HNIW within reach

[Microtek]

First of all, I realize that there are some HNIW/CL-20 threads already. These are, however, quite old and many of them contain a lot of unrelated info, so I thought it would be worth it to open this new thread.

For the last couple of days I have been examining newly published patents regarding HNIW synthesis. I found two that looked very interesting, and in fact makes me confident that ( assuming the processes actually work ) HNIW can be realized in the home lab.

US2004 260086 is the most radically new procedure and the most promising as it removes the need for expensive Pd-catalysts and only involves two steps: Condensation of glyoxal and primary amine R-NH2 to form the isowurtzitane skeleton and isolating this intermediate, then nitrolysis ( with HNO3/H2SO4 ) of the intermediate to form HNIW.
The catch is that the primary amine must be one that can form a stabilized carbocation R+ during the nitrolysis. They mention allylamine as one possibility among many.
One other disadvantage is that they use a relatively large excess of nitrating acids, but other than this, no really exotic solvents, reagents or apparatus is needed; methanol is a preferred solvent, glyoxal as 40 % aqueous soln, most acids will works as catalysts ( though formic acid is preferred ).

On the other hand, US6015898 describes a new way of nitrating a hexa-N-substituted hexaazaisowurtzitane such as tetraacetyldibenzyl- ( TADB ) or tetraacetyldinitroso- ( TADN ) derivative directly using HNO3/H2SO4 in 98 % yield and purity using only a very small excess of acids.
The six substituents can be chosen according to:
up to 6 H-
up to 6 alkyl
up to 6 acyl
up to 2 alkylaryl ( eg. benzyl )
up to 2 -NO
up to 2 -NO2

The novel idea is simply to perform the nitrolysis at about 100-115 C for 4 hrs.

So, the first patent is realizeable in itself, but maybe the two could be combined. For instance using three equivalents of primary alkylamine to one of glyoxal to produce a hexaalkylisowurtzitane according to the first patent, then nitrolysis of this according two the second patent....

Any thoughts would be appreciated.

[SweNMFan]

Microtek. Is Matas still a viable source for H2S04 and HNO3 ?

[IPN]

Project-X vs. Detonator website ( http://pxd.zde.cz/ ) has a working and IMO simple looking synthesis for the intermediate but unfortunately it's written in czech.. Maybe someone can translate the synthesis?

[Microtek]

SweNMfan: Yes they still stock it at most of their shops.

IPN: From what I can deduce from the drawings on that site, they still need Pearlman's catalyst ( Pd(OH)2 on carbon ) which is expensive and besides, I have a strong dislike ( in the home lab ) for reactions involving heterogenous catalysis.

[akinrog]

US2004 260086 is the most radically new procedure and the most promising as it removes the need for expensive Pd-catalysts and only involves two steps: Condensation of glyoxal and primary amine R-NH2 to form the isowurtzitane skeleton and isolating this intermediate, then nitrolysis ( with HNO3/H2SO4 ) of the intermediate to form HNIW.


That patent number 260086 corresponds to an old patent related to fabric stretching mechanism. Am I missing something?

[BLASTER]

Akinrog: search it as "US2004260086" on http://ep.espacenet.com

Microtek: you are right, palladium catalyst is needed in that preparation (fortunately I can read that text ;) )

[VasiaPupkin]

I found one link http://www-sbras.nsc.ru/win/sbras/rep/rep2002/t1-1/him/cem1.html recently. Its a achievement of some chemical institutes in 2002.
See reaction scheme in the centre of the page. They developed a pilot plant mount to HNIW producing by 2 step method from glyoxal and kalium amidosulphonate (kalium salt of sulphamic acid). Sulfamic acid is a widespread chemicals.
Its looks like on a RDX w-process. No Pd catalyst or other shit.
We are trying to do this scheme at home now. But glyoxal is expensive in my city and I gave some intruction to my friend who have a cheap glyoxal.
It seems that he obtained a kalium hexasulphohexaazaisowurtzitane as white precipitate in a good yeild yesterday (6.0g from 5.6g of K-sulphonate).
Tommorow we are going to nitrate this stuff to HNIW with H2SO4/KNO3 mix.
I made RDX by w-method with H2SO4/KNO3 and I think that reaction condition will be the same.

