Anybody tried to make DINGU or SORGUYL?

[Kroways]

Here you can find a description of two French-invited, quite strong explosives:

http://kroways.hyperlink.cz/images/diso1.gif
http://kroways.hyperlink.cz/images/diso2.gif

I have prepared both, but only an amount of 2 grams each. If somebody had more glyoxal than I was able to obtain, he could try and post some report. The synthesis is very simple, I can send detailed info if needed.

[Kroways]

Sorry, I didn't see there already is a topic started about these compounds.

[frostfire]

could you tell us more about this glyoxal,
commercial name perhaps

[cutefix]

I am very interested with this sorguyl because it is unique,the U.S Patent submitted by SNPE indicates it requires a blend of nitric acid and dinitrogen pentoxide in its synthesis.Is your procedure similar to this.?I also noticed that the amount of acid used is enormous, if compared to the preparation of PETN and RDX.Please show us your procedure in preparing this item from glyoxal.

[cutefix]

It is indicated in the links you have given that it is incompatible with TNT,Then how can we make cast explosives from it similar to octol(HMX/TNT).Any way aside from TNT there are already known potential and more powerful replacement for TNT in this cast molding application such as TNAZ(trinitroazetidine) and MTNI(-methyl-trinitroimidazole).Do you think DINGU/SORGUYL make a nice blend with it?

[Kroways]

I have found a russian article about making 1,1,2,2-tetrakis(nitramino)ethane, when I was searching using Beilstein commander. In this procedure they nitrate glycoluril with 98% HNO3 in Ac2O and hydrolyse the tetranitroglycoluril obtained. The corresponding part of article can be seen here:

http://kroways.hyperlink.cz/images/page2779.gif

I now try to make a rough translation into English:

1,5-Di-tert-butyl-1,5-diaza-3,7-dioxabicyclo[3.3.0]octane: Heat 0.1 mol of glyoxal(50% solution) with 0.25 mol of urea to 80-90°C for 1 hour. Maintain the pH to be between 0-1. Cool to room temperature and filter out the solid. Recrystalise the product from water(i suppose this would be a problem when making more than this amount - the glycoluril is VERY badly soluble - maybe try another solvent or do not recrystalise at all). Yield: 11.9g(85%), melting point 218-226°C.
Add 3ml 98% HNO3 to 9ml of acetanhydride stiring vigorously, maintaining the temperature at 20°C. This mixture is mixed 15 min. at 20°C and 0.6g above obtained glycoluril is added. Mix 30 minutes at 20°C and then 2 hours at 25-30°C(i had only an hour and the yield was lower - try to keep the prescript). The solid formed is then filtered out and washed with dichlorethane(i used CH2Cl2 instead). Yield: 0.92g(72%), melting point 226-232°C.

I suppose that the mixture with molten TNT is possible, if TNGU doesn't decompose at contact with it. The unsolubility in TNT means no problem.

[VasiaPupkin]

Hi kroways! Its interesting links. Is there more scanned info about other high explosives? Is it available for downloading?

[Kroways]

Vasia> I have quite extensive archive of copied and scanned documents, but unfortunately I only have a common 56k modem so that few documents can be shared via internet. Another problem is that about a half of books I have is in Czech. If you knew about a free webhosting server, which offers unlimited space(hundreds of megabytes or rather 1-2 gigabytes), I would be able to take my HDD to school and upload it all. Do you have something interesting you can offer, as well? I would prefer English or German(if not Czech), Russian language is also possible.

Others> Today I tried to detonate 1g of dingu with lead azide and failed. Only a quiet "puff" could be heard and a remain of white powder(dingu) was found at the bottom of testing vessel. I wasn't surprised, because I used only 200mg of low density lead azide and that is the amount which is just enough to initiate RDX, which is more sensitive. The dingu was placed into a 1/2" paper tube and pressed with wooden rod. A tiny plastic sack with the primary explosive and fuse was put on the surface and sealed with cotton. I will try the same experimet with sorguyl, its sensitivity to impact is considerable, so I hope the sensitivity to primary explosives will also be highhttp://theforum.virtualave.net/ubb/smilies/smile.gif

[cutefix]

