrated species.

Engager - 8-7-2009 at 11:53

Yes synth was from russian general chemistry journal. Translated to English: A.L.Kovalenko, U.V.Serov, I.V.Tselinskij - New heterocyclic system - 1,5-di-tret-butyl-1,5-diaza-3,7-dioxobicyclo [3,3,0] octane. Journal general chem. (Russian) 1991, 61, 13, page 2778. I have this article but on Russian language.

The WiZard is In - 8-4-2010 at 10:51

Quote: Originally posted by Nitrojet  
I have prepared 15gr of glycolurile through direct condensation of glyoxal and Carbamide. This is the primary step to synthesizing Sorguyl (Tetranitroglycolurile) which is a very interesting explosive because of its very high detonation velocity (9150m/s @ d=1.95gr/cc). The nitrating agent is somehow troublesome to be prepared because it has to be a mixture of HNO3-N2O5 to yield the tetranitro product. does anybody have any experience with such a nitration agent? is it possible to prepare Sorguyl with strong Nitric acid (d=1.523)?



Tetranitroglycoluril and method of preparation thereof
Jacques Boileau et al. Dec 11, 1984

US Patent 4487938

hissingnoise - 8-4-2010 at 14:45

Without some way of producing N2O5 enriched HNO3 TNGU remains more-or-less out of reach. . .
Its ureic oxygen reduces the heat of explosion and its oxygen balance so that while its VoD is higher than RDX and HMX its overall performance is similar.
Its solubility in water is problematic too!


Azane - 11-7-2013 at 08:50

Quote: Originally posted by Engager  
Reciently i've successfully prepared TNGU by nitration of glycouryl. TNGU - colorless or slightly yellowish crystaline compound, insoluble in water and is slowly hydrolized by it to tetranitraminoethane, fast decomposed in alkaline solution. Decomposes by hot ethanol. Very powerfull, and dense explosive, easily pressed, density is 2.02 g/cm3 (from nitromethane), density of technical grade product is 1.98 g/cm3. Slightly more sensitive then PETN, soluble in nitromethane. Decomposition starts slightly above 100C, flash point 200C. Detonation velocity is 9150 m/sec at 1.95 g/cm3. Brisance by sand test is 61.9g of crushed sand (TNT - 48g, PETN - 62.7g). Practitial use is not widespread because of unsufficent hydrolitic stability, partialy decomposed on melt with TNT. Can be used in flegmatized state or with thermoplastic polymeres.


Here is synth procedure i've used:



Production of glycouryl. 5.84g of glyoxal (0.1 mol, 12.3 ml 40%, density 1.19 g/cm3) is mixed with 15g of powdered urea, solution is mixed until urea is completely dissolved and then acidified by sulphuric acid to pH~0 and placed on water bath under reflux condenser. Rection mixture is heated on water bath for 1 hour, cooled and filtered to get glycouryl. Crude product is mixed with 100 ml of boiling water, well stirred and mixture is left to cool to room temperature. Pure glycouryl is filtered and dried at room temperature. Yield is 9.9g (71%).


Synthesis of TNGU. 15 ml of ice cold concentrated nitric acid (density 1.51 ~100%) is slowly added drop by drop with stirring to 45 ml of cold acetic anhydride, not allowing temperature to rise above 15C, mixture is left to stand for 30 minutes at room temperature (Note#1). 6g of finely powdered glycouryl is added by portion with stirring, mixture is stirred at 20C for 30 minutes and then heated to 30C for 2 hours (Note#2). Precipitate of TNGU is filtered on glass filter, washed with 75 ml of ice cold water, 50 ml if ice cold ethanol and dried at dessicator over P2O5. Yield is 7.1g (52%).


Notes:

1. Addition of nitric acid causes slight heating, acid should be added drop by drop with gentle stirring, not allowing temperature to rise above 15C. Acetic anhydride reacts with nitric acid forming acetyl nitrate and N2O5, witch are in equilibrium with each other. Accumulation of this products takes some time. At 20C conversion of acetic anhydride to acetyl nitrate reaches 70%.