[Microtek]

That reaction scheme looks very interesting indeed. Could you elaborate a bit on the process ? I don't understand russian, I'm afraid....

[nbk2000]

"Kalium" being an old alchemist term for potassium.

[Natrix]

"Kalium" being an old alchemist term for potassium.

It does mean potassium in Swedish as well! :-)

[VasiaPupkin]

They wrote only that technology of preparing is developed and pilot plant mount was projected.
Unfortunatelly I could not connect with my friend today to ask him what about nitration of potassium hexasulphoazaisowurtzitane.
Yesterday nitration was failed for bad nitration mixture. He would be try corrected proportions today.
First stage is mixing 2mole K-sulphonate with 1 mole of 40% glyoxal. A little water was added to dissolve all sulphamate. Ph corrected to 5.
After 3 hours of standing at room temperature mixture some changes. Mixture was stirred and milky-white precipitate quickly appears.
After 2h of standing mixture was filtered and precipitate dried at room temperature.
Nitration failed with 23ml H2SO4 and 30g KNO3. It needs more H2SO4 because when I prepared RDX by W-process reaction is not go in similar proportions.

[Myrol]

Hello Folk's! Umm, next week I'll go to a very good Friend of me wich is an Professor at a University and can so order nearly everything I want! :D

Well, I'll pay for one Liter 40% Glyoxal around 19€ and for a kg "pure" Amidosulphamic Acid 14€. I'll just have to neutralize the Acid with Potassium Hydroxide to get Potassiumamido Sulphonate.

So far so good, I can order some of this stuff for sure but I have no patent or a instruction how to make the Hexaazahexasulphopotassioisowurtzitan (damnit, you know.......the Isowurtzitan stuff with the SO3K groups instead of NO2!). I need only a suggestion under wich conditions I have to mix Glyoxal with SO3KNH2, the rest is easy. Umm, actually my knowledge is that I can mix 40% Glyoxal directly with the SO3KNH2 at roomtemperature and let it stand for some hours to go....But I've read something from PH-5.....really? I think Nitirc Acid would be Ideal to do this. But I need (fast) some ideas! :rolleyes: Wich excess of reagents are necessary and you know...under wich conditions??

The order is aimed for Wednesday to Friday.....so my time is rare.....If the reactions do work good, I WILL ORDER some of this stuff. Oleum with 65% SO3 is aimed too, because the Nitration should only work (like Cyclonit W) under anhydrous conditions. RDX needs an Acid with 80% HNO3, 5% H2SO4 and 15% free SO3.....with 65% Oleum I'm easily able to recreate this mix.

I think he will work for sure with HNIW too, the equatations say you just have to Nitrate with HNO3....no N2O5, no Pearlman.......good!

If I have a good instruction to make the Sulphosalt of Isowurtzitan and perhaps for the Nitration too, I will order Glyoxal, SO3HNH2 and H2S2O7 65%. Then I'm able to make some HNIW quite soon. :D Hope it works :rolleyes: ??

[VasiaPupkin]

Dont forget I only supposed that we get this hexasulpho. Some "know-how" may be exist in this technology. Specific catalyst or something else.
But some stuff is precipitated at pH5 is the fact. To get pH5 we used amidosulphonic acid its more convenient way. Excess of reagents is not so important but some k-salt excess may be useful I think.
My friend tried to nitrate this precipitate with KNO3-H2SO4 mix varifying the conditions. Unfortunately no result.
They use for nitration HNO3-H2SO4 mix no oleum. But I think oleum may be the good way to try it.
By the way I got "cyclonite W" without oleum. Reaction go in KNO3-97%H2SO4 mix but yeild is lower (I get approx 45-50%: 3gRDX from 12g K-salt 20g KNO3 30ml H2SO4).
And reaction don't go in NH4NO3-97%H2SO4 mix. In patent gb899692 anhydrous HNO3 is used in second example. Yeild 75%.

