Sciencemadness Discussion Board

New Energetic Materials - Current Research

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franklyn - 10-4-2010 at 20:54

Quote: Originally posted by PHILOU Zrealone  

http://www.sciencemadness.org/talk/viewthread.php?tid=3416#p...
the enthalpy of reaction adds partly to the energy process.
As you know when making most HE, the reaction is exothermic, reason why
cooling is provided. Exothermic means a loss of energy

Quote: Originally posted by PHILOU Zrealone  

http://www.sciencemadness.org/talk/viewthread.php?tid=3416#p...
Explosives that displays less H atoms (more insaturations) displays higher heat of explosions
...multiple bonding increases the energy per volume, and no or little water produced favourise
the best heat output.
N#C-C#N is one of the hottest burning stuff (4000°C vs 3100°C for H-C#C-H)...that's why
I think percyano compounds admixed with pernitrocompounds must be the best binary HE
of all times! It excludes H atoms and contains a lot of unsaturated energy rich bonds per volume.
But who wants to play with tetracyano methane and tetranitromethane


Compounds made mostly of covalently bonded Nitrogen are not alone in storing energy
endothermically. In the Cyano ( Nitrile ) group we see that carbon , beside being a fuel ,
bonded to Nitrogen can also store energy endothermically. TricyanoTriazine the trimer
of Cyanogen hydrolysis readily, even cold is rapidly decomposed by water but it can
provide a framework on which to build. http://pubs.acs.org/doi/abs/10.1021/jo025833h
Chemical Reduction of 2,4,6-Tricyano-1,3,5-triazine and 1,3,5-Tricyanobenzene.
Formation of Novel 4,4‘,6,6‘-Tetracyano-2,2‘-bitriazine and Its Radical Anion

Carbon Nitrogen polymers , US patent 3057808
2,4,6-Tricyano-1,3,5-Triazine , US patent 5086172
Chemistry of Cyanogen Compounds
http://ia311327.us.archive.org/2/items/chemistrycyanog00will...

. . . . . . N == C-CΞN
. . . . . . / . . . . . \
NΞC-C . . . . . .N
. . . . . .\\ . . . . . //
. . . . . . N ---- C-CΞN

Replacing one Cyano group with a Trinitro methane would yield an impressive energetic

NΞC-CΞN + N2O4 might be induced to react gently producing NΞC-NO2 as a trimer thus _

. . . . . . N == C-NO2
. . . . . . / . . . . . \
NO2-C . . . . . .N
. . . . . .\\ . . . . . //
. . . . . . N ---- C-NO2

Synthesis And Chemistry Of Cyanogen
http://pubs.acs.org/doi/abs/10.1021/cr50029a003

It is also very possible a Tetrazine compound can be formed by different means

. . . . . N == C-NO2
. . . . ./ . . . . . .\
. . . .N . . . . . .N
. . . . .\\ . . . . . //
NO2-C ---- N

These will likely easily hydrolyze and be subject to derangement, but indicate areas for
further investigation.

There is much interest in compounding Trinitromethane usually in the form of a salt with
suitable reducing bases. Tricyanomethane has never been isolated and is known only by
it's salts and compounds. It's pKa of -5 means it is more acidic than sulfuric acid.
Trinitromethane is nearly as acidic so the prospect of mutual condensation is dismal.
Hexanitroethane can be considered two Trinitromethanes joined and is a stable molecule
so by example 1,1,1-Tricyano-2,2,2-Trinitroethane is not unthinkable. Cyanoform , HC(CN)3 ,
has an estimated ~ 800 KJ/mol heat of formation, Nitroform , HC(NO2)3 , is - 48.5 KJ/mol.
Synthesis and Thermochemistry of Tricyanomethyl and Other Polycyano Compounds
http://www.anl.gov/PCS/acsfuel/preprint archive/Files/09_1_DETROIT_04-65_0107.pdf

A compound consisting of both groups will be highly endothermic.
Utilizing the detonation calculator utility by forum member Engager , and entering
the nominal value of 1.6 for density and estimated 750 KJ/mol the projected
detonation pressure is 456 Kbar at 8680 m/s , by the Keshavarz method
entering density of 1.8 gives 577 Kbar at 9520 m/s

Tricyanomethane and Trinitromethane form ionic metal salts. A way in which the two
moieties might be compounded is by a solution of equal parts of Magnesium Tricyano -
methanide and Magnesium Trinitromethanide co-crystallized as a double salt , thus
Mg{C(CN)3}2 + Mg{C(NO2)3}2 => 2 Mg{C(CN)3C(NO2)3} => 2 MgO + 10 CO + 6 N2

If one is seeking a powerful " green " primary , one need look no further.

