Sciencemadness Discussion Board - New Energetic Materials - Current Research

4,4,8,8-Tetranitroadamantane-2,6-diyl Dinitrate: A High-Density Energetic Material
Yifei Ling, Xiaoli Ren, Weipeng Lai and Jun Luo
European Journal of Organic Chemistry, 2015; An ASAP article first published online (22. Jan. 2015)
DOI: 10.1002/ejoc.201403449

Thanks Nicodem,

Just for those curious about it:
Quoted from the link:
Abstract:
The novel high-performance energetic material, 4,8,8-tetranitroadamantane-2,6-diyl dinitrate has been synthesized and fully characterized. The synthetic strategy features the construction of the adamantane skeleton with different functional groups at adjacent methylene carbon atoms to overcome the problems associated with the ortho effect and steric crowding, and is amenable to the synthesis of other polynitroadamantanes. The experimentally determined physical properties as well as the calculated detonation properties indicate that this compound exhibits high thermal stability (220 °C), high density (1.852 g /cm³), and excellent detonation velocities (8529 m /s) and pressures (33.43 GPa).

And for those who likes it with images:
4,4,8,8-Tetranitroadamantane-2,6-diyl Dinitrate

4488-Tetranitroadamantane-26-diyl-dinitrate.jpg - 14kB

I think the 2,2,4,4,6,6,8,8-octanitroadamantane would be also interesting and there are two methylene left free that would render possible the making of a tetranitroadamantane-tetrayl-tetranitrate or a dodecanitroadamantane with each methylene holding two nitro groups...

PHILOU Zrealone - 20-3-2015 at 12:03

Thanks Nicodem,

Just for those curious about it:
Quoted from the link:
Abstract:
The novel high-performance energetic material, 4,4,8,8-tetranitroadamantane-2,6-diyl dinitrate has been synthesized and fully characterized. The synthetic strategy features the construction of the adamantane skeleton with different functional groups at adjacent methylene carbon atoms to overcome the problems associated with the ortho effect and steric crowding, and is amenable to the synthesis of other polynitroadamantanes. The experimentally determined physical properties as well as the calculated detonation properties indicate that this compound exhibits high thermal stability (220 °C), high density (1.852 g /cm³), and excellent detonation velocities (8529 m /s) and pressures (33.43 GPa).

And for those who likes it with images:
4,4,8,8-Tetranitroadamantane-2,6-diyl Dinitrate

I think the 2,2,4,4,6,6,8,8-octanitroadamantane would be also interesting and there are two methylene left free that would render possible the making of a tetranitroadamantane-tetrayl-tetranitrate or a dodecanitroadamantane with each methylene holding two nitro groups...

Article is to be found here
4488-tetranitroadamantane-26-diyl dinitrate
Thanks to Mayko via request in References/ Wanted References

[Edited on 20-3-2015 by PHILOU Zrealone]

Nicodem - 2-4-2015 at 11:20

A few early view Angewangte articles:

Sulfates-Based Nanothermites: An Expanding Horizon for Metastable Interstitial Composites
Comet, M., Vidick, G., Schnell, F., Suma, Y., Baps, B. and Spitzer, D.
Angew. Chem. Int. Ed., (2015) 54: 4458–4462.
doi: 10.1002/anie.201410634

The Many Faces of FOX-7: A Precursor to High-Performance Energetic Materials
Gao, H. and Shreeve, J. M.
Angew. Chem. Int. Ed. (2015).
doi: 10.1002/anie.201501973

Energetic Materials with Promising Properties: Synthesis and Characterization of 4,4′-Bis(5-nitro-1,2,3-2H-triazole) Derivatives
He, C. and Shreeve, J. M.
Angew. Chem. Int. Ed. (2015).
doi: 10.1002/anie.201412303

Bert - 3-4-2015 at 09:47

Thanks Nicodem!

The abstract on sulfate based nano thermite article mentions burn rates in a range, high end is given at 2,500 meters/second?! That's faster than several ammonium nitrate based high explosives in common use- Whee! And water of crystalization is considered a FEATURE by author, not a bug?

Time to re-consider sulfate oxidizers, The WiZ may not have covered all possibilities...

What's possible to achieve as an amateur using OTC materials for a reasonably low cost, easily cast/worked DENSE refractory material. I have a little modification of the pyronol torch/linear thermite steel cutting charge family of devices in mind.

(edit)
How to convince micro scale particles of Aluminum to behave like nano scale?
http://www.dtic.mil/get-tr-doc/pdf?AD=ADA534332

[Edited on 3-4-2015 by Bert]

Dornier 335A - 3-4-2015 at 11:12

Bert, the 2500 m/s nano thermite mentioned in Sulfates-Based Nanothermites is probably a CuO/Al mix:

Quote:

While in the literature CuO/Al thermites have not been prepared by reactive
milling or sol-gel methods, unique to CuO/Al thermite is a new synthesis
methodology by Shubhra Gangopadhyay called self-assembly [17]. In this
method, the authors coated copper nanorods (20x100 nm) with a coordinating
polymer (P4VP) followed by coating the coated rods with 80 nm aluminum
powder. The result of this self-assembly process is the thermite with the highest
combustion velocity known of 2400 m/s.

Nanoscale Aluminum - Metal Oxide (Thermite) Reactions for Application in Energetic Materials
Piercey, D. G. and Klapötke, T. M.
http://www.wydawnictwa.ipo.waw.pl/cejem/2-2010/full/klapotke...

The water of crystalization was a problem when I made CuSO₄/Mg flash powder. The hydrated mixture surely burns, but the anhydrous mixture explodes with immense violence when heated. The water lowers the ignition point and increases energy content of the mixture though, so why not. If it wasn't for the slow oxidation of magnesium in water, this mixture could have some use:
https://youtu.be/ix-OTDv0i8s?t=1m8s

Mr.Greeenix - 10-4-2015 at 09:25

hi community

somebody mentioned the Energetic Nitrate Ester : / 2,3-Bis-hydroxymethyl-2,3-dinitro-1,4-butanediol tetranitrate / the synthesis isn't that difficult if you have / 2,2-Dimethyl-5-nitro-1,3-dioxan-5-yl)methanol / needed for the first synthesis.

I found a chinese PDF about this explosiv Attachment: phpJ8WtHo (540kB)
This file has been downloaded 2285 times
started from Nitromethan

Maybe someone is able to write a synthesis???

Star from 2,2-Dimethyl-5-nitro-1,3-dioxan-5-yl)methanol
Attachment: Synthesis of an Energetic Nitrate Ester.pdf (2.5MB)
This file has been downloaded 1057 times

[Edited on 10-4-2015 by Mr.Greeenix]

Microtek - 10-4-2015 at 12:47

Synthesis of 2,2-Dimethyl-5-nitro-1,3-dioxan-5-yl)methanol is very easy if you have nitromethane and 2,2-dimethoxypropane (the dimethyl acetal of acetone) along with some (para)formaldehyde and a few common reagents. There are patents for making the 2,2-dimethoxypropane from acetone and the alcohol, but I never got it to work beyond trace amounts (enough to smell, but nothing more).

PHILOU Zrealone - 10-4-2015 at 14:25

The synthesis is even easier from 1.2-dinitroethane and formaldehyde...
O2N-CH2-CH2-NO2 + 4 CH2=O -base-> (HOCH2)2C(NO2)-C(NO2)(CH2OH)2

Based on the same principle as nitroisobutyl-triol from nitromethane and formaldehyde...
CH3-NO2 + 3 CH2=O -base-> (HOCH2)3C-NO2

Microtek - 10-4-2015 at 22:59

But then, where to get the DNE? I haven't seen this for sale anywhere, and IIRC it is unstable in storage. I haven't come across a reasonable synthesis either.

PHILOU Zrealone - 11-4-2015 at 05:08

from ethylene dibromide:
Br-CH2-CH2-Br + AgNO2 --> O2N-CH2-CH2-NO2 (36%) + ONO-CH2-CH2-ONO (16%) + ONO-CH2-CH2-NO2 (48%)

from tartric acid fumaric acid or maleic acid:
HO2C-CHOH-CHOH-CO2H -halogenation-> HO2C-CHX-CHX-CO2H
HO2C-CH=CH-CO2H (cis or trans) + X2 -->HO2C-CHX-CHX-CO2H
HO2C-CHX-CHX-CO2H + NaNO2 + urea -DMF-or-DMSO->HO2C-CH(NO2)-CH(NO2)-CO2H + HO2C-CH(ONO)-CH(NO2)-CO2H + HO2C-CH(ONO)-CH(ONO)-CO2H

alfa nitro carboxylic acid performs spontaneous decarboxylation...
HO2C-CH(NO2)-CH(NO2)-CO2H --> O2N-CH2-CH2-NO2 + 2 CO2(g)
HO2C-CH(ONO)-CH(NO2)-CO2H --> O2N-CH2-CH(ONO)-CO2H + CO2(g)

in mild acidic media, only the dinitro compound will be unsoluble

Urea increases solubility of nitrite and avoid side nitrosation reaction of the nitrocompound otherwise you would get aswel nitrolic acids...
R-CH2-NO2 + R'-ONO --> R-CH(-N=O)(NO2) + R'OH
R-CH(-N=O)(NO2) <--==> R-C(NO2)(=N-OH)

[Edited on 11-4-2015 by PHILOU Zrealone]

Microtek - 11-4-2015 at 13:24

With those extra steps, I think that the litterature path is about as good, but it would certainly be an interesting experiment.