[cutefix]

I found one link http://www-sbras.nsc.ru/win/sbras/rep/rep2002/t1-1/him/cem1.html recently. Its a achievement of some chemical institutes in 2002.
.
Vasia that is an interesting link but the given equation is too simple to believe that it’s true. The formation of a caged hexaisowurtzitane structure is not that simple IIRC it was derived by the debenzylation of an aromatic material by Dr. Nielsen at his associates in China Lake.
The complexity of that molecule makes it difficult to rationalize that it can be easily formed by random reaction of potassium amidosulphonate and glyoxal..
Even with suitable catalyst it must come from a multi step reaction.
I have previously seen the original papers related to the discovery of that molecule and IMO it was not an easy task.
It would be very interesting if the reaction mechanism of its alternative synthesis could be elucidated. :)

[Microtek]

Cutefix: Take a look at the patent I posted about at the top of this thread; the isowurtzitane skeleton is synthesized in one step from primary amine and glyoxal. They use Brønsted acid catalyst, preferably formic acid, about 40 mol % based on glyoxal.
They preferably use a 50 % excess of amine ( so 3 mol amine to 1 glyoxal ) and they select a primary amine in such a way as to facilitate the nitrolysis by nitronium ion. This is done by having an organic substituent on the amino group which is able to stabilize the positive charge that arises when it is subtituted by +NO2.
Now, given that KOSO2 is a decent leaving group in the Wolfram method of cyclonite synthesis, I do think this is worth looking into.

[hedm]

If HNIW`s cage will be obtained I`ll check it by FT-IR. yesterday I made some potassium amidosulphonate and now I condense it with glyoxal. results will be on monday.
some HE books:
http://my-lair.narod.ru/pyro.htm

[cutefix]

Microtek the patent file that you displayed did show the abbreviation of the production process of HNIW, instead of the usual four stage preparation it can be now done in two steps. But not in one step.

Unfortunately the yield is low. This reminds me of the production of RDX via other methods but was never widely accepted because of the same reason, impractical yields. That procedure in that particular patent application is only suited for you who love to thinker with insignificant amounts of explosives. :)

One of my distrust to such novel procedure is the lack of background information if compared to the pioneering papers of Dr. Nielsen at China Lake which the evolution of that particular caged structure were detailed in various papers.

I also remember in those articles that the venerable professor had indicated from other investigators the failure of glyoxal to form isowurtizitane structure with other pathways(including aliphatic and aromatic precursors) due to the formation of diimines.

Check the J. of Chem Soc (Perkin transactions) 1993 on the paper titled:

Studies of the Synthesis. Protonation and Decomposition of Hexabenzylhexaazatetracyclododecane by Michael Crampton and associates

And check the corresponding papers by Dr. Kliegmann and K Barnes in :

Tetrahedron 1970,26,2555 and Tetrahedron Letters 1969, 1953 and .J. of Organic Chemistry 1970,35,3140.

Currently the four step procedure is successfully scaled up and this is the established procedure for some time.

Now regarding my original post which I asked Vasia about the details of the potassium amido sulfonate pathway to HNIW production I would like to know also if there is any English language papers that discuss the mechanisms of its formation and other salient details related to such revolutionary synthesis.Or if not he can present any satisfactory english translation of artciles related to that process.

It might just be another flash in the pan. Theoretically possible but practically not feasible. :)

Anyway, I am interested in the long term outcome of the alternative process.

[simply RED]

Translation from russian:
--------------------
Institute of Problems of Chemical and Energetic Technologies

{{{{names of the catedras and work in the institute (not connected to HNIW) }}}

The possibility of HNIW preparation via 2 reaction process is shown on the drawing.
The production of HNIW via this process is experimented on a pilot scale industrial production.

{{{{drawing}}}}

Figure. Lay-out of production of hexanitrazaisowurtzitane from potassium salt sulphamic acid and glyoxal
-------------------

The article tells nothing about the reactions itself.
Yes, quite interesting! Time will show is it true or not.