Thanks for the info Kroways,I will study it and try to synthesize it in the lab when I return home.I can procure some glyoxal from a chemist friend of mine.
Frostfire this is what the Merck Index say about glyoxal:
Glyoxal is also known as ethanediol,oxalaldehyde,and diformyl{OHCCHO}.Prepared by the oxidation of acetaldehyde by nitric acid or selenious acid.
Properties:Yellow prisms or interplanar pieces turning white on cooling.Density1.14.m.p.15C.b.p.51C.Vapors are green and burns with purple flame.Mixture with air may explode.Soluble in anhydrous solvents.pH at 40% solution 2.1-2,7.Polymerises quickly on standing.Commercially available as a crystalline dihydrate.[OHCCHO]3.2H2O.crystalline powder,nonhygroscopic or as 40% aqueous solution which contains polymerization inhibitor.Uses: textile,organic synthesis,glues,biocides.Toxicity LD50-2070mg/kg (rats) orally.

I could not find of any commercial name for it.


[This message has been edited by cutefix (edited July 29, 2001).]

[simply RED]

Very good info, but some reactions won't be bad...
What is the chemical formula of glycouril and dinitroglycouril?(I know it is dinitro, but I'm curious).
Please type it easily to read, like "C2H2", I mean don't use: "1-chloro......".

[Hex]

Comprehensive info on the parent compounds for these explosives can be found in "Synthesis of Cyclic Ureas", H. Petersen, Chemical Reviews,243-292 (1973)
It may be possible to prepare these compounds by direct condensation of nitrourea/dinitrourea (M.Syczeweski et al, Propellants, Explosives, Pyrotechnics, 23, 155-158 (1998), but I've never come across any attempts at this in the lit.

[simply RED]

Can you give the structure formulas?

[Hex]

The structures are available from the patents site at http://gb.espacenet.com/
The patent number is US4487938. Hope this helps.
The VoD's are very impressive. However, like keto-RDX, they are pretty prone to hydrolysis.

[Hex]

This is somewhat off the thread, but may be of interest - keto-RDX, another cyclic urea, maybe prepared from a slow release US fertilizer called N-SURE which contains 40% 1-oxo-2,4,6-triazine and is apparently very cheap. The paper which states this also claims that k-RDX is 3-5% more powerful than HMX. If anyone wants any further details...

[Kroways]

Wow! I didn't know that keto-RDX is so powerful. I have a copy of another russian article corresponding to compounds like keto-RDX and others. If I have time, I will scan it.

[cutefix]

I have limited information about keto-RDX.I’m still unsure if it is really called-2,4,6,-trinitro-2A-6-triaza-cyclo-hexanone ,for I have never seen the structural formula.I hear that there are also a mono-di-tri keto-RDX,and there is even a keto-HMX with corresponding higher” isomers.”It was described to be made by reacting urea with 37% formaldehyde solution and tert-butylamine;then the intermediate known only as TBT was reacted with acetic anhydride and absolute nitric acid(a blend of nitrogen pentoxide and nitric acid) in order to form this keto-RDX.I anticipate that the resulting product will not be pure but contains homologues mentioned earlier.It will then have some similarity with RDX made by the anhydride or “E”process.,which is more sensitive(due to the presence of crude HMX,where some isomers are very sensitive to impact) than the pure nitrolysis made material.(direct reaction of hexamine and nitric acid).
This keto-RDX was estimated to have a VOD of 7000m/s,and was said to be more sensitive than RDX to impact test by more than half!Therefore it appears to be more dangerous to synthesize than cyclonite.We don’t have any idea about the impact sensitivity of the crude material containing its homolog,as well as the proper refining process in order to extract the pure material.The reason it was called that way because,one methylene group in the RDX structure was replaced by a keto group.If that’s the case the oxygen balance will be increased a bit due to the oxygen of the keto group(C=O).Indeed this material offers interesting possibilities because the basic material is Urea which is a lot cheaper and easier to obtain than hexamine!More details about this material would be appreciated,in order to confirm the veracity of this information.In addition it will open another interesting subject in the discussion about another powerful explosive.



[This message has been edited by cutefix (edited August 02, 2001).]