2. Additon of glycouryl to acid mixture, produces no or very low heat, but glycouryl must be added by portions to ensure efficient mixing. Glycouryl and product of it's nitration are insoluble in nitrating mixture, so nitration proceeds on the surface of glycouryl particles and precipitate is slowly covered by solid layer of nitration product, blocking acess of acid to inner layers witch can be low nitrated. Because of that all nitration must be carried out with efficent stirring, to ensure complete nitration, not allowing solid layer to settle.






Are there any compounds that can sufficiently dissolve glycoluril and still remain inert in the nitration mixture?
I ask because I think that adding a non-aqueous solution of GU to the nitration mixture may allow one to avoid the formation of insufficiently nitrated particles of GU (protected by TNGU passivation layers), and, therefore, nitrate the predetermined amount of GU more quickly.

Water can't be used because it would hydrolyze the acetic anhydride, negating its viability as a dehydrating agent after the nitration. On top of that, water just isn't a very good solvent for glycoluril (15g/100g H2O @ 100oC).

If there isn't any solvent that fits the description, it's no big deal, because your method at present works just fine.

Also, does a dehydrating agent need to be used?

Adas - 11-7-2013 at 12:53

Quote: Originally posted by hissingnoise  
Without some way of producing N2O5 enriched HNO3 TNGU remains more-or-less out of reach. . .
Its ureic oxygen reduces the heat of explosion and its oxygen balance so that while its VoD is higher than RDX and HMX its overall performance is similar.
Its solubility in water is problematic too!



It hydrolyzes in water and in presence of weak bases to give tetranitraminoethane, which might form some explosive salts of interest.

Motherload - 11-7-2013 at 23:12

I am guessing sulfuric acid based nitrations won't work ?

Mr.Greeenix - 28-5-2015 at 11:14

does someone know where the solubility differnences of Dingu and TNGU are.
TNGU soluable in Nitromethan I know...

I need them to see if there is some DINGU in my TNGU (made by Engangers method)

Thraxx - 16-11-2016 at 10:28

DINGU,Dinitroacetylenediurein
----------------------------------------

-very small white or colorless crystals (my own experience is,that DINGU prepared with only nitric acid is brown and with nitric-sulfuric is white.The brown crystals are smaller.)
-two isomers(1,3)small amount and unwanted, decomposed with boiling watter, (1,5) decomposed of amonia at RT
-stable in acid medium
-readily decomposed at alkaline hydrolysis
-decomposition beginns at 130C
-deflagration point at 225-250C
-sensitivity –much less sensitive than HMX,reffered like insensitive HE (IHE)
-solubility in conc. Nitric acid,in DMSO
-insoluble in water,nitrometan and in ordinary org solvents
-density-1,94
-rate of detonation-at 1,75 it is 7580 m/s

TENGU-soluble in nitrometan,
in dioxan /17g/100ml at 27C/
in glacial acetic acid /15g/100ml at 25 C/


History:
1888-Franchimont and Klobbie-synt.:1part of Glycoluril + 5 parts abs.nitric acid
1889-Ibid
1944-Blatt-synt.: nitrating Glycoluril +98%HNO3+aceticanhydrid at below 5C
1973-Boileau,Emeury,Kehren-Fr.patent : 7327038



[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

nlvince - 22-11-2016 at 05:03

This seems to be pretty high yielding:

To a 500 mL round-bottom flask equipped with a stirbar was added 100 mL of H2O, glyoxal (20 g, 0.345 mol, 1.00 eq, 50 ml of a 40 wt. percent solution in H2O), and urea (51.7 g, 0.862 mol, 2.50 eq). The reaction mixture was heated to 90 oC and was stirred for 5 min. Concentrated H2SO4 (4 mL) was added dropwise over 5 min, and a white solid formed 10 minutes after addition of the acid. The reaction mixture was stirred for an additional 12 h. The reaction mixture was cooled to room temperature, and a 50percent aqueous solution of NaOH was added until the pH of the reaction was adjusted to 14. The stirring was stopped, and the reaction mixture was cooled to 0 oC. The suspension was isolated by vacuum filtration on a Büchner funnel, and the solid was washed with cold water (2 x 500 mL). The solid was left to dry on the Büchner funnel under suction for 3 h, was transferred to a 700 mL beaker, and was dried for 16 h at 80 oC to yield 45.0 g (0.304 mol, 92percent yield) of glycoluril (1) as an off-white powder. m.p. =335.19 oC