Relative solvation and strength of polycyano- and polynitromethanes in water
http://www3.interscience.wiley.com/journal/109741371/abstrac...

Trinitromethanide and Tricyanomethanide Salts Restricted to C, H, N, and 0 Atoms
http://handle.dtic.mil/100.2/ADA254523
redirects to _
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA254523&Locati...

1. Superior Energetic Materials That Contain Coexisting Carbocations and Anions
2. Energetic Materials Restricted in Composition to C, H, N, and 0 Atoms
http://handle.dtic.mil/100.2/ADA275449
redirects to _
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA275449&Locati...

Tricyanomethane (Cyanoform), Carbamyldicyanomethane, and Their Derivatives
http://pubs.acs.org/doi/abs/10.1021/jo01049a021


Depicted below are possible structures utilizing the Cyano ( Nitrile ) group
I do not have a notion how these could be made.

Cyano cyclic.gif - 4kB

[Edited on 11-4-2010 by franklyn]

chemoleo - 12-4-2010 at 16:24

Quote:

. . . . . . N == C-NO2
. . . . . . / . . . . . \
NO2-C . . . . . .N
. . . . . .\\ . . . . . //
. . . . . . N ---- C-NO2

This is essentially the oxidation product of melamine....a similar derivative of triazine exists, i.e. the cyanuric triazide (replace the NO2's by N3's).

The_Davster - 13-4-2010 at 10:42

Quote: Originally posted by franklyn  


It is also very possible a Tetrazine compound can be formed by different means

. . . . . N == C-NO2
. . . . ./ . . . . . .\
. . . .N . . . . . .N
. . . . .\\ . . . . . //
NO2-C ---- N

These will likely easily hydrolyze and be subject to derangement, but indicate areas for
further investigation.



Dinitro-1,2,4,5-tetrazine was a much sought after target for a long time. The aminonitro dioxide has been made and found to be hydrolytically and thermally unstable. Nice density though, at >1.9. Mind you, to make this uses hypofluorous acid...

franklyn - 3-5-2010 at 05:46

Tricyanomethane (Cyanoform), Carbamyldicyanomethane, and Their Derivatives
http://pubs.acs.org/doi/abs/10.1021/jo01049a021
related post
http://www.sciencemadness.org/talk/viewthread.php?tid=8544#p...

Crystal structures & thermal behavior of Tricyanomethanides ( reference citation )
http://www.znaturforsch.com/ab/v63b/63b0285.pdf

Alkali or Alkaline Tricyano methanides US patent 20100094040

.

Anders Hoveland - 15-6-2010 at 18:48

C2(NO2)2(N3)2 should be about just as powerful as tetranitrotetrahedrane. I think having a N atom in a pentagonal ring with positive charge and double bonded to a side group C(NO2)2 would be a good way to add a powerful functional group to an energetic compound. Draw it on paper, it has some complex resonance states that will provide high stability. This is analogous to nitroformate's stability C(NO2)3- cation, but with the group covalently bonded to the main molecule.

I would like to add that some of the past posts have presented possible new molecules that have decomposition products with high energies of formation. These heats of formation are inadequate to predict energetic performance. The C-N bonds are strong and will consume much energy in breaking, futhermore I would expect the molecules, which are highly electron deficient because of lack of hydrogen atoms, to be too sensitive for commercial use.

Also having a C=O bond is a waste. It does little to add power, and much to add sensitivity (for example there is an RDX compound with 2 of the H's are replaced by an Oxygen. Why add an oxygen that is going to take up space when it won't add energy by oxidizing something? That is why I am not fond of urea based compounds.

[Edited on 16-6-2010 by Anders Hoveland]

[Edited on 16-6-2010 by Anders Hoveland]

Microtek - 16-6-2010 at 23:55

C=O generally gives a higher density than CH2. Higher density at the cost of a little energy is preferable over the reverse situation when high brisance (VOD, Pcj) is the goal.

Anders Hoveland - 17-6-2010 at 15:55

Higher density is only good if it packs in more energetic material. For example, ethyl nitrate is more dense than methyl nitrate, but also has a lower det. velocity. Amine groups added onto a compound usually cause the molecules to pack closer together, whereas I am not sure about using a CO instead of a CH2.
Other reasons amine groups are good is they are electron-donating, increasing stability. They can also add nitrogen, which can add power if the carbon it is conncected to will get oxidized, otherwise an amine group can actually decrease the power of the energetic compound. An example is ethylene 1-amine, 2-nitrate. Also, if the energetic material is highly very energetic, the amine group, while having power, will actually reduce the "energetic density", somewhat analagous to mixing TNT with RDX.
Another comment also, adding a CN will likely increase the temperature of the decomposition gases, but will not do much to add actual energy. Perhaps some of the energy in an explosive is wasted on gases/ steam with high specific heats, that absorb much energy in boiling/ expanding.