[Hex]

This is bang up to date stuff on k-RDX from this years ICT conference. (H. Ritter, S.Braun, M.Schafer - you might find the paper somewhere more accessible if you try searching the abstacts for these guys)
They give the VoDmax as 8899m/s(!) at d=1.85 and impact sensitivity of 15cm (HMX=32cm)
I've read the original synth (AR Mitchell et al, Propellants,Explosives, Pyrotechnics, 19, 232-239 (1994). Tert-Butyl triazone can be made, as Cutefix says, in about 50% yield from tertbutylamine, formaldehyde and urea. Nitration of TBT gives k-RDX in 57% max yield. The same paper reports synth from triazone (recovered from N-SURE fertiliser - $0.56/lb bulk cost!) in 49% yield.
The trouble with these synths is the super pure nitric.
You could try searching for H Boniuk, W Pilecki, T Stawinski, M Syczewski. I've got a copy of a paper of theirs from an ICT conference, but unfortunately I don't know what year it's from! Anyway, they made k-RDX from nitration of hexamine in the presence of dinitrourea, or from the hexamine salt of dinitrourea. It doesn't say, but I suspect this synth relies on the in situ formation of dimethylol nitramide, so there might be possibilities for a synth from nitramide, formaldehyde and dinitrourea. It'd have to be in organic solvents of course, rather than aqueous formaldehyde.
I'm thinking of getting my (tech-nerd) brother to sort me out some web space so I can put up some scans of some of my hard to get info (but only public domain stuff, guys - sorry!)
Cheers

[cutefix]

Hex,is TBT or tert-butyl-triazone,is similar to the triazone found in slow nitrogen release fertilizer used in lawn/turf grass maintenance?N-sure was said to contain 72% total triazone(triazone and substituted triazones).I think triazones have heterocyclic structures,(cyclical structure)and one of the condensation products of urea and formaldehyde.It was the result with the reaction in the presence of amines.Triazone has an empirical formula of C3H6N3R.Therefore if triazone is extracted from N-sure ,or made from urea it can be nitrated by nitric acid in presence of two dehydrating agents acetic anhydride and nitrogen pentoxide.But the yield is not high,even if the amount of added N205 is said to be about 20%.I was thinking of an anhydrous nitrating medium composed of N2O5/organic solvent/P2O5.This particular system was able to produce about 14%Nitrogen content nitrocellulose,about 50/50 yield of TNT/DNT from single nitration of toluene,and 95% yield of PETN.It could possibly improve the yields.Anyway is there any published papers (public domain) of this subject (keto-RDX)in the net?I find this topic very interesting but I have no time to check it in the library,because I’m always traveling now.This subject made me remember about other explosives that can be made from urea,such as:
The alternative way of making HMX/RDX by starting with urea,which is nitrated to form urea nitrate,then this is reacted with sulfuric acid to yield nitrourea,then this nitrourea is reacted with formalin solution in the presence of sodium hydroxide and the resulting intermediate is reacted with ammonia water in order to form DPT(1,5-methylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane) which is an intermediate in the production of RDX/HMX.(check USPatent 4,338,442)It is a circuitous route but feasible.I see even by this process,that the yield of the desired product is not high,in the same range as the yield for keto-RDX from from urea or triazone( as you mentioned).I realize therefore that urea and formaldehyde are the current basis for nitramine explosives,not hexamine!


[This message has been edited by cutefix (edited August 02, 2001).]

[Hex]

I would expect that the triazone in all slow release fertilisers is 2,4,6-triazacyclohexan-1-one (there are loads of ways of naming it) TBT, as you suggest is alkylated at the 4-position. If fertiliser triazones are substituted at the 4-position, ease of nitration will depend on the nature of the substituent. My information is that the active ingredients of N-SURE are 40% triazone and 12%urea., and that simple removal of the solvet/water whatever else is in there in a rotary evaporator leaves a blue sludge which is good enough for nitration. Even if the yields are a bit shitty, the starting material is pretty cheap!
I think it may be possible to synthesise k-RDX without isolating the triazone from dinitrourea(DNU). If one was to make some DNU, hyrolyse some of the batch to nitramide (NH2NO2), I suspect that k-RDX would form from 1 equivalent each of the nitramide and DNU in a solvent saturated with gaseous formaldehyde (which can be made from the pyrolysis of paraform at 170C) It might even be possible to use paraform itself, or trioxan, but obviously aqueous formaldehyde would hydrolyse the DNU pretty rapidly.
DNU isn't that hard to make - it may be possible to get away with using 70% Nitric as long as the nitrating acid is made up with 30% oleum.
To be honest, I've never done any work with P2O5, so I can't really offer much of an opinion on it's merits in nitrations. I try to avoid using N2O5 if I can. It's a pain to make, and a pain to use, though it does admittedly give great results for N-acetyl nitrations. I think there are some general misconceptions - in most circumstances, it's probably less effective than acetyl nitrate.
Hydrolysis of nitrourea to nitramide is probably what the DPT synthesis Cutefix mentioned depends on. DPT, and it's homologue have both been prepared from formaldehyde, nitramide and ammonia (or ethylene diamine, in the case of the homologue)DPT can also be prepared from hexamine and KNO3/sulphuric or hexamine dinitrate/sulphuric, in pretty low yields (20% or so). Nitration of DPT, to RDX or HMX, in all the papers I've seen, unfortunately requires 99.5 nitric. DPT itself doesn't display any explosive properties.
I'm not sure about where you could get this stuff on the net - I'm lucky enough to be able to order paper copies of just about anything. If the journal Propellants, Explosives, Pyrotechnics is published anywhere online, it has recently had loads of material on k-RDX and DNU. If the proceedings of the ICT conferences held annually at Karlsruhe, Germany, are available on the net, then that would also be v.useful. Like I say, I hope to be able to get some scans up on a site soon for the benefit of those without access to journals.