PHILOU Zrealone - 12-4-2015 at 13:08

There is also an electrolytic dimerization of secondary nitrocompounds ammonium salts... :cool:

2 (R)2C(NO2)NH4 -electrolysis-> (R)2C(NO2)-C(NO2)(R)2

Based on that principle:
CH3-NO2 + 2 CH2=O --> (HOCH2)CH-NO2
(HOCH2)CH-NO2 + NH3 --> (HOCH2)C=N(O)-ONH4
2 (HOCH2)C=N(O)-ONH4 -electrolysis-> (HOCH2)C(NO2)-C(NO2)(CH2OH)2

Maybe the alcool function has to be protected first against electro-oxydation by acetylation...the resulting dinitro-tetraacetyl ester would then be unsoluble while the ammonium salt would be soluble, yielding and easier isolation.

[Edited on 12-4-2015 by PHILOU Zrealone]

Mr.Greeenix - 22-4-2015 at 05:14

I put the detailed syn. of / 2,2-Dimethyl-5-nitro-1,3-dioxan-5-yl)methanol / from the chines paper in a translater.
That's my result.
(sorry for the realllly bad English) Maybe someone can translate it into good English

methyl nitro-methane (TN):
In the bottom flask fitted to 37% of the formaldehyde in water (327.5 G, 4
mol), and water bath heated to 50 degrees C, add the appropriate amount baking soda to adjust
pH 8.0 sites, increase the temperature to 55 degrees C, drop the nitro-methane (76.9 G, 1.25
mol), and maintain pH sites 8.5, the contribution that the agitation response 40 min to drop to a 10%
of the sulfuric acid adjustment response fluid pH sites 5, heating the reaction fluid temperature up to
80 degrees C, reducing enrichment, cooling, and by a large white needle-like crystals, the
Filter, vacuum drying, and in 3 of methyl nitro-methane 160.8 G / yield 85.2%. / m.p. 152~153 Celsius / C4H9NO5

2,2-Dimethyl-5-nitro-1,3-dioxan-5-yl)methanol:
Adds three methylol nitromethane in the round flask (120.8 g, 0.8 mol), acetone (176.4 mL), stirring,
heating in water bath to 60 degrees Celsius. After three hydroxy A base nitromethane dissolve
completely, ices the water bath to make the solution cool to 10 degrees Celsius by below, the
separation massive acicular crystals. Adds by drops the boron trifluoride etherate solution
(189.8 g, 0.84 mol), Canada finishes, responded 5 min the heating in water bath to
50~55 degrees Celsius, will respond that the fluid poured into the sodium hydrogencarbonate in the
ice water saturated solution, stirring, regulator solution pH close neutrality, pulled out filters
the white solid, the ice water washed 2 times, after the vacuum drying,
2,2- dimethyl - 5- methylol - 5- nitro groups - 1,3- two oxygen mixed hexamethylene 133.1 g,
yield 87.1%. m.p. 130~131 degrees Celsius; C7H13NO5

The only problem is "Boron trifluoride diethyl etherate" but I think some are able to buy it.

Microtek - 22-4-2015 at 12:54

If you use 2,2-dimethoxypropane instead of acetone as I mentioned above, there is no need for BF3. Of course, 2,2-DMP isn't exactly OTC either...

Anyway, the article can be had in english and is also discussed elsewhere on this site, so you don't have to go through a machine translation.

Edit: Now I'm confused: You posted the article in english yourself just a few posts back, so what is it you are asking?

[Edited on 22-4-2015 by Microtek]

Mr.Greeenix - 23-4-2015 at 03:29

I posted 2 articels.

1 is in English and starts from 2,2-Dimethyl-5-nitro-1,3-dioxan-5-yl)methanol
and the 2 one is the chinese paper were one synthesis route ist improved from 85->95% and it starts from Nitromethan.

Microtek - 23-4-2015 at 08:11

Oh, OK. Tris-nitro (tris(hydroxymethyl)nitromethane) is easy to make in high yield. It is used as a biocide, and there are lots of patents on its preparation.

The second step, I found to be not so easy. In the end I just ordered the 2,2-DMP through Sigma-Aldrich after having tried (unsuccesfully) to synthesize it myself. There are patents about that part also, but in my experience they didn't work as advertized.

Mr.Greeenix - 25-4-2015 at 13:33

It was mentioned before but here is the pdf of Tetranitro-propane diurea and
an other very insensitiv compound
Attachment: TNPDU.pdf (110kB)
This file has been downloaded 1246 times

[Edited on 25-4-2015 by Mr.Greeenix]

Mr.Greeenix - 20-5-2015 at 07:08

Hydrazinium 5-Aminotetrazolate

* incredible high value (9516 m/s) was obtained for the detonation velocity
* it is incredibly insensitiv
* easy preparation

Attachment: Hydrazinium 5-Aminotetrazolate.pdf (498kB)
This file has been downloaded 1035 times

What do you think?

[Edited on 20-5-2015 by Mr.Greeenix]

Dornier 335A - 20-5-2015 at 12:41

Azole-Based Energetic Salts reports a more reasonable 8786 m/s at 1.54 g/cc.
I don't think it should be compared with RDX in terms of brisance though, because the detonation pressure is much lower at 248 kbar. Still very impressive for something so simple.

Mr.Greeenix - 24-8-2015 at 07:11

I recently found an alternativ and very easy synthetic route of / 2,2-dimethyl-5-hydroxymethyl-5-nitro-1 ,3-dioxane /
which is one precursor of the super explosiv BHDBT

It was dicussed one site before.

//

The way to obtain 2,2-dimethyl-5-hydroxymethyl-5-nitro-1,3-dioxane is illustrated by the following example.

To a mixture of 15.1 g (0.1 mol) of Tris-(hydroxymethyl)nitromethane and 50 ml of (0.68 mol) of acetone
with stirring and a temperature of 10°C sprinkled 5 g of phosphorus pentoxide. Stirred the reaction mass for
10 minutes, then poured into 100 ml saturated potassium carbonate solution with ice. Stir to dissolve the ice,
then the product is filtered, washed with cold water and dried in air. Gain of 11.5 g (71%) of
2,2-dimethyl-5-hydroxymethyl-5-nitro-1,3-dioxane with TPL 133-134°C.

http://russianpatents.com/patent/252/2529498.html

[Edited on 24-8-2015 by Mr.Greeenix]

PHILOU Zrealone - 24-8-2015 at 09:14

I recently found an alternativ and very easy synthetic route of / 2,2-dimethyl-5-hydroxymethyl-5-nitro-1 ,3-dioxane /
which is one precursor of the super explosiv BHDBT

It was dicussed one site before.

//

The way to obtain 2,2-dimethyl-5-hydroxymethyl-5-nitro-1,3-dioxane is illustrated by the following example.

To a mixture of 15.1 g (0.1 mol) of Tris-(hydroxymethyl)nitromethane and 50 ml of (0.68 mol) of acetone
with stirring and a temperature of 10°C sprinkled 5 g of phosphorus pentoxide. Stirred the reaction mass for
10 minutes, then poured into 100 ml saturated potassium carbonate solution with ice. Stir to dissolve the ice,
then the product is filtered, washed with cold water and dried in air. Gain of 11.5 g (71%) of
2,2-dimethyl-5-hydroxymethyl-5-nitro-1,3-dioxane with TPL 133-134°C.

http://russianpatents.com/patent/252/2529498.html

[Edited on 24-8-2015 by Mr.Greeenix]

Very nice finding!

(CH3)2C(OCH2)2C(NO2)-CH2OH could also be halogenated to (CH3)2C(OCH2)2C(NO2)-CH2I;
then allowed to react with AgC(NO2)3 to yield (CH3)2C(OCH2)2C(NO2)-CH2-C(NO2)3;
then deprotected to yield (HOCH2)2C(NO2)-CH2-C(NO2)3 and finally nitrated to (O2NOCH2)2C(NO2)-CH2-C(NO2)3 (2-methylol-2,4,4,4-tetranitro-butanol dinitrate = C5H6N6O14)

An energetic material with slightly positive OB:
C5H6N6O14 --> 5 CO2 + 3 H2O + 3 N2 + 1/2 O2

Mr.Greeenix - 22-9-2015 at 06:29

I found that:

Attachment: Azole-Based Energetic Salts, Chemical Reviews.pdf (1.6MB)
This file has been downloaded 791 times

10b-2 : -> the ammonium salt of 5,5'-Bis(1H-tetrazolyl)amine
D (m/s): 9926m/s
P (GPa): 34.9

Has anybody an paper how to synthesis 5,5'-Bis(1H-tetrazolyl)amine ?=? 5-azido-1H-tetrazole??

/
/

Also I want to ask if someone can post this paper or just a synthesis of 5-Azido-1H-tetrazole (from 5-AT):

5-Azido-1H-tetrazole – Improved Synthesis, Crystal Structure and Sensitivity Data
http://onlinelibrary.wiley.com/doi/10.1002/zaac.200800003/ab...

Because the hydrazinium salt is quite interesting. Vod >9000
Attachment: ADA504339.pdf (138kB)
This file has been downloaded 598 times

/
/

I can't find this paper in somewhere here so I will just post it

It is easy to synthes
Attachment: Diaminouronium 5-nitriminotetrazolate.pdf (3.2MB)
This file has been downloaded 1132 times

halogen - 23-9-2015 at 06:36

http://en.cnki.com.cn/Article_en/CJFDTOTAL-BGXB200001006.htm
LU Ming jiu (Xi′an Modern chemistry Research Institute, Xi′an 710065,China)
The synthetic, structure, properties, and some applications of a new explosive 2,4,6,8,10,12 hexanitro 2,4,6,8,10,12 haxaaza tricyclo〔7.3.0.0 3.7 〕dodecane 5,11 dione(HHTDD) are described. The crystal density and detonation velocity of HHTDD were determined as 2.07 g/cm 3 and 9546 m/s.(ρ=1.995 g/cm 3) respectively. It is the first explosive with so high detonation velocity reported in references up to now.