[Microtek]

Well I agree that the apparant simplicity of the process would suggest that it had already been tried. But then, history is full of inventions that in retrospect were obvious and should have been introduced many years earlier.
Now, about the process presented in the patent - they achieve yields ( of the condensation process ) of about 20-60 % depending on substrate and catalysts. This is actually quite good ! The only problem as I see it, is the effort involved in working up the substituted hexaazaisowurtzitane ( for instance, the allyl-substituted intermediate is air-sensitive ).

Regarding the novel condensation reaction involving glyoxal and K-amidosulfonate, it really isn't any simpler than the original China Lake patent:

"The synthesis of the first isolated intermediate compound, hexabenzylhexaazaisowurtzitane (HBIW), involves condensation of benzylamine with glyoxal (40% aqueous solution) in aqueous acetonitrile or methanol solvent with formic acid catalyst at 0.degree. to 250.degree. C. The best yield obtained (81%) requires slow addition of the aqueous glyoxal (1.0 mole-equivalent) to a solution of benzylamine (slightly more than 2 mole-equivalents) and formic acid (slightly more than 0.2 mole-equivalent) in aqueous acetonitrile, while keeping the temperature at 0.degree. to 250.degree. C. The optimum addition time for the aldehyde under these conditions is about one hour. After addition of all the glyoxal solution is complete, the reaction mixture is allowed to stand at ambient temperature (250.degree. C.) overnight (16 to 18 hours) to complete the formation of the product which rapidly precipitates from the reaction mixture in rather pure form."

This is pasted from a copy of the patent on:

http://www.dodtechmatch.com/DOD/INDEX.ASPX

I'm convinced that the 0-250 C indicated should actually be 0-25 C, the extra zero coming from a double transcribtion of the "degree" sign.

So, I realize that the feasibility of this method ( the K-amidosulfonate one ) will never be proven to be true or false by arguing, but my reasoning behind purchasing chemicals is this:

- The synthesis of the hexaazaisowurtzitane skeleton is essentially the same no matter which amino derivative is used.
- It has been shown ( in the referenced patent ) that a number of molecules other than benzylamine can be used for the condensation.
- It is well known that formaldehyde condenses with K-amidosulfonate under similar conditions to form the potassium salt of 1,3,5-triazacyclohexanesulfonic acid ( Urbanski ) which is used in the W-process, and that this can be nitrated to give cyclonite.


At any rate, I have condensed glyoxal with K-amidosulfonate and obtained a white powder which is slightly watersoluble but non-hygroscopic. I have reacted this powder with 98.5 % nitric acid at elevated temps for 4 hrs and obtained a minute amount of white powder which completely insoluble in water.
When I have experimented some more I will provide a report of my findings. I have access to both H2SO4, Ac2O and P2O5 so I will test a number of different nitrating systems, but in the mean time it would be very helpful to know whether the intermediate is even the one we hope it is.

[Microtek]

I have been conducting some of the experiments which I outlined in the above post.
So far, I have been reacting "hexa(potassiumsulfonate)hexaazaisowurtzitane" ( hereafter referred to as HKIW ) with different nitrating systems. Note that I am aware that the condensation product may not even be HKIW but for the sake of brevity, I will make that assumption for now.

I also discovered that it is advantageous to perform the condensation reaction in as high a concentration of reactants as possible. This increases yield and makes practically all of the product precipitate within about 40 hours.
The method I used was as follows:
- Sulfamic acid ( 9.71 g/ 0.1 mol ) was slurried in 5 ml demineralized water.
- A soln of KOH ( 5.6 g / 0.1 mol ) in 6 ml H2O was added slowly with swirling and cooling. Additional KOH in water was added until soln was just alkaline.
- Just enough water to dissolve all solids at room temp was added, along with solid sulfamic acid to lower pH to 3-5.
- Glyoxal ( 40 % soln, 4.84 g/ 0.033 mol ) was added dropwise with stirring over the coourse of 60 minutes.
- After 3 hrs continued stirring, the solution started becoming opague. Over the next 40 hrs the soln was stirred frequently.
- Soln was filtered at room temp to give more than 6.2 g corresponding to a yield of 63 % from glyoxal ( assuming that the product is in fact HKIW ).