[PHILOU Zrealone]

It seems that the K-6 has a better performance than HMX due to its better OB but also due to its density and ring strain since C=O is sp2 hybridation it forces the 3 atoms N-CO-N to be coplanar while in RDX related molecule the N-CH2-N is free of move and addopt the stable less stressed conformation!
As known stress in rings enhance heat of combustion and thus of detonation.

We(friends and me) are coworking on ketoHMX and diketoHMX!It seems that diketo and triketo RDX are rather unprobable (too much stress means also fast hydrolysis and poor stability).We are currently investigating the UN and DNU way of synthesis!
I have a beautifull idea of a kind of dimeric ketoRDX that would be exceptionnal!

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

[Hex]

Philou,

Have you yet had a chance to attempt the k-RDX synthesis using DNU, nitramide and formaldehyde? I'm fairly sure that is how the DNU/hexamine salt and DNU/hexamine processes work. Doing it with nitramide/formaldeyde would avoid RDX contamination. It could be done in organic solvent with gaseous formaldehyde, to avoiding hydrolysis problems with DNU. Another way would be to use 1,3-dichloro-2-nitro-2-azapropane /DNU. I can dig out a reference for this compound if you're interested.

[coenvh]

Hex,
I'm one of the friends Philou talked about and I would be very interested in the paper/reference! I'm sure Philippe is too.
If you would have the time to take a look for it, I would appreciate it.

Coen

[Hex]

the ref is patent no US 4 085 123 (JE Flanagan, MB Frankel). They use the dichloro compound to make the 1,3 diazido compound.

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

[Hex]

ps - don't forget to send me my percentage when you patent this process for k-RDX!!! Let me know how this synthesis goes - I haven't got time to do any DNU work at the moment. How is diketo HMX synthesised? From DNU/formaldehyde?

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

[Mr Cool]

Hehe, my brain's starting to hurt from reading this thread!

Anyway, here's something similar to the K-RDX: Nitrotriazolone.

Triazolone is made by reacting formic acid with semicarbazide - the latter is urea with one H replaced by NH2. The triazolone is then reacted in a HNO3/H2SO4 mix to make 4-nitro-2,3,5-triazol-1-one (or 3-nitro-1,2,4-triazol-5-one etc, whatever you want to call it). The whole reaction sounds very simple and gives a <77% yield. Look in the "links" thread in misc. for the text. They used crystaline semicarbazide hydrochloride and dissolved it in 88% formic acid solution (aqueous I assume), and then nitrated the triazolone without seperating it from this reaction mixture, using 100% HNO3 and 98% H2SO4 - this means that if you seperated and dried the triazolone, you could easily get away with less pure HNO3. Does anyone have any ideas on how to synthesise the semicarbazide? I was thinking about dissolving nitrourea in an organic solvent (to prevent the re-formation of urea nitrate. Would an alcohol like methanol work?), and then reduce the NO2 group with NaHS (Edit: or is it Na2S4 that's made with NaOH and S?), but would this affect the C=O instead of the NO2?? If that works I might even try to make this explosive.

So this triazone in fertilisers - I get the impression from reading this thread that it is basically non-nitrated K-RDX. Is that correct?