Mr.Greeenix - 26-9-2015 at 10:05

In my previous post I described the hydrazinium salt of 5,5'-Bis(1H-tetrazolyl)amine (not the ammonium salt. A fault in the document)
Synthetic route to 5,5'-Bis(1H-tetrazolyl)amine is decribed here:

Quote:

Synthesis of H2BTA•H2O (C2H3N9•H2O), (1)
As described in the literature[4], (Fig. 1) 4.45 g sodium dicyanamide (50 mmol) and 6.50 g sodium azide (100 mmol) were dissolved in 40 mL ethanol and 25 mL water, and then 75 mL of 2 M HCl was added dropwise over 4 h with stirring. The resulting mixture was refluxed for further 48 h. After cooling to room temperature, 10 mL of 12 M concentrated HCl was added and then 60 white precipitates were filtered. The crude white solids were dissolved in hot water, and then cooled to give white crystals 1.
IR (KBr): ν = 3455(s), 3030(s), 2932(s), 2857(s), 1651(vs), 1611(s), 1555(s), 1456(m), 1353(m), 1261(m), 1152(w), 1108(m), 1072(s), 1043(m), 1003(m), 903(m,br), 820(m), 740(m), 688(m), 509(m,br), 405(m) cm–1.

This is then allowed to react with hydrazine to yield the compound with vod of over 9900m/s
Attachment: 201310-123.pdf (336kB)
This file has been downloaded 868 times

Is there an other route to 5,5'-Bis(1H-tetrazolyl)amine? Pretty difficult

How to get sodium dicyanamide?
BTW does someone know how to syn. 5-Azido-1H-tetrazole? Maybe start from 5-Aminotetrazole?

The_Davster - 26-9-2015 at 12:11

BTW does someone know how to syn. 5-Azido-1H-tetrazole? Maybe start from 5-Aminotetrazole?

Cyanogen bromide and NaN3 is the easiest.

PHILOU Zrealone - 27-9-2015 at 10:52

Quote: Originally posted by The_Davster

BTW does someone know how to syn. 5-Azido-1H-tetrazole? Maybe start from 5-Aminotetrazole?

Cyanogen bromide and NaN3 is the easiest.

Or hydrazino tetrazole and HNO2...
HN4C-NH-NH2 + HONO --> HN4C-N3 + 2 H2O

PHILOU Zrealone - 27-9-2015 at 10:58

In my previous post I described the hydrazinium salt of 5,5'-Bis(1H-tetrazolyl)amine (not the ammonium salt. A fault in the document)
Synthetic route to 5,5'-Bis(1H-tetrazolyl)amine is decribed here:

Quote:

This is then allowed to react with hydrazine to yield the compound with vod of over 9900m/s

Is there an other route to 5,5'-Bis(1H-tetrazolyl)amine? Pretty difficult

How to get sodium dicyanamide?
BTW does someone know how to syn. 5-Azido-1H-tetrazole? Maybe start from 5-Aminotetrazole?

This must be interesting to you...by Boffis in preparation folder:
Bis-(5-tetrazolyl)-amine

Mr.Greeenix - 30-9-2015 at 12:48

I found that.
Some very energetic salts based on 5-hydrazino-1H-tetrazole (5-Hydrazinotetrazole) (HTZ)

High energetic compounds with easy synthetic route. The only drawback is that you have to use the silver salt. I guess otherwise you will have some impurities. The only common is silver nitrate

Attachment: Nitrogen-rich salts based on 5-hydrazino-1H-tetrazole.pdf (736kB)
This file has been downloaded 1010 times

Glycolite

Laboratory of Liptakov - 7-11-2015 at 12:45

It was tested a little-known plastic explosive. The working title is Glycolite. It shows very good results. It contains 12% water, NaClO4 and diethyleneglycol. This is the basic composition. Sensitizing are: aluminum and microballoons 1-3%. VoD is estimated to be 5,000 m / s or more. According to the charge diameter and length of course. Details on Channel Laboratory of Liptakov........ :cool:

PHILOU Zrealone - 8-11-2015 at 12:34

Quote: Originally posted by Laboratory of Liptakov

It was tested a little-known plastic explosive. The working title is Glycolite. It shows very good results. It contains 12% water, NaClO4 and diethyleneglycol. This is the basic composition. Sensitizing are: aluminum and microballoons 1-3%. VoD is estimated to be 5,000 m / s or more. According to the charge diameter and length of course. Details on Channel Laboratory of Liptakov........ :cool:

Very nice!

Glycerol could be used aswel with slight variation of the % for OB --> glycerolite

This would be more viscous, denser and so VOD will be slighly better.
One may even think to a syrupy mix of erythritol and glycerol for even better density.
Or suggar syrup (corn syrup).

The use of NH4ClO4, HONH3ClO4 or N2H5ClO4 in the formulation will boost things up even more.

I wonder if NaClO3 what is more soluble and sensitive could be used instead of NaClO4...?
In principle nothing is against its use (no NH4, nor acid nor sulfur) in the original formulation.

[Edited on 8-11-2015 by PHILOU Zrealone]

Glycolite

Laboratory of Liptakov - 9-11-2015 at 13:25

Huuh...NaClO3? It is interesting idea. Easy prepare from bleach. I hope, that NaClO3/DEG somebody will trying.
Liptakov
Hello! is there somebody for trying?

Detonationology - 9-11-2015 at 13:37

Despite having a lower oxygen balance than perchlorates, chlorates tend to be much more unstable and sensitive to heat, friction, and shock. From my experience, chlorates should be avoided due to the susceptibility for an accidental detonation, degradation and sensitivity over time.

[Edited on 11-9-2015 by Detonationology]

Nicodem - 16-11-2015 at 10:12

Potassium 4,5-Bis(dinitromethyl)furoxanate: A Green Primary Explosive with a Positive Oxygen Balance
Chunlin He and Jean'ne M. Shreeve
Angew. Chem. Int. Ed. 2015, 54, early view
DOI: 10.1002/anie.201509209

Tetranitratoethane
Joerg Stierstorfer, Thomas M Klapoetke and Dennis Fischer
Chem. Commun., 2015, Accepted Manuscript
DOI: 10.1039/C5CC09010E

PHILOU Zrealone - 19-11-2015 at 10:51

Potassium 4,5-Bis(dinitromethyl)furoxanate: A Green Primary Explosive with a Positive Oxygen Balance
Chunlin He and Jean'ne M. Shreeve
Angew. Chem. Int. Ed. 2015, 54, early view
DOI: 10.1002/anie.201509209

Tetranitratoethane
Joerg Stierstorfer, Thomas M Klapoetke and Dennis Fischer
Chem. Commun., 2015, Accepted Manuscript
DOI: 10.1039/C5CC09010E

Nicodem,
I like that!
I have requested those two articles in the reference section

[Edited on 19-11-2015 by PHILOU Zrealone]

PHILOU Zrealone - 21-11-2015 at 12:17

Nicodem,
I like that!
I have requested those two articles in the reference section

Both articles are now available (a little after my request thanks to Solo in the reference section under pdf format (see link hereabove).

And hereunder are some infos from Franklyn on tetranitratoethane related methylene dinitrate or dinitratomethane (CH2(ONO2)2 geminal dinitrate ester of dihydroxymethylene (formaldehyde hydrate aka CH2(OH)2 <=> CH2=O + H2O).
Methylene dinitrate

This is a new interesting family of compounds (H-(C(ONO2)2)n-H) that shows maybe promising HE properties, but they are easily hydrolysable although the tendency seems to be reduced by increasing n.
Only two compounds of that familly are known up to now...
H-(C(ONO2)2)1-H = CH2(ONO2)2
H-(C(ONO2)2)2-H = (O2NO)2CH-CH(ONO2)2

When n increases so do:
-density
-Oxygen Balance (already positive!)
-VOD
-stability towards heat and hydrolysis

So maybe...
n=3
H-(C(ONO2)2)3-H = (O2NO)2CH-C(ONO2)2-CH(ONO2)2
hexanitratopropane

n=4
H-(C(ONO2)2)4-H = (O2NO)2CH-(C(ONO2)2-)2-CH(ONO2)2
octanitratobutane

n>4

...would prove to be even better on all those detonic and physico chemical aspects

MANGANIT

Laboratory of Liptakov - 19-2-2016 at 14:42

It was tested a new energetic material ( mixture) on KMnO4 based. No hygroscopic, cheap and easy get of oxidizer. But fuels are expensive and difficult find for somebody. Basic mix is KMnO4 55, commerce nitrocellulose 12,5 to 17,5, shotgun double powder 12,5 - 17,5, aluminium Bright type 10-20 by parts of weight. Estimate VoD 2000 m/s by 1,25 g/cm3. At 10g charge from detonator No.8. Working name Manganit on Liptakov channel.... :cool:

...LL

ecos - 19-2-2016 at 15:30

Quote: Originally posted by Laboratory of Liptakov

It was tested a new energetic material ( mixture) on KMnO4 based. No hygroscopic, cheap and easy get of oxidizer. But fuels are expensive and difficult find for somebody. Basic mix is KMnO4 55, commerce nitrocellulose 12,5 to 17,5, shotgun double powder 12,5 - 17,5, aluminium Bright type 10-20 by parts of weight. Estimate VoD 2000 m/s by 1,25 g/cm3. At 10g charge from detonator No.8. Working name Manganit on Liptakov channel.... :cool:

...LL

the VoD is very low !! what is the benefit of that ?

PHILOU Zrealone - 19-2-2016 at 15:52

Quote: Originally posted by Laboratory of Liptakov

...LL

Beware for friction sensitivity...
KMnO4 is hell a catalyst for sensitization...
Strange that you only reach 1,25g/cm3 with 55% KMnO4 at d= 2.7g/cm³ and 10-20% Aluminium also d=2.7g/cm³?
Maybe a lot of air trapped inside.