I also have the reference but am not sure where to upload it

Thraxx - 22-11-2016 at 09:48

in the 50 ml of Glyoxal dissolve 86g of urea and put there quickly solution of 22 ml water + 37ml conc.H2SO4.It will heat and turn white and you will shake it all the time of heating and if you want,then can you put the flask into the 65 C watterbath for 1 h.and then filtering washing drying.

nlvince - 22-11-2016 at 11:55

This patent describes the synthesis of sorguyl using 100% nitric acid and acetic anhydride. They claim 85% yield.

https://worldwide.espacenet.com/publicationDetails/originalD...


PHILOU Zrealone - 22-11-2016 at 13:59

Most amine base for common caged nitramine are high yielding...
-hexamine from aqueous CH2O and aqueous NH3
-glycoluril from urea and glyoxal
-...

Mr.Greeenix - 8-12-2016 at 09:47

Does somebody know anything about the compound 1,1,2,2-tetranitroaminoetanu, which is supposedly the hydrolisation product of TNGU.

Detonation velocity is 9500m/s
Detonation pressure 41GP

The only thing I can find on this compound is a polish paper which i unfortunatly can not read. :mad:
Maybe someone who speaks polish is so keen and translates the synthesis and/or other important information.
I am really interested but there is nothing. If someone knows something please feel free to post it. :P

Attachment: 1,1,2,2-tetranitroaminoetanu.pdf (652kB)
This file has been downloaded 71 times

Thank you!


PHILOU Zrealone - 9-12-2016 at 13:28

Quote: Originally posted by Mr.Greeenix  
Does somebody know anything about the compound 1,1,2,2-tetranitroaminoetanu, which is supposedly the hydrolisation product of TNGU.

Detonation velocity is 9500m/s
Detonation pressure 41GP

The only thing I can find on this compound is a polish paper which i unfortunatly can not read. :mad:
Maybe someone who speaks polish is so keen and translates the synthesis and/or other important information.
I am really interested but there is nothing. If someone knows something please feel free to post it. :P

Thank you!


Such geminal nitramines (*) are powerful but quite sensitive (shock, heat, friction) vs parent nitramines and they also lacks stability for storage...they are very acidic and reacts with metals to make sensitive metal nitramines...the H onto the NH is even more acidic than into carbon nitramines holding max one nitramine per carbon atom (viccinal nitramines)(**).
They will be very happy to split off a nitramide molecule (H2N-NO2 (unstable)) and to provide a nitroimide group.
R-CH(-NH-NO2)2 <--==> R-CH=N-NO2 + H2N-NO2
H2N-NO2 ---> H2O + N2O + N2 + O2

(*)
Methylene dinitramine CH2(-NH-NO2)2
Ethylene bis-dinitramine (N,N,N',N'-tetranitro-ethylene-1,2-diamine) (O2N-NH-)2CH-CH(-NH-NO2)2
(**)
Methyl nitramine CH3-NH-NO2
Ethylene dinitramine O2N-NH-CH2-CH2-NH-NO2
Propane trinitramine O2N-NH-CH2-CH(-NH-NO2)-CH2-NH-NO2

Microtek - 10-12-2016 at 09:21

When I wrote my dissertation, I investigated the possibilty of condensing tetranitraminoethane with disulfaminotetrahydroxypiperazine and then nitrolysing the sulfonic groups to form HNIW without annoying catalytic hydrodebenzylation.

Unfortunately, the results were inconclusive.

About the paper: Why don't you copy/paste it into google translate? It won't be a perfect translation, but usually enough to catch the essentials (especially if you know something about the subject).

[Edited on 10-12-2016 by Microtek]