As I stated in the above post, I attempted to nitrate this HKIW with highly concentrated nitric acid at elevated temperatures ( 50-80 C ). However, NOx evolution increased as temp approached 80 C, and even though it wasn't a runaway ( the decomposition didn't cause an increase in temp and so wasn't self sustaining ) I didn't feel like raising the temp all the way up to 115 C as was my original plan.
Instead I drowned the mix in water and got a small amount of precipitate ( perhaps 0.1 g from 1 g HKIW and 2 ml HNO3, 98 % ). I found that the product was insoluble in water and ethanol ( didn't try acetone ), darkened and decomposed without melting and didn't burn properly but instead charred to a black residue.
So, this was definately not HNIW. I don't even think it was a partially nitrated product that could be subjected to further nitrolysis.

The second ( and so far most promising ) attempt was done as follows:

- 0.8 g HKIW was dissolved in a mix of 3 ml HNO3, 98% and 0.5 ml H2SO4, 96%. The mixed acids were cooled in an ice bath during slow addition with stirring.
- Temp was allowed to rise to 20C with stirring over the course of 2 hrs.
- Mix was stirred another 4 hrs at ambient temperature and then poured over crushed ice. A fairly large amount of fluffy white solid precipitated. This was washed and isolated.

The dried product burned much like RDX, with a hissing orange flame. It explodes when struck quite firmly with a hammer ( about as difficult to set off as RDX ). On heating, it eventually melts with decomposition. It is somewhat soluble in acetone.
Unfortunately, there wasn't enough for a regular detonation test, but the qualitative tests that I did perfom seem to indicate that the product is in fact an energetic material. What the structure might be I don't know, nor which degree of nitration I have achieved, but I do think that the results so far are quite interesting.


I also tried a Ac2O/HNO3 system and right now I am conducting an experiment with HNO3/P2O5, but neither seem as good as the HNO3/H2SO4 procedure described above.

[VasiaPupkin]

Uhhh! Its looks like promising. You can try to identify HNIW by acetone solubility.
At room temperature its approx. 75g/100ml acetone.

[simply RED]

Molecule mass measuring test will be very good as it will show if polymers or other impurities are presented.

[simply RED]

Have you achieved some interesting resaults from the research.
What happened with the caged structure IR?

[nbk2000]

I've recently seen sulfamic acid powder at Lowe's as a tile cleaner for about $4/pound, and it's called 'DryLok' etching powder, and is 100% sulfmaic acid, according to the MSDS. :)

[akinrog]

Recently I was searching the net regarding CL-20 related stuff and have learnt that HNIW (aka CL-20) was also used for making low signature propellants.

Please check patents : 6863751 Low Signature Propellant and 6790299 ditto.

[akinrog]

Recently I was searching the net regarding CL-20 related stuff and have learnt that HNIW (aka CL-20) was also used for making low signature propellants.

Please check patents : 6863751 Low Signature Propellant and 6790299 ditto.

[akinrog]

Recently I was searching the net regarding CL-20 related stuff and have learnt that HNIW (aka CL-20) was also used for making low signature propellants.

Please check patents : 6863751 Low Signature Propellant and 6790299 ditto.

[cutefix]

Recently I was searching the net regarding CL-20 related stuff and have learnt that HNIW (aka CL-20) was also used for making low signature propellants.

Please check patents : 6863751 Low Signature Propellant and 6790299 ditto.

Yes, but what makes the formulation really low signature is the presence of ammonium dinitramide which displaces the ammonium perchlorate the standard composite propellant oxidizer and the absence of particulate metals..
Having no chlorine molecule in such formulation makes it produce less visible smoke( mostly steam and carbon and nitrogen oxides); unlike the perchlorate based composites, which tend to promote the formation of distinct white smoke due to the formation of hydrogen chloride ammonium chloride during combustion.
that is exacerbated by the aluminum oxide particulate that contributes to the opaqueness of the combustion products.
So whatever the high explosive oxidizer used maybe RDX. or HMX in finely divided form and bonded with energetic polymer PGN,BTTN it does not affect the signature of such propellant.
There is one thing amiss with that patent why would the author say of low signature when the component of his formulation are more of a modified double base plastic bonded propellants with mostly energetic plasticizers and binders? :) which can be classified as smokeless powders.
Therefore with such composition all of it will come out as low signatures propellants: unlike the composite formulation used in the space shuttle boosters.