Beware for sternutative effect of ultrafine KMnO4 dust and also everything arround turning purple upon contact with moisture and finally brown from oxydation into MnO2 spots very hard to get rid of!

@LL,
I like the comparative test flashpowder vs Manganex

[Edited on 20-2-2016 by PHILOU Zrealone]

nitro-genes - 19-2-2016 at 16:41

Nice comparison Liptakov,

The patent below was posted many years back by quicksilver, might also be interesting to look at, especially considering the OTCness of terephtalic acid.

The perchlorate version needs a lot of confinement to "detonate" from fuse only, but they are nearly insensitive to normal stimuli. Don't think other oxidizers were included, maybe KMNO4 may be a nice tradeoff between fuse sensitivity and confinement requirements.

Pyrotechnic burster composition
US 6521064 B1

Manganex / Manganit

Laboratory of Liptakov - 20-2-2016 at 00:32

This mixture has not an especially advantage. Only one. When you have a not another or better oxidizer, but have every all other compounds. This mix working much better with NH4ClO4 and working good with KClO4, NH4NO3, best with TeACN and TeACP. But it is another energetic material, another question, and nothing a new. Next thing, VoD is low. Well. But it is potassium permanganate. Is miracle, that sample was be detonated. And no only deflagration, similarly as flash powder.
... :cool:

...LL Thanks for everybody of your feedback. https://www.youtube.com/watch?v=4lTIAhJLjmo

[Edited on 20-2-2016 by Laboratory of Liptakov]

octonitrocubane - 25-3-2016 at 10:39

My proffesor has synthesised hexamine where the nitro bonds are replaced with 'niflo' bonds. I have no idea how he did it. It seems unbelievably sensitive - apparentely, it exploded in a shockproof container in a climate controlled atmosphere. He tamed one kilo of it, and ignited it with 0,5 grams ETN. It vapourised the metal at the centre and shredded the metal at the edges. Detonation velocity is around 9-10000 metres/second. If I can find how to synthesise it, I will tell you.

PHILOU Zrealone - 25-3-2016 at 11:56

Quote: Originally posted by octonitrocubane

My proffesor has synthesised hexamine where the nitro bonds are replaced with 'niflo' bonds. I have no idea how he did it. It seems unbelievably sensitive - apparentely, it exploded in a shockproof container in a climate controlled atmosphere. He tamed one kilo of it, and ignited it with 0,5 grams ETN. It vapourised the metal at the centre and shredded the metal at the edges. Detonation velocity is around 9-10000 metres/second. If I can find how to synthesise it, I will tell you.

Can you make a chemical drawing of the putative nitro-hexamine and niflo-hexamine? Maybe ask you teacher.

I'm sceptical about the veracity of the story...maybe your teacher told you a beautiful story...

1°) 1 kg of an explosive in a shockproof container is way too much for testing.

2°) synthetising 1 kg of an unknown sensitive explosive material is also way too much.

aga - 25-3-2016 at 12:38

Lolololol

My teacher made and detonated a small atomic bomb in her jacket pocket yesterday.

No idea how how she managed to contain the half-megaton explosion using just Tweed and leather elbow patches ...

Maybe it was Harris Tweed.

hissingnoise - 25-3-2016 at 12:49

Quote:

Maybe it was Harris Tweed?

-

Laboratory of Liptakov - 25-3-2016 at 13:44

You, all experienced chemists, too bad your time for answered for Octonitrocubane. He writes nonsenses. Registered 17. 3. 2016, first and only post 25. 3. 2016.... :cool:

[Edited on 25-3-2016 by Laboratory of Liptakov]

DubaiAmateurRocketry - 18-5-2016 at 15:21

Dany's post from 2013 on nitrated-cyclodextrine, this contains all information you need
Link:
http://www.sciencemadness.org/talk/viewthread.php?tid=25823#...

2 years ago, I theorized on another forum of Cl-20 being caged into the cavity of cyclodextrine and its nitrated form. ( it is in another language, the original paper theorized it could reduce the impact sensitivity of certain compounds):
Link:
http://tieba.baidu.com/p/2993864161

and guess what, this thing actually got synthesized recently on a paper published on CEJEM

Direct link:
http://www.wydawnictwa.ipo.waw.pl/cejem/Vol-13-Number-1-2016...

MineMan - 18-5-2016 at 20:18

Interesting, does this look like a synthesis an amateur could follow??

From previous research my understanding was 1gram of CL-20 would be $10 to produce...

Does this paper show a more economic alternative...? I am hoping it is finally time for HMX to step aside!!

Microtek - 19-5-2016 at 02:38

On an amateur basis, CL-20 has proven to be very elusive. There are a few routes that seem like they could lead somewhere (condensation of 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine with 1,1,2,2-tetranitraminoethane, or some routes using sulfaminates), but despite how promising they look on paper, they haven't yet taken off.
I wrote my thesis on this topic (among others). It was inconclusive in the end.

IMO, ionic energetic materials are a much more promising way for the amateur to achieve performance in excess of what HMX can give.
I have been experimenting with some of the new materials (aminonitroguanidinium nitrate and the bis(triaminoguanidinium) salt of bis(dinitroethyl)nitramine, though I'm not quite done with the latter).
Aminonitroguanidinium nitrate is easy to synthesize and crystallizes in very well-defined crystals, however they change over time in the open, possibly due to loss of nitric acid (only a hypothesis based on the low basicity of aminonitroguanidine - I need to investigate a little more thoroughly).

[Edited on 19-5-2016 by Microtek]

Laboratory of Liptakov - 19-5-2016 at 04:14

I cant a find data about amino nitroguanidine. It is nitroguanidine? Easy prepare you says? Hmm... And VoD? Thanks for answer...:-) Dr.

kratomiter - 19-5-2016 at 08:55

I'm also interested in the synthesis of aminonitroguanidine. I'm gonna try the synthesis of guanidine perchlorate and dinitroguanidine, but perhaps aminonitroguanidine nitrate is more interesting. Is a secondary, right?

DubaiAmateurRocketry - 19-5-2016 at 15:30

Quote: Originally posted by kratomiter

but perhaps aminonitroguanidine nitrate is more interesting. Is a secondary, right?

That compound is infact one of my favorite energetic material. Synthesized by Prof.Klapotke in 2012.

The synthesis is far less exotic than some of the other energetic materials. All you need is nitroguanidine, easily found, and hydrazine

The hydrazinolysis of nitroguanidine results in 1-amino-3-nitroguanidine, (ANQ)

ANQ nitrate has a density of 1.91, very high considering how many gas it produces, and a VoD of 9550 m/s ! Also very high. This compound also has a perfect OB. The sensitivity of ANQ nitrate is 10 J.

reference

Thomas M. Klapötke et.al, (2014) :1-Amino-3-nitroguanidine (ANQ) in High-performance Ionic Energetic Materials
Zeitschrift für Naturforschung B. Volume 67, Issue 6, Pages 573–588, ISSN (Online) 1865-7117, ISSN (Print) 0932-0776, DOI: 10.5560/znb.2012-0066

Direct link:
http://www.degruyter.com/view/j/znb.2012.67.issue-6/znb.2012...

Edit:
Corrected VoD from 9950 to 9550. Typo

[Edited on 20-5-2016 by DubaiAmateurRocketry]

PHILOU Zrealone - 19-5-2016 at 16:16

Theorically hydrazinolyse of nitroguanidine could lead to 2 compound depending on the amount of N2H4...
Just like guanidine may form aminoguanidine, diaminoguanidine and triaminoguanidine...
So here:
1°) (H2N-)2C=N-NO2 + H2N-NH2 --> H2N-NH-C(-NH2)=N-NO2 + NH3 (g)
Aminonitroguanidine (ANG)
2°) H2N-NH-C(-NH2)=N-NO2 + H2N-NH2 --> (H2N-NH-)2C=N-NO2 + NH3 (g)
Diaminonitroguanidine (DANG)

The later would be even more promising because it could be protonated twice
--> diaminonitroguanidine dinitrate, diperchlorate, dinitroformiate, bis-dinitramide
DANGDN
DANGDP
DANGDNF
DANGBDN

Also not to neglect the fact the initial compound (ANG) is basic...then it must be able to form transition metal complexes of oxoanions (nitroformiate, chlorate, nitrate, perchlorate, and maybe bromate, iodate, perbromate, periodate) with energetic properties.
Maybe copper is too oxydant but Zn, Cd, Co, Ni, ... might do...
-->for example Ni(II) nitrate --> Ni(NO3)2. 6 ANG (if ANG monodentate) , Ni(NO3)2 . 3 ANG (if ANG bidentate), Ni(NO3)2 . 2 ANG (if ANG tridentate).

Same of course would apply for DANG but here the dentition of the complexes might be more complex (without willing to make a bad word play

) --> polymeric complexes?

DubaiAmateurRocketry - 19-5-2016 at 16:46

Same of course would apply for DANG but here the dentition of the complexes might be more complex (without willing to make a bad word play

) --> polymeric complexes?

haha, I wish that was the case, but let me give you a sad news:

I am not sure why, but guanidine in abbreviation is denoted by Q

Microtek - 19-5-2016 at 21:46

The reason for the choice of acronym is probably that abbreviating nitroguanidine as NG would lead to confusion (with nitroglycerine), especially since both are used regularly in formulations of smokeless powder.

kratomiter - 20-5-2016 at 08:48

Wow, synthesis of DNQ seem pretty easy and straightforward for an amateur. I have some nitroguanidine waiting for hydrazinolysis right now :cool:

The yield is pretty low (45%), but its isolation is easy because it isn't water soluble. I'll try it this weekend.