[Edited on 17-6-2010 by Anders Hoveland]

not_important - 17-6-2010 at 23:02

Well, hey, if we're talking theoretical stuff, abet under research in this case, how about

Polymeric Nitrogen Stabilized on Carbon Nanotubes: A Highly Energetic, Green Explosive




Attachment: manning-polymeric-nitrogen.pdf (996kB)
This file has been downloaded 2418 times


The_Davster - 18-6-2010 at 03:39

WOW......19.73 km/s detonation velocity. Too bad it is not stable except under extreme conditions.

Anders Hoveland - 18-6-2010 at 13:21

I saw one researcher prepare compounds with the ---CCSF5 group, a triple bond between the carbons. The SF5 is relatively inert, but the formation of HF makes it potentially powerful, too bad the S--F bond is so strong.

Microtek - 21-6-2010 at 22:55


Quote:

Higher density is only good if it packs in more energetic material.


Take a look at keto-RDX that you mentioned yourself; it has a higher density than RDX and a significantly higher VOD (a few percent better performance than HMX). It is true that dinitroureas are often hydrolytically unstable, but that is a different matter. Generally speaking they exhibit very high performance (in terms of brisance, not heaving power).

[Edited on 22-6-2010 by Microtek]

franklyn - 22-6-2010 at 00:19


A variation on the theme of compounding cyano and nitro salts is to combine
Dicyanamide and Dinitramine moieties co-crystallized as a double salt.
Magnesium dicyanamide plus Magnesium dinitramide , thus
Mg{N(CN)2}2 + Mg{N(NO2)2}2 => 2 Mg{N(CN)2.N(NO2)2} => 2 MgO + 2 CO2 + 2 CO + 6 N2

Very high density is to be expected , over 2 , with a high heat of explosiion.

.

Anders Hoveland - 22-6-2010 at 21:36

First off, dinitramide is only stable under fairly basic conditions. Mg(NO3)2 for example is acidic and a very strong dehydrating agent. It is not possible to dry the hydrate by heating.
What about adding picric acid to neutralize the other amine in Hydrazinium perchlorate?

Keto-RDX is only more powerful because the O makes it more electron withdrawing and unstable, not because of density, even though it does in fact have a higher "density".
In a good energetic compound one should aim for high energies of formation in the decomposition products, not trying to make everything as unstable as possible.

By the way, I mixed acetone with a solution of bromine to make bromoacetone. Then made tri Bromoacetone-peroxide. Then absorbed it into benzene and added AgNO3. Might have used AgClO4.

[Edited on 22-6-2010 by Anders Hoveland]

[Edited on 24-6-2010 by Anders Hoveland]

franklyn - 23-6-2010 at 17:51


Quote: Originally posted by Anders Hoveland  
dinitramide is only stable under fairly basic conditions.
The dinitramide of Mg would be nearly impossible to make,
and would have to be kept away from any moisture.

@ Anders Hoveland

If this reply sounds piqued it's because having otherwise exhibited competence
in your posts , you continue stating related mistaken assumptions after repeatedly
being corrected. Post too many wrong assertions and readers will be dismissive
of anything else you say. Read up on the item before commenting on something
you evidently have no knowledge of. The Magnesium salt is readily made by treating
aqueous solution of Ammonium Dinitramide with Magnesium hydroxide.
Magnesium Dinitramide hexahydrate, Mg{N(NO2)2}2 • 6H20 then crystallizes out.
Disclosed here => http://www.springerlink.com/content/r44x114150263563
Because Dinitramidic acid decomposes , it is formed as the ammonium salt
which is commercially available.


While on the subject , some references _

Advances In Energetic Dinitramides
http://www.worldscibooks.com/chemistry/6618.html

Synthesis of Ammonium Dinitramide by Nitration of
Potassium and Ammonium Sulfamate

http://www.sid.ir/en/VEWSSID/J_pdf/84320080110.pdf

Detonation Properties and Reaction Rate Modeling of
Melt Cast Ammonium Dinitramide

http://www.intdetsymp.org/detsymp2002/PaperSubmit/FinalManus...

ADN – New Oxidizer for an Environmentally Friendly Smokeless Propellant
http://www.jatm.com.br/papers/vol1_n2/JATMv1n2_p153-160_ADN-...

New Insensitive High Explosives
http://preterhuman.net/texts/terrorism_and_pyrotechnics/expl...