Hex: "DNU isn't that hard to make. It may be possible to get away with using 70% nitric as long as the nitrating acid is made up with 30% oleum." Why not use 100% H2SO4 and anhydrous metal nitrates or ammonium nitrate?

Also, can you post any more detail on the formation of nitramide?

P.S. - did someone mention that hydrolysis was a problem with K-RDX? Well NTO can be recrystalised from water, so I'm guessing that it doesn't share this problem...

P.P.S. - if an acid mix with H2SO4 can be used to make NTO, then surely an H2SO4/metal nitrate mix would also work? If so then this explosive could be a very good, very easy choice!

[This message has been edited by Mr Cool (edited August 26, 2001).]

[This message has been edited by Mr Cool (edited August 26, 2001).]

[This message has been edited by Mr Cool (edited August 26, 2001).]

[cutefix]

It is not very difficult ,it is just a lengthy procedure if you plan to produce it from basic building blocks like urea and hydrazine(I think you don’t like this material!).
Preparing semicarbazide from Nitrourea is suitable only in industrial scale.It requires hydrogenation at about 70 atmospheres of pressure,in the presence of sulphuric acid using a rhodium catalyst,the reaction is this way,forming another salt;semicarbazide sulfate where it can be converted to hydrochloride as desired.
NH2CNHNO2 +3H2 +H2SO4 --> NH2CONHNH2.SO4+2H2O
The stipulated acid /NU ratio is 20/1 respectively….
The latest laboratory method of preparing semicarbazide is by reacting urea and hydrazine in these proportions…
60 gram of urea and 55 gram of (64%hydrazine solution) were refluxed at 115-120C for 3 hours until no more ammonia gas is evolved.It is then evaporated under vacuum(preferably about 10 torr pressure) leaving semicarbazide and some byproducts like hydrazoazodicarbonamide.
That mixture is then digested with boiling methanol for 45 minutes in order to precipitate the hydrazoazodicarbonamide.The solid material is filtered out and the filtrate is cooled to 10 C and 98 grams of 37%hydrochloric acid was added to precipitate the semicarbazide hydrochloride.This material is then washed with methanol and dried……

Keto-RDX is made by nitrating triazone,with acetic anhydride/nitric acid/N2O5 and this triazone is made by condensing urea,formalin,and tertbutylamine.Keto RDX is stable I think just like RDX….

As far as I know nitramide (H2NNO2)is unstable and should be made fresh;it decomposes at 72-75 C.it is known to be made from a less known material potassium nitrocarbamate.Nitramide is soluble in water,ether,acetone and is precipitated by petroleum ether or chloroform…

The laboratory scale preparation of NTO is done this way:
230 ml of 85% formic acid was added to 223 gram of semicarbazide hydrochloride in a 1 liter 3-necked round bottom flask.it is heated with stirring until the dissolution.The excess formic acid is removed by distillation until crystallization occurs.A 300 ml water is added to it and distillation is continued until the mixture is nearly dry.This is the precursor TO(1,2,4 triazole-5 one).Now to convert it to NTO you have to cool these precursor to 25C then gradually add 500 ml of 70%HNO3.Heat this to boiling while stirring.Nitrogen oxides (brown fumes) will be evolved and heating is done until no more fumes are produced.Cool it to 5C,this will precipitate the crude NTO,collect this by filtration on buchner funnel.This precipitate is then washed with ice water to remove excess acids.It is recrystallized in water and dried in oven at about 70C for 24 hours.
I think a metal nitrate/H2SO4 is a possible alternative way to do the nitration...


[This message has been edited by cutefix (edited August 27, 2001).]

[Hex]

Nitramide is probably best made form hydrolysis of Dinitrourea. The classic synth is from the ammonium salt of nitrourethane, but that method is a nightmare. I make it by dumping my DNU/nitrating acid mix straight into ice/water (250ml for DNU prepared from 3g of urea by the published methods) and extract with 3 or 4 portions of ethyl acetate. I wash that with water and leave it with droplets of water suspended in it overnight to complete the hydrolysis, before drying it over mag sulphate and evaporating.
The yield is about 40-50% from urea. (although that DNU synth is a weird one - it sometimes fails for no reason. Take care to get the driest materials you can)

Triazone is basically non-nitrated k-RDX. Not too sure about nitrating it with H2SO4/metal nitrate, I don't think it would be very stable in sulphuric. You never know, though.