PHILOU Zrealone - 20-5-2016 at 10:02

Same of course would apply for DANG but here the dentition of the complexes might be more complex (without willing to make a bad word play

) --> polymeric complexes?

haha, I wish that was the case, but let me give you a sad news:

I am not sure why, but guanidine in abbreviation is denoted by Q

A simple letter paradox is not a sad news...
ANQ or ANG; DANQ or DANG... Who really cares as long as we know what we are talking about...reason why I wrote the complete name aside (I try to do that (and it is a good reflex for every user of SMF I think) everytime I use accronyms)

PHILOU Zrealone - 20-5-2016 at 10:09

Quote: Originally posted by kratomiter

Wow, synthesis of DNQ seem pretty easy and straightforward for an amateur. I have some nitroguanidine waiting for hydrazinolysis right now :cool:

The yield is pretty low (45%), but its isolation is easy because it isn't water soluble. I'll try it this weekend.

By DNQ, because you wrote hydrazinolysis, did you meant ANQ (ANG aminonitroguanidine), DANQ (DANG diaminonitroguanidine) or really DNQ (dinitroguanidine)?

DNQ is (O2N-N=C(-NH2)-NH-NO2)
ANQ is (O2N-N=C(-NH2)-NH-NH2)
DANQ is (O2N-N=C(-NH-NH2)-NH-NH2)

PHILOU Zrealone - 20-5-2016 at 10:59

Theorically hydrazinolyse of nitroguanidine could lead to 2 compound depending on the amount of N2H4...
Just like guanidine may form aminoguanidine, diaminoguanidine and triaminoguanidine...
So here:
1°) (H2N-)2C=N-NO2 + H2N-NH2 --> H2N-NH-C(-NH2)=N-NO2 + NH3 (g)
Aminonitroguanidine (ANG)
2°) H2N-NH-C(-NH2)=N-NO2 + H2N-NH2 --> (H2N-NH-)2C=N-NO2 + NH3 (g)
Diaminonitroguanidine (DANG)

The later would be even more promising because it could be protonated twice
--> diaminonitroguanidine dinitrate, diperchlorate, dinitroformiate, bis-dinitramide
DANGDN
DANGDP
DANGDNF
DANGBDN

Also not to neglect the fact the initial compound (ANG) is basic...then it must be able to form transition metal complexes of oxoanions (nitroformiate, chlorate, nitrate, perchlorate, and maybe bromate, iodate, perbromate, periodate) with energetic properties.
Maybe copper is too oxydant but Zn, Cd, Co, Ni, ... might do...
-->for example Ni(II) nitrate --> Ni(NO3)2. 6 ANG (if ANG monodentate) , Ni(NO3)2 . 3 ANG (if ANG bidentate), Ni(NO3)2 . 2 ANG (if ANG tridentate).

Same of course would apply for DANG but here the dentition of the complexes might be more complex (without willing to make a bad word play

) --> polymeric complexes?

To add up more complexity

There are also other interesting compounds that may form:
3°) Because the amino group of ANG may react on another molecule of NQ
2 (H2N-)2C=N-NO2 + H2N-NH2 --> O2N-N=C(-NH2)-NH-NH-C(-NH2)=N-NO2 + 2 NH3 (g)
--> N3,N3'-bisnitroguanidine (or N1,N2-bis-nitroformamidin-hydrazine (BNFAH) or 2,5-bis-nitroimino-1,3,4,6-tetraaza-hexane (BNITAH))

The later may be oxydised to a diazo compound
O2N-N=C(-NH2)-NH-NH-C(-NH2)=N-NO2 -ox-> O2N-N=C(-NH2)-N=N-C(-NH2)=N-NO2 + H2O
-->N1,N2-bis-nitroformamidin-diazene (BNFADA) or 2,5-bis-nitroimino-1,3,4,6-tetraaza-hex-3-ene (BNITAHE)

4°) Because the amino group of DANG may react on another molecule of ANG or of DANG
H2N-NH-C(=N-NO2)-NH-NH2 + H2N-C(=N-NO2)-NH-NH2 --> H2N-NH-C(=N-NO2)-NH-NH-C(=N-NO2)-NH-NH2 + NH3 (g)
--> 3,6-bis-nitroimino-1,2,4,5,7,8-hexaaza-octane (BNIHAO)

The later may be oxydised to a diazo compound
H2N-NH-C(=N-NO2)-NH-NH-C(=N-NO2)-NH-NH2 -ox-> H2N-NH-C(=N-NO2)-N=N-C(=N-NO2)-NH-NH2 + H2O
---> 3,6-bis-nitroimino-1,2,4,5,7,8-hexaaza-oct-4-ene (BNIHAOE)

5°) ANG may also react with itself leading to a cyclic tetrazane
O2N-N=C(-NH2)-NH-NH2 + H2N-NH-C(-NH2)=N-NO2 --> O2N-N=C(-NH-NH-)2C=N-NO2 + 2 NH3(g)
--> 3,6-bis-nitroimino-1,2,4,5-tetraazacyclohexane (BNITACH)

The later by virtue of resonance (nitroimino - nitramino) and oxydability of the hydrazine moeities will probably turn into a cyclic tetrazine
O2N-N=C(-NH-NH-)2C=N-NO2 -ox-> O2N-NH-C(N4)C-NH-NO2 + H2O
--> 3,6-bis-nitramino-1,2,4,5-tetraazabenzene (BNITAB) or 3,6-bis-nitramino-1,2,4,5-tetrazine (BNITaz)
It may prove to be very unstable and easily hydrolysable because nitramine on highly electron withdrawing aromatic rings tends to split off NO2 as nitronium.
O2N-NH-C(N4)C-NH-NO2 + 2 H2O --> H2N-C(N4)C-NH2. 2 HNO3
--> diaminotetrazine dinitrate
(O2N-NH-C(N4)C-NH-NO2 --> (-)NH-C(N4)C-NH(-) + 2 NO2(+))
(2 H2O + 2 NO2(+) --> 2 H(+) + 2 HO-NO2)
((-)NH-C(N4)C-NH(-) + 2 H(+) --> H2N-C(N4)C-NH2)

The nitraminos will be very acidic and may form interesting salts but this should be done without water.

6°) There is also the possibility of chain formation in a polymeric fashion
(-C(=N-NO2)-NH-NH-)n and oxydation products like (-C(=N-NO2)-N=N-)n

All those compounds may, just like 1°) and 2°) should, allow for complexation with transition metal complexes of oxoanions (nitroformiate, chlorate, nitrate, perchlorate, and maybe bromate, iodate, perbromate, periodate) with energetic properties.

[Edited on 20-5-2016 by PHILOU Zrealone]

Microtek - 20-5-2016 at 11:16

Klapötke et al discuss the mechanisms involved in the formation of ANQ and some of the others that Philou speculate on. It seems that DANQ is too unstable to be isolated from this medium, since adding more hydrazine simply results in a reduced yield of ANQ.

I include the full paper here, so everyone can see for themselves:

Attachment: Aminonitroguanidine nitrate.pdf (3.9MB)
This file has been downloaded 782 times

PHILOU Zrealone - 21-5-2016 at 04:19

Quote: Originally posted by Microtek

Klapötke et al discuss the mechanisms involved in the formation of ANQ and some of the others that Philou speculate on. It seems that DANQ is too unstable to be isolated from this medium, since adding more hydrazine simply results in a reduced yield of ANQ.

I include the full paper here, so everyone can see for themselves:

Interesting paper. Thank you.
In the paper they explain that hydrazinolysis may go through 2 ways...
1) Substitution of the NH2
(H2N-)2C=N-NO2 + H2N-NH2 --> H2N-NH-C(-NH2)=N-NO2 + NH3(g)
This process of formation of ANG is not favourised because they only got 45% yield while 2 NH2 are available over 1 N-NO2...statistically one would then expect 66% yield.
2) Substitution of the =N-NO2
(H2N-)2C=N-NO2 + H2N-NH2 --> (H2N-)2C=N-NH2 + H2N-NO2
The later amino guanidine (AG) may react further to diamino guanidine (DAG) and triamino guanidine (TAG)

Part of the aminonitroguanidine in 1) may also react with excess hydrazine to DANG, DAG and TAG.

I suspect DANG would have more chance to be done in workable quantities if working from ANG and no exces N2H4!

[Edited on 21-5-2016 by PHILOU Zrealone]

Microtek - 21-5-2016 at 07:26

According to a paper by Castillo-Melendez and Golding, the yield of ANQ can be as high as 60% given the right reaction conditions (55 C, 15 minutes reaction time). The paper is from 2004, so it's older than the one I posted by Klapötke, et al. This could indicate that it is quite difficult to reach those numbers. I think this is supported by the fact that the yield peak is quite narrow.

Attachment: Amino-nitroguanidine prep 2004.pdf (428kB)
This file has been downloaded 720 times

glymes - 21-5-2016 at 08:08

Would 5-aminotetrazole be basic enough to form 5-aminotetrazole perchlorate? It'd either work and be a fantastic oxidiser or there wouldn't be a reaction.

PHILOU Zrealone - 21-5-2016 at 09:43

Would 5-aminotetrazole be basic enough to form 5-aminotetrazole perchlorate? It'd either work and be a fantastic oxidiser or there wouldn't be a reaction.

With a pKa of 6.0 it is a weak acid in the range of H2CO3... so with a pKa of -8 HClO4 is 10¹⁴ times more acidic.
--> 5-ATz will indeed form a perchlorate.

glymes - 21-5-2016 at 13:00

Oh right... That rather changes things up!

So would it be [(C-NH2)-N3-NH]ClO4? The OB looks good. Indeed, would it be able to form nitroformate salts? I feel an investigation coming on....

kratomiter - 21-5-2016 at 13:14

It was a mistake, I mean ANQ nitrate. I'll post results tomorrow if I get something interesting.

glymes - 21-5-2016 at 13:30

Right.

Perdifluoroaminohexamethyenetetramine. C6N16F24 --> 6CF4 + 8N2.