Methods of Forming Dinitramide Salts
Patent US5198204

Process for Forming Dinitramide Salt by Reaction Between
Ammonia and a Nitronium Containing Compound
Patent US5316749

Process for Preparing Ammonium Dinitramide
Patent US5714714

Propellant Formulations Based on Dinitramide Salts
and Energetic Binders
Patent US5498303 and US5741998

Method of Preparing Dinitramidic Acid and Salts Thereof
Patent US5976483

Methods of Producing Salts of Dinitramidic Acid
Patent US20080226533

Preparation of Ammonium Dinitramide Crystals and
Energetic Composites Containing Them
Patent US20090090441

.

[Edited on 24-6-2010 by franklyn]

Ammonium Dinitramide.gif - 24kB

JohnWW - 23-6-2010 at 18:23

Quote: Originally posted by franklyn  
(cut)
ADN – New Oxidizer for an Environmentally Friendly Smokeless Propellant
http://www.jatm.com.br/papers/vol1_n2/JATMv1n2_p153-160_ADN-...
. (cut)

The file was not found on the server in this URL.

Anders Hoveland - 23-6-2010 at 18:29

All right, I take it back; I was incorrect and could easily have checked to see whether the dintramide of magnesium existed. But only one reference was really necessary to disprove me. You seemed to go at great, unnecessary lengths to show that the salt exists. I am not aware of other "mistaken assumptions" that I have been corrected on that I continue to post. In just a few cases however, I have not found the evidence strong enough to change my view. (for example, I am still of the opinion that Cl2O7 is unreactive in many cases, although it is prone to explode with just about anything) Save your "piqued" responses for those other cases.
Microtek keeps going on about keto-RDX having a higher density and being more powerful. I do not disagree with that; I am just saying that in this case higher density is not what is making it more powerful.

not_important - 23-6-2010 at 21:26

John - the URL worked for me, just watch out for characters the board&browser stick in, and is the 1st hit if you search for the paper title.

http://www.jatm.com.br/papers/vol1_n2/JATMv1n2_p153-160_ADN-...

shortened
http://7.ly/3K


Quote:
Quote:
You seemed to go at great, unnecessary lengths to show that the salt exists.
...you continue stating related mistaken assumptions after repeatedly
being corrected.
Quote:
...I do not disagree with that; I am just saying that in this case higher density is not what is making it more powerful.


There's a partial answer. And in response to your reason for doing as you did, I would say that you should - especially until you establish yourself supply somewhat detailed reasons as to why your assertion is true, and if possible links or quotes from reference materials such as journal paper and technical reports. And you can ask for similar from those with differing views, they need to be able to back up their assertions too.




Microtek - 24-6-2010 at 04:19

I don't know what you mean when you say that keto-RDX is more powerful because it is more unstable. Would you care to elaborate on what links stability with brisance?

Also, high energy of formation of the decomposition products would be undesirable. I presume you meant to say the reverse.
In any case brisance is only weakly dependent on energy and much more strongly on density. You could take a look at the Kamlet-Jacobs equation for predicting the VOD and Pcj of explosives.

Anders Hoveland - 24-6-2010 at 21:55

I mean to say that some of the bonds in keto-RDX are weaker, because of the electron withdrawing effect of the oxygen, and the lack of two hydrogens that are somewhat electron donating. keto-RDX is easy to make, just use urea and less formaldehyde. In my opinion, the added strength is not worth the added sensitivity, if one is trying to get a high "power to instability ratio". Also, more unstable compounds are more brissant than more insensitive compounds in small quantities. Consider Ethyl Perchlorate. I do not think it is a particularly strong explosive when compared to others in bulk, but small quantities are capable of being almost instantly set off by a very small trigger, whereas a small sample of RDX would not go off together so simultaneously because it has a higher threshold to detonate.
To illustrate what I mean about density, you could add an iodine onto the methyl group in TNT. That would increase density, but not add more power. You could mix lead powder with your explosive. Obviously that would not make it more powerful. Adding non-functional groups might increase density, but just dilutes the explosive.

[Edited on 25-6-2010 by Anders Hoveland]

The_Davster - 24-6-2010 at 22:38

For comparison of CHNO energetics, density and heat of formation are both the driving factors with a subtle interplay between them. Naturally, the incorporation of heavy atoms can lead to high densities (eq, lead azide) but heavy-atom energetics do not display high VODs.

If keto-rdx is less stable than RDX, said instability would be manifested as a more positive heat of formation.
k-RDX -41.9 KJ (Thermochimica Acta Volume 426, Issues 1-2, February 2005, Pages 53-60 )
RDX +58 KJ/mol (Journal of Hazardous Materials Volume 133, Issues 1-3, 20 May 2006, Pages 30-45 )

So we see keto RDX is a more stable compound, posessing stronger bonds, with an exothermic heat of formation
RDX on the other hand has a positive, endothermic heat of formation.
In the case of RDX vs keto RDX the higher detonation parameters of k-RDX is soley due to density, and is in spite of the more exothermic heat of formation.