[cutefix]

Recently I was searching the net regarding CL-20 related stuff and have learnt that HNIW (aka CL-20) was also used for making low signature propellants.

Please check patents : 6863751 Low Signature Propellant and 6790299 ditto.

Yes, but what makes the formulation really low signature is the presence of ammonium dinitramide which displaces the ammonium perchlorate the standard composite propellant oxidizer and the absence of particulate metals..
Having no chlorine molecule in such formulation makes it produce less visible smoke( mostly steam and carbon and nitrogen oxides); unlike the perchlorate based composites, which tend to promote the formation of distinct white smoke due to the formation of hydrogen chloride ammonium chloride during combustion.
that is exacerbated by the aluminum oxide particulate that contributes to the opaqueness of the combustion products.
So whatever the high explosive oxidizer used maybe RDX. or HMX in finely divided form and bonded with energetic polymer PGN,BTTN it does not affect the signature of such propellant.
There is one thing amiss with that patent why would the author say of low signature when the component of his formulation are more of a modified double base plastic bonded propellants with mostly energetic plasticizers and binders? :) which can be classified as smokeless powders.
Therefore with such composition all of it will come out as low signatures propellants: unlike the composite formulation used in the space shuttle boosters.

[cutefix]

Recently I was searching the net regarding CL-20 related stuff and have learnt that HNIW (aka CL-20) was also used for making low signature propellants.

Please check patents : 6863751 Low Signature Propellant and 6790299 ditto.

Yes, but what makes the formulation really low signature is the presence of ammonium dinitramide which displaces the ammonium perchlorate the standard composite propellant oxidizer and the absence of particulate metals..
Having no chlorine molecule in such formulation makes it produce less visible smoke( mostly steam and carbon and nitrogen oxides); unlike the perchlorate based composites, which tend to promote the formation of distinct white smoke due to the formation of hydrogen chloride ammonium chloride during combustion.
that is exacerbated by the aluminum oxide particulate that contributes to the opaqueness of the combustion products.
So whatever the high explosive oxidizer used maybe RDX. or HMX in finely divided form and bonded with energetic polymer PGN,BTTN it does not affect the signature of such propellant.
There is one thing amiss with that patent why would the author say of low signature when the component of his formulation are more of a modified double base plastic bonded propellants with mostly energetic plasticizers and binders? :) which can be classified as smokeless powders.
Therefore with such composition all of it will come out as low signatures propellants: unlike the composite formulation used in the space shuttle boosters.

[hedm]

A week ago there was a ICT conference about energetic materials (Karlsruhe, Germany), so I found article about HNIW sulphamate technology:


http://darkman.pienista.net/P141.pdf

download and enjoy!
hedm

[franksun]

A week ago there was a ICT conference about energetic materials (Karlsruhe, Germany), so I found article about HNIW sulphamate technology:


http://darkman.pienista.net/P141.pdf

download and enjoy!
hedm

i am wondering that if the sulphamate technology was achieved why they not had Patent application.

[cutefix]

Patents takes time to be approved.
If you will look at the USPTO there are several examples of energetic materials patents that was patented many years after its invention.
Another thing also that delays the patent issuance, is that some new developments in the field of energetic materials are subject to classified information status....

[hereno]

And from the way it reads, they are yet to isolate the HNIW, rather they are reporting the reaction conditions from which the highest proportion of HNIW was achieved. Seems to always yield di/tetra/hexanitro products in various ratios. Pitty they didnt say what percentage was hexanitro.

[franksun]

is there anyone got hniw from the way it reads?

[franksun]

ha,there is nobody?
what are you busy now?