C6N4H12 + 12N-bromosuccinide --> C6N4Br12 + succinide

C6N4Br12 + 12HNF2 --> C6N16F24

Bromine is generally a good leaving group. For the sake, call it PDF HMTA, as I'd rather make it sound like a photocopier than a mouth orgy.

DubaiAmateurRocketry - 21-5-2016 at 14:20

Oh right... That rather changes things up!

So would it be [(C-NH2)-N3-NH]ClO4? The OB looks good. Indeed, would it be able to form nitroformate salts? I feel an investigation coming on....

It would be a decent oxidizer, however not good enough.

I personally do not like to introduce carbon atoms in the anion because they increase the overall average molecular weight of the exhaust in a propellant.

If you take a look at the ANQ-dinitramide-monohydrate, it is very stable, has a VoD of nearly 9200, produces more gas than ANQ-Nitrate.

However if you put a nitroformate in there, the gas produced, L/kg will be significantly lower.

Edit:

Anyone have any idea if the ANQ-Dinitramide-monohydrate could be turned into... maybe ANQ-Dinitramide-monohydroxylamide ?

[Edited on 21-5-2016 by DubaiAmateurRocketry]

glymes - 22-5-2016 at 01:23

Hold up.

Where on earth are you fitting the dinitramide groups, as ANQ is NO2-(C=NH)-NH2? Would it just be [NO2(C=NH2)-NH2]- 2[NO2-N-NO2]+ or something like that?

If that works, forming NO2CNHNH2(NO2-N-NO2]2 * H2O I see no reason why HO-NH2 should not be able to kick the H2O out and form NO2CNHNH2(NO2NNO2)2 * HONH2

More neatly:
CH3N3O2 + NH3N3O4 --> CH3N6O6 + NH3
CH3N6O6 + H3NO --> C3H6N7O7

PHILOU Zrealone - 22-5-2016 at 04:18

Oh right... That rather changes things up!

So would it be [(C-NH2)-N3-NH]ClO4? The OB looks good. Indeed, would it be able to form nitroformate salts? I feel an investigation coming on....

Octonitrocubane, A nitrogen rich explosive, Eosin Y, Eosin Y again, Glymes or whatever new pseudo you will use...
The forum will be positively critical and it is not personnal, it is for your own good...that way you could progress and improve quality.

But I have the feeling you will do like you want, because you almost never took our advices seriously...this is proven by the chemical mistakes you keep on posting the same way through your diverse ID's...

THINK Twice AND EVEN MORE before posting

Again you have lost a proton in your chemical story :mad:

NH3 + HCl --> NH4Cl
N2H4 + HNO3 --> N2H5NO3
CH3-NH2 + HClO4 --> CH3-NH3ClO4
so
H2N-CN4H + HClO4 --> O4ClH3N-CN4H

PLEASE LEARN FROM YOUR REPETITIVE MISTAKES!

PHILOU Zrealone - 22-5-2016 at 04:32

Right.

Perdifluoroaminohexamethyenetetramine. C6N16F24 --> 6CF4 + 8N2.

C6N4H12 + 12N-bromosuccinide --> C6N4Br12 + succinide

C6N4Br12 + 12HNF2 --> C6N16F24

Bromine is generally a good leaving group. For the sake, call it PDF HMTA, as I'd rather make it sound like a photocopier than a mouth orgy.

It is not because it works on paper that a reaction will work.
1°)Is there a trace of your putative per-bromination of HMTA (hexamethylenetetramine) via N-bromo succinimide somewhere into the chemical litterature or on a website?
NO
=N-CH2-N= might be the representative linkage of HMTA and why would Br(+) attack the methylene and take H(+)?

2°) Is there a trace of your putative reaction of HNF2 with a geminal alkyl dibromide to make a geminal alkyl bis-difluoroamino compound into the chemical litterature or on a website?
NO

3°) As explained by many at one of your previous ID's, the driving force of difluoroamino compounds is the formation of HF and this explains the explosive power of those compounds, just like HCl is the driving force of -NCl2 (dichloroamines).
So no hydrogen and F linked to N what is slighly less electropositive than C (to make CF4) means no great reaction energy...so your compound might be just as interesting as a teflon block...

PLEASE LEARN FROM YOUR REPETITIVE MISTAKES!

PHILOU Zrealone - 22-5-2016 at 04:46

Hold up.

Where on earth are you fitting the dinitramide groups, as ANQ is NO2-(C=NH)-NH2? Would it just be [NO2(C=NH2)-NH2]- 2[NO2-N-NO2]+ or something like that?

If that works, forming NO2CNHNH2(NO2-N-NO2]2 * H2O I see no reason why HO-NH2 should not be able to kick the H2O out and form NO2CNHNH2(NO2NNO2)2 * HONH2

More neatly:
CH3N3O2 + NH3N3O4 --> CH3N6O6 + NH3
CH3N6O6 + H3NO --> C3H6N7O7

LEARN LEARN LEARN
ANQ is amino nitroguanidine, the formula has been posted many times and you are not even able to copy paste it!
Guanidine is (H2N-)2C=NH
Nitroguanidine is (H2N-)2C=N-NO2
Aminoguanidine is (H2N-)2C=N-NH2
Aminonitroguanidine is H2N-NH-C(-NH2)=N-NO2
(the double bond may change postion arround the C but then a H change also position)

What you wrote (NO2-(C=NH)-NH2) is C-nitro-formamidine (resulting form the putative addition of NH3 on nitryl cyanide).

Look at Klapote paper (provided by Microtek) on ANQ nitrate to learn the structure of ANQ dinitramide...you have again lost a proton!

Quoted from you:
"If that works, forming NO2CNHNH2(NO2-N-NO2]2 * H2O I see no reason why HO-NH2 should not be able to kick the H2O out and form NO2CNHNH2(NO2NNO2)2 * HONH2"
If you see no reason:
-then maybe look at hydroxylamine pKa and pKb versus those of ANQ and follow the acido-basic rules (the stronger acid goes with the stronger base, the weakest acid with the weakest base)
-then ask yourself why hydroxylamine dinitramide is not made yet
-then maybe change hobby

glymes - 22-5-2016 at 04:53

Actually, I stand corrected. That was a stupid post.

The following is how I would synthesise it right from the start:

CaCN2+NH4NO3-->[C(NH2)3]NO3
[C(NH2)3]NO3-dehydration with 98% H2SO4->NO2-N=C-(NH2)2 (probably nitroimine form as the resonance is stabilised compared to the nitroamine.)
NO2-N=C-(NH2)2+N2H4-->NO2-N-(NH2-)C-NH-NH2
And from there on:
NO2-N-(NH2-)C-NH-NH2+HN3-->NO2-N-(NH2-)C-NH-NH3-N3
3-amino 1-nitroguanidium azide would have around the following properties:
Nitrogen content by weight: 70%
Friction sensitivity: High
Shock sensitivity: High
Heat sensitivity: High
Can you see where this is going? I also expect that it would be both highly toxic and extremely explosive.
I also hypothesise that:
NO2-NH-(C-NH2)-N-NO2+N2H4-->NO2-NH-(C-NH-NH2)-N-NO2 (3-hydrazino 1,5-nitroguanidine.)
Therefore, by extension:
NO2-NH-(C-NH-NH2)-N-NO2+HN3-->NO2-NH-(C-NH-NH3)-N-NO2-N3
3-hydrazino 1,5-nitroguanidium azide. Which is a little bit silly.
And also (less nitrogen but better OB and density)
NO2-NH-(C-NH-NH2)-N-NO2+N-(NO2)2-->
[NO2-NH-(C-NH-NH2)-N-NO2]+ [NO2-N-NO2]-
3-hydrazino 1,5-nitroguanidium dinitramide.
I rest my case. I also don't think that any protons ran away!

[Edited on 22-5-2016 by glymes]

[Edited on 22-5-2016 by glymes]

glymes - 22-5-2016 at 09:52

These should make it clearer. If the following compounds do exist, they'd be spectacular explosives.

I believe that I screwed up the NH3: it's meant to be NH2, meaning that it takes NH from the hydrazine, yielding gaseous ammonia.

[Edited on 22-5-2016 by glymes]

kratomiter - 23-5-2016 at 03:50

Need some help with ANQ nitrate. ANQ disolved instantly in large excess 67% HNO3 at 70ºC. Then I let it cool down but nothing crystallizes from the solution, not even in the freezer. My nitric acid is very old, so probably is less than 67%. In the paper, HNO3 used was at 40%. IDK if it should be more diluted or just wait.

glymes - 23-5-2016 at 03:52

My final lot of theories.
1. NO2-N=C-(NH2)2 + N2H4 --> NO2-N=(C-NH2)-NH-NH2 + NH3
NO2-N-(C-NH2)-NH-NH2 can form salts. The azide (NO2-N-(C-NH2)-NH-NH2-N3 looks promising because of its high nitrogen content (69%.) It is also predicted to be highly sensitive.
2. I also believe that NO2-N-(C-NH2)-NH-NH2 can be nitrated with dinitrogen pentoxide in chloroform, as suggested in Klapotke's paper:
NO2-N-(C-NH2)-NH-NH2 + N2O5 --> NO2-N-(C-NH2)-NH-NO2 + H2O + NO2 + N.
This would also be able to form salts, such as 3-amino 1,5-dinitroguanidium azide.
3. I also believe that NO2-N-(C-NH2)-NH-NO2 can be hydrazinolysed in the same way as (1) where the NH2 group is hydrazinolysed to NH-NH2 and free ammonia gas.
NO2-N-(C-NH2)-NH-NO2 + N2H4 --> NO2-N-(C-NH-NH2)-NH-NO2 + NH3.
This could again form salts, such as 3-hydrazino 1,5-dinitroguanidium azide.
4. I also believe that NO2-N-(C-NH-NH2)-NH-NO2 may be able to be nitrated with N2O5 in chloroform in the same way as (2) in the following:
NO2-N-(C-NH-NH2)-NH-NO2 + N2O5 > NO2-N-(C-NH-NO2)-NH-NO2 + H2O + NO2+ N
This may also form salts such as 1,3,5-trinitroguanidium azide, which would be extremely explosive due to its high nitrogen content and high oxygen balance.
5. If diaminonitroguanidine is synthesised and it can be protonated twice, it may form salts such as diaminonitroguanidium diazide, NO2-N-C-(NH-NH2)-NH-NH2 2N3, or CH6N12O2. This would be extremely powerful also.
6. Some other salts may be formed from the hydrazinolysis of nitrourea:
NH2-(C=O)-NH-NO2 + N2H4 --> H2N-NH-(C=O)-NH-NO2.
If this forms salts, it may form 1-hydrazino 3-carboxyl 5-nitrourea nitrate, which would be a promising high explosive.
7. Potentially, 1-hydrazino 3-carboxyl 5-nitrourea may be able to be nitrated:
NH2-NH-(C=O)-NH-NO2 + NO2-BF4 --> NO2-NH-(C=O)-NH-NO2 + BF4
which could form 1,5-dinitro 3-carboxyl azide and other salts in the same vein.