HEDM parameters.JPG - 21kB

[Edited on 25-6-10 by The_Davster]

Microtek - 25-6-2010 at 05:14


Quote:

Also, more unstable compounds are more brissant than more insensitive compounds in small quantities. Consider Ethyl Perchlorate. I do not think it is a particularly strong explosive when compared to others in bulk, but small quantities are capable of being almost instantly set off by a very small trigger, whereas a small sample of RDX would not go off together so simultaneously because it has a higher threshold to detonate.


It seems to me that you are confusing the concepts of stability and sensitivity. With regards to your statement about brisance of small amounts, that is true but irrelevant; it is the difference between what we call primary and secondary explosives.

-=HeX=- - 27-6-2010 at 13:33

Primaries and secondaries are totally different.

With secondaries, we talk about Brisance and VoD and 'work potential' and so on.

With PRIMARIES, we discuss unequivocality, DDT threshold, etc.

Now, lets consider this. A primary goes in TINY amounts, and the good ones can do incredible work in such amounts... But they are unsuitable to use in anything over, say, 1 gram.

1 gram TNT, RDX, etc aint much. Thats cos secondaries are for use in bigger amounts.

Density is useful cos shockwaves travel faster through more dense stuff, and cos you can pack more energy containing molecules into less volume. Though tagging on useless shit like Iodine onto the Methyl in TNT is totally pointless cos it wont help the energy.

However, high density matter tends to allow us to pack more energy into smaller volume, hence better cos more more VoD. I am hungover right now and cant explain but it is simple science. Microtek can explain better, as he is the 'God of Micro Charges'.

Anders Hoveland - 29-6-2010 at 16:57

Perhaps picric acid will neutralize the other amine in hydrazinium perchlorate, forming a double salt.
The picric acid would improve the oxygen balance and add stability.

-=HeX=- - 30-6-2010 at 12:01

Ok. Can you draw a nice picture to go with that, cos all I can think of is a co-ppt of Hydrazine-Picrate and Hydrazine Perchlorate. Though, I know that Hydrazine-Azide and hydrazine-perchlorate, at OB neutral, is damn fine.
Or are you meaning something like in my shit attach picture?
I cant think straight, tired and stressed BTW. Sorry.

EDIT.
Pic wont fit or something. Fuck it. Basically it was
Picrate-(H2H4)-Perchlorate

[Edited on 30-6-2010 by -=HeX=-]

Anders Hoveland - 1-7-2010 at 19:40

Yes, (NO2)3PhO(-) (+)NH3NH3(+) ClO4(-)

Where there are N2H6 (+2) cations and a mix of picrate and perchlorate.

Now, let me throw in something to make it even MORE confusing.

Acetone forms a temporary condensation product with hydrazine; this is utilized in a modified Raschig synthesis (wikipedia).

Picric acid, as I have recently described in another post, likely will be able to react through a tautomeric ketone to condense with NH2OH... or with NH2NH3(+) ! There is a diagram somwhere in "Quinone Explosives" topic.

Thus, may get the salt (NO2)3PhNNH3(+) ClO4(-)
This would be even more powerful, since it is the dehydrated form of the double salt I described.
Ph = phenyl obviously

franklyn - 16-7-2010 at 21:12


Who knew that a seeming inert ceramic , Boron Nitride , can serve as fuel
in a sprengel admixture. This is literally OTC but details are sparingly available.
It appears that BN powder soaked with fuming nitric acid is comparable to
some blends of aromatics with tetranitromethane.

The Future of Warheads Armor & Ballistics
mentiond on page 7
http://www.mater.upm.es/ISB2007/Proceedings/PDF/Volume_1/Vol.I(1)GS01.pdf

Reaction Mechanisms in Shocked, Intercalated Graphite and Boron Nitride
http://hal.archives-ouvertes.fr/docs/00/25/37/51/PDF/ajp-jp4...

related thread _
http://www.sciencemadness.org/talk/viewthread.php?tid=13189

.

franklyn - 16-7-2010 at 21:23

Regarding the Silicon explosive compound disclosed here _
http://www.sciencemadness.org/talk/viewthread.php?tid=1970&a...

Another investigation of it.
Explanation of the Colossal Detonation Sensitivity of Silicon Pentaerythritol Tetranitrate (Si-PETN) Explosive
http://www.wag.caltech.edu/publications/sup/pdf/806.pdf

A related thread _
http://www.sciencemadness.org/talk/viewthread.php?tid=1244#p...