[Bert]

The thread most pertinent to your question is here...
http://www.roguesci.org/theforum/water-cooler/2774-newbies-forums-unwritten-rules-written-down.html#post39108
When you post a topic, do not reply to it 30 minutes later saying "U guyz suk cuz u havnt anzwured me!!!". This is NOT a chatroom, it is a bulletin board, which means that you post a message...people read it...and reply to it if they feel like it. Sometimes it's within minutes, sometimes days, and sometimes never. If no one replies to your post, there's two possible reasons:

1. You've so completely and exquisitly covered the subject in detail, that no one would dare defile such a masterpiece with their unworthy words, for fear of being as barbaric as pissing on the Mona Lisa.

2. You've so completely and exquisitly made clear that you know absolutely nothing about the subject, and are such a barbarian that you would piss on the Mona Lisa, that no one would dare to be seen associating with you by replying.

In all probabilty, the reason for no one replying to your post is because of it being #2. If you have any doubt, it's a #2, and there's no doubt about it.

Just because you posting something doesn't automatically mean that you are entitled to our time, which means a reply. Just as in the real world, people can and will ignore you, so you should already be used to it already.

[Cindor]

But Bert... you spent your time on franksun when you search this post and answer him with it :P;)

[Bert]

NBK 2000 will likely spend a few seconds on him as well.

[megalomania]

Actually he waited 3 months between the last post and his most recent. However, having phrased his question in a most asinine and simplistic way he has run afoul of my ire. Would you care to expound on your question in something better approximating the English language, franksun, or shall I stake you out in the hot sun for the beast to catch a whiff of your scent?

[franksun]

Oh,I am sorry!
maybe the way I spoke is WRONG.

[VasiaPupkin]

This story is in continue. :)
I have met one man from IPCET. He have opinion that sulphamate technology is not perspective.
All this years they could not to get a yeild more than 1% and therefore this route is not patented. And they are use classic HNIW technology.
I have tried many attempts to obtain a HNIW from sulfamates and it seems he is true. I varied temperatures, pH, dosage, acidic catalysts
(I even tried lantanide triflate catalyst) etc. The white precipitate is always formed. When I try to nitrate and isolate the
nitration product its disapear when water is added. But he also said that tetranitro-dioxa-azaaisowurtzitane derrivative ("Aurora" or "AA" codename) could be formed with acceptable yeild.
Its scaled-up and used for diamond synthesis. VoD=8680m/s at 1.96g/cm3. density 2.02g/cm3. Unfortunately I could not to obtain this stuff too.
Is anybody have any info about "Aurora's" sulfamate synthesis?

Also some of his friends have an private communications with French scientiests who patented 2-stage HNIW technology. They has an aim only to patent this route for future. In reallity this patent has no applications because the yeild is poor and purity of final product is low. Classic technology is more economical.

[SYNC12]

I think VasiaPupkin is right.
I have tried the sulphamate technology and got nothing,neither HNIW nor dioxo isowurtzitane.

[The_Duke]

When I try to nitrate and isolate the nitration product its disapear when water is added.

You can't put that final nail in the coffin until you can successfully isolate and identify the nitration product(s).

Perhaps the nitration product is soluble in water? Or if hydrolysis will not allow you to crash the reaction into water than you may want to at least try a few other tricks before giving up. Perhaps filtering out the mass of precipitated crystals through an acid resistant filter first, then washing with a solvent will allow you to recover some product…

[klasac]

The thing is during the nitration of condensation product of glyoxal with K-sulphamate a sheer solution forms and the product should precipitate form the reaction mixture upon quenching in ice/water mixture in sufficient amount so there is no local overheating=hydrolysis.
I have tried many experiments on this, read the article many times but it just wont work. Mostly you get mixture of polymers and dipotassium-2,3,5,6-tetrahydroxypiperazine-1,4-disulphonate. By nitrating it you will get either polymeric nitrated product or TEX in very low yield.
I tried many reactions with various conditions (pH, temperature, concentration,medium,reaction time,...). Obtaining the condensate is never a problem,,something always forms, but the nitration always yields minute amount of nitramine(?)