I also theoreticise that nitration cannot go on for ever: it may not be possible to force a second nitro- group onto 1-hydrazino 3-carbonyl 5-nitrourea, even with nitronium tetrafluoroborate.

[Edited on 23-5-2016 by glymes]

PHILOU Zrealone - 23-5-2016 at 06:53

It would be a decent oxidizer, however not good enough.

I personally do not like to introduce carbon atoms in the anion because they increase the overall average molecular weight of the exhaust in a propellant.

If you take a look at the ANQ-dinitramide-monohydrate, it is very stable, has a VoD of nearly 9200, produces more gas than ANQ-Nitrate.

However if you put a nitroformate in there, the gas produced, L/kg will be significantly lower.

Edit:
Anyone have any idea if the ANQ-Dinitramide-monohydrate could be turned into... maybe ANQ-Dinitramide-monohydroxylamide ?

If the addition of C into a molecule induces heavier exhaust products and thus less good propelling abilities; it is not always bad for detonic/explosive parameters....
See dinitrobenzene, trinitrobenzene and hexanitrobenzene...
HNB has a density of arround 2.0 and a VOD of 10000 m/s while it contains not a single H atom (what is mandatory for a good propellant) and it only produces heavy gases like CO2 or CO and N2 or NxOy.

ANQ-Dinitramide-monohydrate can't be turned into ANQ-Dinitramide-monohydroxylamide because the hydroxylamine is more basic than the terminal H2N- of the hydrazino moeity...
So HA will react with the dinitramidic acid and ANQ will form a zwiterionic compound (it contains both a basic and an acidic group that will neutralize...reason why ANQ has to be neutralised in strong acid solutions to avoid precipitation of the zwiterionic species)
H2N-C(=N-NO2)-NH-NH3N(NO2)2 + HO-NH2 --> HO-NH3N(NO2)2 + O2N-N(-)-C(=NH)-NH-NH3(+)
The resulting HADN (hydroxylamine dinitramide) is probably too unstable to exist (never heard of it anywhere) and will then decompose into H2O, N2 and NxOy.

PHILOU Zrealone - 23-5-2016 at 06:55

These should make it clearer. If the following compounds do exist, they'd be spectacular explosives.

I believe that I screwed up the NH3: it's meant to be NH2, meaning that it takes NH from the hydrazine, yielding gaseous ammonia.

[Edited on 22-5-2016 by glymes]

N2H4 will react as a base with the two acidic -NH-NO2 groups and will more likely not make the compound you want.
Hydrazine DiNitroGuanidate or Dihydrazine dinitroguanidate are for sure interesting to investigate.

Microtek - 23-5-2016 at 07:39

Kratomiter: Remember that ANQ nitrate has a non-zero solubility in nitric acid. If you used "a large excess", you may simply not have enough product to supersaturate the solution on cooling, in which case nothing will precipitate.

DubaiAmateurRocketry - 23-5-2016 at 07:54

It would be a decent oxidizer, however not good enough.

I personally do not like to introduce carbon atoms in the anion because they increase the overall average molecular weight of the exhaust in a propellant.

If you take a look at the ANQ-dinitramide-monohydrate, it is very stable, has a VoD of nearly 9200, produces more gas than ANQ-Nitrate.

However if you put a nitroformate in there, the gas produced, L/kg will be significantly lower.

Edit:
Anyone have any idea if the ANQ-Dinitramide-monohydrate could be turned into... maybe ANQ-Dinitramide-monohydroxylamide ?

Umm makes sense.

Hydroxylamine dinitramide has a stable zwiterionic form, I was very excited about it few years ago.

the zwiterionic form of hydroxylamine dinitramide exists in this manner:

[H3N+O-] [[NH3OH+]2]2+ [HONH2] [[N(NO2)2]2]2- Empirically N10H14O12.

glymes - 23-5-2016 at 10:22

Ok.
Urea might hydrazinolyse:
NH2-(C=O)-NH2 + N2H4 --> NH2-NH-(C=O)-NH2
Which would then be able to form the nitrate:
NH2-NH-(C=O)-NH2 + NO2BF4 --> NH2-NH-(C=O)-NO2 + BF4
Which can form the azide upon addition of HN3:
NH2-NH-(C=O)-NO2 + HN3 --> [NH2-NH-(C=O)-NO2]+ N3- (I can't work out where the H should go?)
Empirically:
CH4N6O3, with a high nitrogen content.
Or we could hydrazinolyse the urea twice:
NH2-NH-(C=O)-NH2 + N2H4 --> NH2-NH-(C=O)-NH-NH2
And then nitrate this twice:
NH2-NH-(C=O)-NH-NH2 + 2NO2BF4 --> NO2-NH-(C=O)-NH-NO2 + 2BF4
And then this compound 3-carboxyl 1,5-dinitrourea could do the following:
NO2-NH-(C=O)-NH-NO2 + HN3 --> [NO2-NH-(C=O)-NH-NO2]+ N3- (still no bloody idea where the H goes) forming 1,5-dinitrourea azide (DNUA.)
Or, it could react with hydrazine again, forming hydrazine 1,5-dinitroureate (HDNU,) N2H5- [NO2-NH-(C=O)-NH-NO2]+.
DNUA = CH2N7O4
HDNU = CH7N6O4
Clearly, DNUA is the more promising explosive.

Cryolite - 23-5-2016 at 11:49

Ok.
Urea might hydrazinolyse:
NH2-(C=O)-NH2 + N2H4 --> NH2-NH-(C=O)-NH2
Which would then be able to form the nitrate:
NH2-NH-(C=O)-NH2 + NO2BF4 --> NH2-NH-(C=O)-NO2 + BF4
Which can form the azide upon addition of HN3:
NH2-NH-(C=O)-NO2 + HN3 --> [NH2-NH-(C=O)-NO2]+ N3- (I can't work out where the H should go?)
Empirically:
CH4N6O3, with a high nitrogen content.
Or we could hydrazinolyse the urea twice:
NH2-NH-(C=O)-NH2 + N2H4 --> NH2-NH-(C=O)-NH-NH2
And then nitrate this twice:
NH2-NH-(C=O)-NH-NH2 + 2NO2BF4 --> NO2-NH-(C=O)-NH-NO2 + 2BF4
And then this compound 3-carboxyl 1,5-dinitrourea could do the following:
NO2-NH-(C=O)-NH-NO2 + HN3 --> [NO2-NH-(C=O)-NH-NO2]+ N3- (still no bloody idea where the H goes) forming 1,5-dinitrourea azide (DNUA.)
Or, it could react with hydrazine again, forming hydrazine 1,5-dinitroureate (HDNU,) N2H5- [NO2-NH-(C=O)-NH-NO2]+.
DNUA = CH2N7O4
HDNU = CH7N6O4
Clearly, DNUA is the more promising explosive.

BF4? What is BF4? I don't think a single one of your proposed "equations" is balanced.

Before you risk maiming or poisoning yourself with such dangerous reagents (NO2BF4!! HN3!!!), and before you attempt to propose novel explosive compounds and lecture others on safety, I advise you to sit down and actually learn chemistry from the basics, especially if you want to be taken at all seriously here.

glymes - 23-5-2016 at 11:51

And finally the pinnacle of insanity. Triaminoguanidium diazide.
[NH2-NH-(C-NH-NH2)-NH-NH2]+ 2N3- or, empirically, CH9N12. 89% N.
I believe that this compound is like an angry genie. Tap on your round bottomed flask three times and the genie will appear with a loud report, a puff of nitrogen and a shower of glass.

Marvin - 23-5-2016 at 12:29

Your charges don't balance.

I'm not sure this sort of chemistry by scrabble rules discussion is beneficial to anyone.

glymes - 23-5-2016 at 12:58

Yes it is. It is a discussion about theoretical energetics. And therefore, Scrabble rules can yield interesting results.

Dornier 335A - 23-5-2016 at 14:42

Drawing new energetics is certainly fun Glymes, but not exactly useful if the theoretical compounds aren't investigated a bit further.

First off: could the molecule even exist in reality? This is pretty basic, counting hydrogens and balancing charges. Looking up pKa if it's a salt could be a good idea; your triaminoguanidinium diazide would not keep together for example.

Second: would it be worth the hassle to try to make this material? This means either a VoD > 9 km/s or an extremely insensitive energetic. So calculate the density with your method of choice (I like a fragment addition method), predict the enthalpy of formation with a quantum chemistry program like FireFly and finally calculate the detonation performance. This can be done with a simple formula like Kamlet-Jacobs.