.

franklyn - 22-7-2010 at 05:18

Ramiel had cited this some time back
http://www.sciencemadness.org/talk/viewthread.php?tid=1970&a...

Syntheses of 1,2,3,4-Tetrazine Di-N-oxides, Pentazole Derivatives, Pentazine Poly-N-oxides, and Nitroacetylenes
http://handle.dtic.mil/100.2/ADA445136
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA445136&Locati...


Synthesis of 1,2,3,4-Tetrazines, 1,2,3,4-Tetrazine Di-N-oxides, Pentazole Derivatives, Pentazine Poly-N-oxides, and Nitroacetylenes
http://handle.dtic.mil/100.2/ADA430332
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA430332&Locati...

.

franklyn - 22-7-2010 at 15:48

No explosive properties discussed but related to this previous post
http://www.sciencemadness.org/talk/viewthread.php?tid=1970&a...

High Temperature Oxidation of Boron Nitride
http://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/2001006...

Intercalation of Hexagonal Boron Nitride by Strong Oxidizers
http://www.physics.berkeley.edu/research/zettl/pdf/234.SolSt...

.

.

Nothing but Nitrogen

franklyn - 22-7-2010 at 22:29

Novel High Pressure Structures of Polymeric Nitrogen
http://mysbfiles.stonybrook.edu/~aoganov/files/Nitrogen-PRL-...

Novel High Energy Density Materials Synthesis by Megabar Hot Pressing
http://www.osti.gov/bridge/servlets/purl/231384-GWqCC5/webvi...

Attachment: Polymeric Nitrogen.pdf (673kB)
This file has been downloaded 1619 times

maxidastier - 18-8-2010 at 08:50

Has this been postet already:

http://teroras.sprogmenys.net/kestonei/Nitroureas%20II.%20Sy...

maxidastier - 4-9-2010 at 08:36

Does someone have this pdf?

http://onlinelibrary.wiley.com/doi/10.1002/prep.19940190504/...

Anders2 - 4-9-2010 at 12:27

Have been working on a new site for lesser known energetic compounds:

https://sites.google.com/site/energeticchemical/home
or for the site directory:
https://sites.google.com/site/energeticchemical/system/app/p...

MonoMethyl Hydrazinium Nitroformate has a det. velocity of 9.134km/sec. This compares with 8.93 for RDX. MMHNF is also 212% more powerful than TNT on a weight basis, compared with 163% for RDX. The two compounds have similar sensitivity. The article claims, "The decrease in impact sensitivity on alkyl substitution can be explained on the basis of the increase in basicity of hydrazine on alkyl substitution, entailing stronger holding of the nitroformate group, leading to greater stability." However, I am uncertain if this is correct. I would think adding methyl groups would decrease basicity, as holds true for amines (with the exception of the tetramethyl ammonium anion that serves as a superbase). A more likely reason would be that the methyl groups are more inert to combustion, and so dilute the more sensitive hydrazine, while at the same time improving the oxygen balance.

Journal of Chem. Tech. Vol12 2005
"Synth, Characterization, and thermal behaviour of hydrazinium nitroformate..."
H.S. Jadhav, M.B. Talawar (India)



maxidastier - 7-9-2010 at 12:07

Someone got more about this.
Please!

http://resources.metapress.com/pdf-preview.axd?code=h623qq36...

Dinitro-[di-Furazanyl-Hydrazine]

AH-Poster - 17-10-2010 at 12:27

This is an experimental compound that very few people know about. There was a very short synthesis on the "Controversial Chemlab",
http://web.mit.edu/semenko/Public/Military%20Manuals/RogueSc...
but now here is a more substancial synthesis. I do not know how powerful this compound is, but Azidonitroazoxyfurazan, which is the same thing exept with a --N=N-- in the center instead of --NHNH--, is stated as having 120% the power of HMX in a patent.

This compound has a structure of (NO2)(C2N2O)NHNH(C2N2O)(NO2), where (C2N2O) is a furazan ring. It is also known as dinitrohydrazofurazan. This compound probably has a power between RDX and HMX, with a lower sensitivity. The gas products from decomposition would be hoter than that from RDX, but the compound is probably less energetic than the nitramines. The linking hydrazine group may make the compound less chemically and thermally stable than the nitramines, although since the hydrazine is electron donating, it will be less susceptable to oxidation than otherwise. The furazan rings do not lend themselves to aromaticity, so the extent of the hydrazine stabilizing the molecule through electron donation will be severely curtailed. The presence of the hydrazine will allow molecules to pack closer together through hydrogen bonding, the hydrazine also serving to link together two nitrofurazan groups, giving a higher density than the nitramines.