[Mr Cool]

Really sorry if this has already been discussed, but it's midnight and I need some sleep and can't be bothered to check... so if it is already here then just ignore me and I'll find it in the morning...

Can someone tell me whether or not nitramide can be reacted with formaldehyde to form RDX (and HMX)?
3 NH2NO2 + 3 CH2O --> C3H6N6O6 + 3 H2O
And if not, why not?!
I had a quick look and I can find nitramide + formaldehyde + DNU --> K-RDX, but I didn't notice anything about normal RDX... I know it'd be harder than most other methods, I'd just like to know if it'd work, to improve my undertsanding a bit...
Again, sorry if this is already here...

Another edit: can DPT be converted to RDX using an H2SO4/metal nitrate mixture? Since H2SO4 is used in the prevous step I can't imagine it being much of a problem... Also, can someone post the chemical formula? I'm having trouble visualising it...

Thanks!

[This message has been edited by Mr Cool (edited August 30, 2001).]

[This message has been edited by Mr Cool (edited August 30, 2001).]

[simply RED]

NH2NO2 is said to be extremely unstable. It decomposes by the next equation.
NH2NO2 --> N2O + H2O

[cutefix]

In order to form RDX or HMX from nitramide you must first make DPT(dinitropentamethylenetetramine) by reacting nitramide with formaldehyde and ammonia in this scheme
2NH3 + 5CH2O +2NH2NO2-(CH2)5N4(NO2)2(DPT)
To form HMX it is reacted directly with nitric acid
(CH2)5N4(NO2)2 +2HNO3 -(CH2)4N4(NO2)4(HMX)
To form RDX only it is dissolved in H2SO4 then reacted with HNO3
(CH2)5N4(NO2)2 + HNO3 - (CH2)3N3(NO2)3(RDX)
If H2SO4 can be used in making RDX then it is possible also that acid/metal nitrate would work but again the yields will be lesser.
Both RDX and HMX can be made in the presence of ammonium nitrate and acetic anhydride.
2(CH2)5N4(NO2)2 + 6(CH3CO)2O + 2NH4NO3 + HNO3-(CH2)4N4(NO2)4 +(CH2)3N3(NO2)3 + 12 CH3COOH +3CH2O + 2NH3
The yield will be in the ratio of 22/78 hexogen/octogen if the ratio of DPT to ammonium nitrate is1:1 or 55/45 if the ratio is 1:2.It is then purified by digesting with 70% HNO3 then washed and refluxed in acetone until dissolved then the solution was diluted with water to form 70% acetone to start precipitation and the slurry refluxed again,then additional water is added to form 50 % thereby increasing the concentration of precipitate.Then acetone is distilled until only about 10% of acetone remains.It is further refluxed after which the residual ketone is gone.The purified crystals is then mixed with iodobenzene and centrifuged.The lower layer will be the HMX fraction which settles and the upper floating layer will be the RDX rich fraction.The separated fractions can be purified and dried.

[Hex]

The failure of nitramide to react with formaldehyde is something that bothers me. Even in DMSO, stable addition products like 1,3,5-trinitro-1,3,5-triazapentane (made by other means) won't react with formaldehyde (as paraform, trioxan or a saturated solution of gaseous CH2O) to form RDX. Strangely enough, methylene dinitramine reacts at ambient temperature in DMSO to produce longer chain polymethylene nitramines and free nitramide.
The only cyclisation to form RDX from a linear compound I've seen was the reaction of 1,3,5-triaza-1,3-dinitropentane nitrate with paraform under strong nitration conditions. I'm on holiday right now, so I can't get the reference dug out, but I think it was by two cats called Dunning and Dunning, and was in the JCS around 1966 if someone wants to search the abstracts.
Mr Cool,
DPT is like HMX with two NO2 groups on opposite sides missing,with the two nitrogens those two NO2's "should have been on" linked together by a CH2 group. Sorry, I don't have the tech to put up pictures, hope this helps..



[This message has been edited by Hex (edited August 31, 2001).]

[Mr Cool]

Cutefix and Hex: Thank you both for your help!

Ah, I see what you mean about DPT now... there's a nitrosamine equivalent of that too, which is made with hexamine, NaNO2 and HCl but under different conditions to R-Salt. Strangely, the nitrosamine apparently IS detonatable, whereas someone said that DPT isn't! Well I suppose nitrosoguanidine is as sensitive as lead azide, so maybe most nitrosamines are more sensitive than the nitramine equivalents.