Third: synthesis. Presenting something like polynitrogen ( -[NH-NH]-, VoD ~30 km/s) is useless unless there is at least an idea for a synthesis. These should of course be based on the literature. It will likely take multiple trials to get a working, preferably high yield, route to the new compound.

NeonPulse - 23-5-2016 at 17:20

Looks like Nitrogen rich explosive is back.

PHILOU Zrealone - 24-5-2016 at 07:05

Quote: Originally posted by Microtek

According to a paper by Castillo-Melendez and Golding, the yield of ANQ can be as high as 60% given the right reaction conditions (55 C, 15 minutes reaction time). The paper is from 2004, so it's older than the one I posted by Klapötke, et al. This could indicate that it is quite difficult to reach those numbers. I think this is supported by the fact that the yield peak is quite narrow.

Thank you for that paper too!

PHILOU Zrealone - 24-5-2016 at 07:11

It would be a decent oxidizer, however not good enough.

I personally do not like to introduce carbon atoms in the anion because they increase the overall average molecular weight of the exhaust in a propellant.

If you take a look at the ANQ-dinitramide-monohydrate, it is very stable, has a VoD of nearly 9200, produces more gas than ANQ-Nitrate.

However if you put a nitroformate in there, the gas produced, L/kg will be significantly lower.

Edit:
Anyone have any idea if the ANQ-Dinitramide-monohydrate could be turned into... maybe ANQ-Dinitramide-monohydroxylamide ?

Interesting DAR.
Do you have the physico-chemical detonic/propellant properties of that compound under hand? Or the paper about it?

PHILOU Zrealone - 24-5-2016 at 08:16

NO2-N-(NH2-)C-NH-NH2+HN3-->NO2-N-(NH2-)C-NH-NH3-N3
3-amino 1-nitroguanidium azide

I also hypothesise that:
NO2-NH-(C-NH2)-N-NO2+N2H4-->NO2-NH-(C-NH-NH2)-N-NO2 (3-hydrazino 1,5-nitroguanidine.)
Therefore, by extension:
NO2-NH-(C-NH-NH2)-N-NO2+HN3-->NO2-NH-(C-NH-NH3)-N-NO2-N3
3-hydrazino 1,5-nitroguanidium azide.

NO2-NH-(C-NH-NH2)-N-NO2+N-(NO2)2-->
[NO2-NH-(C-NH-NH2)-N-NO2]+ [NO2-N-NO2]-
3-hydrazino 1,5-nitroguanidium dinitramide.
I rest my case. I also don't think that any protons ran away!

If ANQ needs > 40% HNO3 or HClO4 (what are very strong acids with pKa <-2) to be protonated and avoid zwiterionic autoprotonation...then the poorly acidic HN3 (pKa = 4,6 what is at least 10⁷ times order of magnitude less acidic than HNO3 and HClO4 (10⁷= 10.000.000 times)) won't be able to join the molecule and freebase gas you to death!

You obviously can't read! I already explained that the dinitroguanidine will simply form a salt of hydrazine, a mono hydrazine or a dihydrazine salt, no NH3 will escape to make your compound.

In your last formula you lost a proton again... hydrogen dinitramide is HN(NO2)2

NO2-N-(C-NH2)-NH-NH2 can form salts. The azide (NO2-N-(C-NH2)-NH-NH2-N3

2. I also believe that NO2-N-(C-NH2)-NH-NH2 can be nitrated with dinitrogen pentoxide in chloroform, as suggested in Klapotke's paper:
NO2-N-(C-NH2)-NH-NH2 + N2O5 --> NO2-N-(C-NH2)-NH-NO2 + H2O + NO2 + N.

This would also be able to form salts, such as 3-amino 1,5-dinitroguanidium azide.

3. I also believe that NO2-N-(C-NH2)-NH-NO2 can be hydrazinolysed in the same way as (1) where the NH2 group is hydrazinolysed to NH-NH2 and free ammonia gas.
NO2-N-(C-NH2)-NH-NO2 + N2H4 --> NO2-N-(C-NH-NH2)-NH-NO2 + NH3.
This could again form salts, such as 3-hydrazino 1,5-dinitroguanidium azide.

4. I also believe that NO2-N-(C-NH-NH2)-NH-NO2 may be able to be nitrated with N2O5 in chloroform in the same way as (2) in the following:
NO2-N-(C-NH-NH2)-NH-NO2 + N2O5 > NO2-N-(C-NH-NO2)-NH-NO2 + H2O + NO2+ N
This may also form salts such as 1,3,5-trinitroguanidium azide, which would be extremely explosive due to its high nitrogen content and high oxygen balance.
5. If diaminonitroguanidine is synthesised and it can be protonated twice, it may form salts such as diaminonitroguanidium diazide, NO2-N-C-(NH-NH2)-NH-NH2 2N3, or CH6N12O2. This would be extremely powerful also.
6. Some other salts may be formed from the hydrazinolysis of nitrourea:
NH2-(C=O)-NH-NO2 + N2H4 --> H2N-NH-(C=O)-NH-NO2.
If this forms salts, it may form 1-hydrazino 3-carboxyl 5-nitrourea nitrate, which would be a promising high explosive.
7. Potentially, 1-hydrazino 3-carboxyl 5-nitrourea may be able to be nitrated:
NH2-NH-(C=O)-NH-NO2 + NO2-BF4 --> NO2-NH-(C=O)-NH-NO2 + BF4
which could form 1,5-dinitro 3-carboxyl azide and other salts in the same vein.

I also theoreticise that nitration cannot go on for ever: it may not be possible to force a second nitro- group onto 1-hydrazino 3-carbonyl 5-nitrourea, even with nitronium tetrafluoroborate.

All wrong again
1°)ANQ can only form salts with very strong acids. HN3 is way to weak .

2°)Why nitrate ANQ (made from NQ) to get DNQ what can be made directly from NQ (and that is what is written in Klapote's paper...but yes of course you can't read)

A dinitro(amino)guanidine would be even more acidic than ANQ and so formation of an azide is even more elusive.

3°)DNQ won't hydrazinolyse, it will form a (di)hydrazinium salt.
Here also no HN3 salt possible!

4°) Trinitroguanidine TNQ is only theorical at this date, it will be super acidic vs DNQ and so forming a HN3 salt of it...you know the song now...

5°) If you have chance DANQ or DANG (diaminonitroguanidine) and that it is basic enough then maybe one HN3 will fix on it, certainly not 2.
Here also you forgot 2 protons NO2-N=C-(NH-NH3N3)-NH-NH3N3

6°) Hydrazinolysis of nitrourea?
Is nitrourea stable enough to hydrazinolyse?
NU and DNU are sensitive to water already...DNU forms NH4 and K salts in the cold with 50% loss in the process by hydrolysis...
Why would N2H4 favor NH3 elimination and not NH2-NO2 elimination?

7°)"1-hydrazino 3-carboxyl 5-nitrourea" There is something all wrong with the numbers of that formula.
Why start from 3-amino-1-nitrourea to make 1,3-dinitrourea while it can be done directly from urea?

Again Ochus Pochus NH2 disappear as dark matter...

BF4NO2 = BF3 + F-NO2 = BF4(-)NO2(+) = nitronium salt
Why would a NO2(+) replace a NH2(+) (very hard if not impossible to make)?

No HN3 will join in a salt with DNU...which is way too acidic!

8°)"I also theoreticise that nitration cannot go on for ever: it may not be possible to force a second nitro- group onto 1-hydrazino 3-carbonyl 5-nitrourea, even with nitronium tetrafluoroborate."
Wow, so your daydreaming have limits...glad to read that...and at least something you wrote that is right!

Which would then be able to form the nitrate:
NH2-NH-(C=O)-NH2 + NO2BF4 --> NH2-NH-(C=O)-NO2 + BF4
Which can form the azide upon addition of HN3:
NH2-NH-(C=O)-NO2 + HN3 --> [NH2-NH-(C=O)-NO2]+ N3- (I can't work out where the H should go?)
Empirically:
CH4N6O3, with a high nitrogen content.
Or we could hydrazinolyse the urea twice:
NH2-NH-(C=O)-NH2 + N2H4 --> NH2-NH-(C=O)-NH-NH2
And then nitrate this twice:
NH2-NH-(C=O)-NH-NH2 + 2NO2BF4 --> NO2-NH-(C=O)-NH-NO2 + 2BF4
And then this compound 3-carboxyl 1,5-dinitrourea could do the following:
NO2-NH-(C=O)-NH-NO2 + HN3 --> [NO2-NH-(C=O)-NH-NO2]+ N3- (still no bloody idea where the H goes) forming 1,5-dinitrourea azide (DNUA.)

Again you have lost some NH2 somewhere over the rainbow!

The molecule H2N-NH-CO-NO2 would be too unstable to exist and is not nitrourea or aminonitrourea what should be H2N-CO-NH-NO2 and H2N-NH-CO-NH-NO2.

Nitrate is from nitric acid -O-NO2 or ONO2(-) or NO3(-)...-NO2 is nitro. To make semicarbazine (aminourea) or carbazine (diaminourea) nitrate or dinitrate is simply a matter of adding dilluted HNO3

ANU (aminonitrourea) and DNU would be too acidic to make a salt with HN3!

And finally the pinnacle of insanity. Triaminoguanidium diazide.
[NH2-NH-(C-NH-NH2)-NH-NH2]+ 2N3- or, empirically, CH9N12. 89% N.
I believe that this compound is like an angry genie. Tap on your round bottomed flask three times and the genie will appear with a loud report, a puff of nitrogen and a shower of glass.

Maybe TAG (triaminoguanidine) will form a mono hydrazoate or a dihydrazoate.
H2N-N=C(-NH-NH3N3)-NH-NH2
and
H2N-N=C(-NH-NH3N3)2 depending on the pKb1, pKb2 and pKb3 of TAG.

DubaiAmateurRocketry - 24-5-2016 at 13:24