Synthesis:
To 25mL ethanol in a 100mL round bottomed flask, 0.013g (0.00022 moles) glacial acetic acid was added. To this was added 0.05g (0.0002 moles) DinitroAzoFuroxan, and 0.5g iron wire (Zn powder may substitute). This is stirred at reluxed for one hour, then 25mL water and about 1g sodium bicarbonate was added. This was extracted with three 20mL allotments of methylene chloride CH2Cl2. The extracts were washed twice with water and the resulting solution was then dried with anhydrous MgSO4 and filtered. The solvent was removed to leave yellow crystals, which had a melting point over a a 160-171degC transition. The compound exothermically decomposes at 215C. If heated rapidly 12deg beyond this, it detonates.

DinitroAzoFurozan Precursor:
In a 250mL round bottomed flask, 0.40g AminoNitroFurazan was dissolved in 16mL concentrated HCl (0.53mol). 0.95g (0.006mol) Potassium permanganate was dissolved in 105mL water. The acid solution in the round bottomed flask was heated to 40degC, then the permanganate solution was slowly dripped into the round botomed flask, over the period of 1 hour. The resulting dark brown solution was heated to a little under 57degC for 2 hours with continued stirring. The solution was cooled, then it was extracted with four 50mL allotments of methylene chloride. The extracts were washed with water, then dried with anhydrous MgSO4 and filtered. The remaining solution was evaporated under reduced pressure until an orange oily liquid remained, which contains Diamino di-Furazanyl-Hydrazine; to crystallize the compound out, it must be repeatedly dried with organic solvent and evaporated, and finally be chilled.

AminoNitroFurazan
100mL flask placed in ice bath and constantly stirred, 56mL 50% H2O2 solution (0.97mol) was added, keeping temperature under 5degC. 5g of sodium tungstate Na2WO4 was added, 1.1g of DiaminoFurazan was added and allowed to react for 12 hours. The resulting yellow solution was neutralized with sodium carbonate until neutral pH was reached. The solution was filtered and extracted, similar to the procedures described above. Yellow Crystals were obtained on evaporation, melting over 120-125degC, with explosion at 170degC.

These are tested procedures, however a theoretical shortcut would be to bubble a limited quantity of NO2 into the furazan of ethylene, giving mono-nitrofurazan, which has a significantly lower vapor pressure than the original reactant, then addition of chlorine will make nitro,chloro furoxan. This will condense with symetric diacetyl hydrazine, and this will slowly hydrolyze in hydrazine hydrate to form Dinitro-[di-Furazanyl-Hydrazine]. Diacetyl hydrazine can be made by treating concentrated N2H4 with Ac2O, no unsymetric diacetyl hydrazine will be produced. Note that both nitrogen dioxide and chlorine react at room temperature with the furazan of ethylene, since double bonds exist on the carbon.


[Edited on 17-10-2010 by AH-Poster]

franklyn - 31-10-2010 at 11:44

Quote: Originally posted by AH-Poster  
Dinitro-[di-Furazanyl-Hydrazine]
" I do not know how powerful this compound is, but Azidonitroazoxyfurazan, which is the
same thing exept with a --N=N-- in the center instead of --NHNH--, is stated as having
120% the power of HMX in a patent." / / " also known as dinitrohydrazofurazan "


Given the comparable density of ~ 1.8 , my understanding is that performance can be
expected to closely coincide with that of PETN.
A depiction of the structure goes a long way to obviating confusion arising from naming
conventions. Numbers 6 & 12 in the chart below is I suppose the two mentioned compounds.

" Azido " necesarilly means the presence of an azide group - N3
and an azo group " --N=N-- in the center " is certainly not an " azoxy " group
http://en.wikipedia.org/wiki/Azoxy. hydrazo properly termed hydraza

If known , stating the number of said patent goes a long way to providing a basis for dialog ,
could this perhaps be it ? => Attachment: Furazan Derivatives US 20100132856.pdf (642kB)
This file has been downloaded 942 times

Providing references similarly goes a long way to assessing the procedures stated.

See pdf index page 37 ( 2.12 ) , 73
Structures & Chemistry of Amino & Nitrofurazans
http://handle.dtic.mil/100.2/ADA378735
Redirects to :
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA378735&Locati...

Attachment: Review of Energetic Materials Synthesis - Furazans .pdf (135kB)
This file has been downloaded 933 times

Structure of Nitrofurazans .gif - 45kB

AndersHoveland - 2-3-2011 at 16:33

I made a modest compilation of information about octonitrocubane:
https://sites.google.com/site/energeticscribble/comparison-w...