I tried to nitrate DPT (from hexamine, KNO3 and H2SO4) with an H2SO4/KNO3 mixture today, but it seems to have failed... not yet sure why http://theforum.virtualave.net/ubb/smilies/frown.gif I used 14g of powdered hexamine mixed with 20g of powdered KNO3, and slowly added this to 78g of 90% H2SO4. I added it while stirring and keeping the temperature below 15*C (it was at c.12C for most of the time), addition took about 1.5 hours since I only had an ice bath and not much ice to keep it cool, so I did it slowly. I figured this was plenty of time for it to react, so I then added it slowly, while at c.10*C, to 45mL of H2SO4 and 177g of KNO3. After it was all added, I stirred it for about half an hour at room temperature (23*C) and dumped it into 1.5L of crushed ice/water. So far I have got no precipitate, and I don't think I will get any!

When making the DPT, it foamed a lot. Anyone know what this gas was? It wasn't NO2 and didn't smell much. The only thing I can think of is ethene but that seems very unlikely to me...

Is there any way I can precipitate and purify the DPT before I nitrate it? I'm sure this would help.

Unfortunately I can't get Ac2O and I can't be bothered to make 100% HNO3, so I'm always looking for methods that don't need either... and besides, my distillation setup is broken so I couldn't make HNO3 even if I wanted too http://theforum.virtualave.net/ubb/smilies/frown.gif Perhaps I should just go to the trouble of making some Ac2O, it doesn't seem all that complicated.

One more question: can you condense nitrourea with formaldehyde to make diketodinitro-HMX? Per mole it's missing the same amount of oxygen as HMX, and is probably detonatable. If not, you could probably nitrate it further to diketo-HMX. I just thought I'd ask, since NU is VERY easy to make and CH2O is VERY easy to buy! If so, what solvent would you do it in?

I hate it when things don't react how you want them to. Nitramine + formaldehyde would be so simple!

[cutefix]

I see your reaction favors the decomposition of hexamine, that is the reason of gas evolution. and not the formation of DPT.The immediate contact first with nitronium ion and not the sulfate ions is needed with this reaction.How about if the nitrate salt was reacted first with the acid in order to liberate nitric acid.?Then add hexamine gradually.That condition of temperature is suitable for hexamine dinitrate formation but in the same manner that the reacting medium should be heavily laden with nitrate ions before the gradual addition of hexamine.Even though the reaction will still occur slowly(formation of hexamine dinitrate first).Then this product can then be reacted with acetic anhydride to form DPT.
.The fastest way of making it is by nitration with(98%) nitric acid in cold condition to prevent undesirable oxidation of hexamine. This should be added gradually to the nitrating medium.Another important part is after the addition of last portion of hexamine.It should be drowned immediately with ice water to precipitate some RDX that is produced also.The filtrate which smells formaldehyde is promptly neutralized with aqueous ammonia/sodium carbonate solution to a pH of5.6(use bromcresolgreen as indicator-it will appear barely blue at this pH.).In the span of 15 minutes DPT will precipitate .This material is not as stable as RDX .It is easily decompose by heat.(boiling water will decompose it rapidly.DPT can be purified by recrystallization from acetone.

I think condensation of nitrourea and formaldehyde will form an intermediate that upon neutralization with ammonia water will form DPT.To be clear, the reactions starting from urea will be like this;

H2NCONH2(urea) +HNO3 => CO(NH2)2HNO3(urea nitrate)
CO(NH2)2HNO3 if reacted with H2SO4 will formNH2CONHNO2(nitrourea)
NH2CONHNO2 +CH2O=>H2NCONNO2(CH2OH)(intermediate)
H2NCONNO2(CH2OH) +CH2O +H2O=>O2NN(CH2OH)2 +CO2 +NH3
And 2O2NN(CH2OH)2 + NH3 +CH2O=>(CH2)5N4(NO2)2(DPT)
The DPT yield will be around 50% based on nitrourea,while conversion of hexamine dinitrate with acetic anhydride will give 30% yield.
Then this DPT can be purified and used for preparation of RDX or HMX.

Indeed chemistry can be exasperating when your reaction predictions does not occur!

[Mr Cool]

Thanks!

Yes, I thought it might be because I mixed the nitrate and hexamine first, I'm not sure why I did that! I think I'll use hexamine dinitrate and sulphuric acid, to avoid all the K2SO4.
I'll try again...

In the last line of that equation you gave, surely you need 2NH3 if you have 2O2NN(CH2OH)2?

Edit: so could I just dissolve 10.5 grams of nitrourea and 7.5 grams of formaldehyde in some methanol + a bit of water, and maybe heat it/cool it? Or would I need to do each stage seperately?
Any temperatures for the NU -> DPT reaction would be appreciated if you know them.

[This message has been edited by Mr Cool (edited September 01, 2001).]

[cutefix]

Yeah,I missed that double NH3,thanks for reminding.
I think the following step is easier:
I would prefer by dissolving the NU in 37% formaldehyde solution(formalin),then heat it to 45C.[If you use 10.5 grams NU you will need double that amount of formaldehyde(22 grams or 60 grams of the formalin).Excess of CH2O,than what is theoretically needed is desirable.].. Stir until the NU is dissolved.
Cool the solution to 25C and adjust pH (2-3) with 5%NaOH.At this point you will see the beginning of gas evolution .Stir it until no more gas comes out.
Then this solution is heated to 65C and stirring it ,or until no more gas is released(about 60 minutes).
Now, cool it at room temperature,then adjust pH(6-7) with 43% NH4OH solution.You will see precipitation at this point(that will be the first crop of DPT).Filter it out,then treat the filtrate with more NH4OH, to produce more crops of DPT.Repeat the filtration and alkali treatment until no more precipitation occurs…

[Mr Cool]

Thanks a lot!
That method seems very simple. I have about 1.5kg of urea nitrate, but unfortunately I'll have to go and buy some more H2SO4 before I can make it into nitrourea and try this...

[VasiaPupkin]

Additional info from my books: nitramide - is a very soluble hydroscopic solid matter. Its inclined to decomposition but sufficiently stable with non long keeping . Quick decomp. temperature is 172 C (sometimes with explode) but it could be vapourised in vacuum.. It has a weak acidic properties, momentary decomposes when Ph >7 (in OH- solution). Its known only Hg a little stable salt. (Many scientists are suppose the decomposition of AN in a two stadium NH4NO3=>NH2NO2+H2O=>N2O+H20 decomp. of NH2NO2 is a quick). From literature I saw also NH2NO2 can easy condense (as amide). For example with CH2O in ethylacetate/water solution, it result in termoresistant HE polymer with linear structure [-CH2NNO2-]n with great yeilds. I think its possible to control "n" in main by using a special catalyse of cyclisation. By anology I think Li+ will lead to HMX. Also I think this condensation is possible with glyoxal (it has a big condence potencial too) in unknown conditions (I think its maybe non known for public new HNIW technology - I heard some from one university teacher - more effective and simple way of HNIW preparing is exist. I cannot to estimate its reliability, because many russians HNIW's operations is confidence). Nitramide can be prepared by ammonolise of nitronium salts, from nitrouretanes or nitroureas (In the chemistry dictionary'95 only simple reaction without details and conditions NH2CONHNO2=>NH2NO2 + HNCO. In a two weeks I will try to get more detailed info. HNCO must condence to a very little soluble trimer or polymer (0.3% at room temp)- it may be usefull for puryfing). And DPT is inclined to make a better HMX yeild. Its use for classic HMX preparing.
To Kroways: What the shit with your mail box? I cannot mail to you now. And mail.ru has non stable reputation.

[CodeMason]

Could nitramide be prepared under the following reaction?

<font face="courier new" size="2">KNO₃ + NH₃ -> NH₂NO₂ + KOH</font>

I don't see why not, and if it can... it's simply a matter of making an ammonia generator from a coke bottle (containing ammonium sulfate fertilizer + caustic soda + water) with a tube leading into a solution of potassium nitrate.
The only problem I can forsee is as someone said it has mildy acidic properties so the KOH might cause some trouble.

[Mr Cool]

Well VasiaPupkin said it decomposes when the pH is above 7, so the reaction wouldn't work like that. And if you added a stronger acid to react with the KOH and keep the pH down then it'd react with the ammonia and you'd get no nitramide...

[CodeMason]

Damn, and I was thinking I had a quick and dirty way to produce nitramide. Oh well.