The final step uses bi-(trimethylsilyl) amino lithium as an alkaline reagent. Nitrosyl chloride is bubbled in, then treatment with ozone (oxidizing the nitroso groups to nitro) to get eight nitro groups on the cubane cage, the yield was 55% in this step.

octanitrocubane has a heat of formation of 257.20 kcal/mol

octonitrocubane has a calculated heat of formation of 594kcal/mol , with an observed det veloc of 9.9 km/sec (at a density of 1.979 g/cm3)

Heptanitrocubane has a density of 2.028 g/cc


(there did not seem to exist a topic devoted to octonitrocubane, so this seemed like the best place to put it)

madscientist - 2-3-2011 at 18:53

Where are your references? Your source doesn't cite a single one!

AndersHoveland - 23-5-2011 at 16:29

In Germany, Thomas Klapötke and Davin Piercey of the University of Munich, synthesized a double ringed tetrazole compound that contains a continuous chain of 10 nitrogen atoms, with the formula C2H2N10.
The bis tetrazole joined by an azo linkage proved to be so explosive that the dry compound easily exploded, destroying glassware and setting off further explosions as glass shrapnel hit other samples of the compound around the lab.

http://www.rsc.org/chemistryworld/News/2011/March/16031102.a...

could someone please attach the picture to this forum, in the event the link later becomes non-functional?

I think the correct chemical name for this is N,N’-azo-1,1'-bistetrazole. Please correct me if I am wrong.
The structure (in the event the attached picture becomes unavailable in the future) is
{HCN4}N=N{N4CH}
where both carbon atoms are bonded to hydrogen atoms, and the central diazo linking group is bonded to nitrogen atoms on each of the rings, not the carbon atoms, making this compound structurally different from most of the other azo-bis-tetrazole compounds that have been prepared.
[file]14298[/file]

[Edited on 27-5-2011 by quicksilver]

009 - 1-6-2011 at 03:13


here is the image:


And youtube video
http://www.youtube.com/watch?v=Txa0fgIwiLA

"setting off further explosions as glass shrapnel hit other samples of the compound around the lab."

That is an exaggeration due to pluralization. Only one other went off.

ps. if anyone here makes this, please be careful. It is a bastard child of HMX and NI3

[Edited on 1-6-2011 by 009]

PHILOU Zrealone - 6-6-2011 at 04:45

I wonder if the very same molecule but bridged by the carbon into a tricyclic compound would exist...
C2N10
Three tetrazine rings (two pentarings and one hexaring) glued together in a coplanar fashion must be much denser and so even more energetical but stil quite unstable.



The left form would be less stable than the right one, because the chain of N atoms in the right one is shorter and that usually calls for stability...

[Edited on 7-6-2011 by PHILOU Zrealone]

DicyanoDinitroMethane

franklyn - 13-6-2011 at 06:20

Continuing the investigation of this earlier post
http://www.sciencemadness.org/talk/viewthread.php?tid=1970&a...

This hypothetical reaction of Malononitrile with Dinitrogen Tetroxide serves only to obtain
thermodynamic data in kilocalories for estimation. Cited values from NIST Chemistry WebBook
CH2(CN2)2 + 2 N2O4 => 2 HNO2 + / C(CN)2(NO2)2 => CO2 + 2 CO + 2 N2
+ 44.9 + 2 (- 4.7) => 2 (- 18.3 ) / + 72.1 Kcal/mol => - 94 + 2 (- 26.4 ) = - 218.9 Kcal/mol ∆He (Heat of explosion)
calculated ∆Hf (Heat of formation)

To derive a value for the density I have applied the method of H. H. Cady outlined in
LA-7760-MS , http://www.sciencemadness.org/lanl2_a/lib-www/la-pubs/003214...
Estimation of the Density of Organic Explosives from Their Structural Formulas

Density ( ρ ) is weight divided by volume ( mol weight )( k ) / V
1 5 6. 0 7 x 0.7686 / 6 9. 0 8 Derived value comes to ρ = 1.736 gm/cm³

Dividing the ∆He Heat of explosion of 1 mol of the compound by it's molar weight , - 2 1 8.9 / 1 5 6.07
obtains ∆He Heat of explosion = - 1 4 0 2 Kcal per kilogram of compound ' Q '

To estimate the Detonation pressure generated and Velocity of Detonation ,
I have applied the method of M.J. Kamlett, S.J. Jacobs outlined in
The Journal of Chemical Physics , vol 48 , num 1 , http://handle.dtic.mil/100.2/AD661483
A Simple method for Calculating Detonation Properties of C-H-N-O Explosives

Values for M is 36 , for N it's 0.256

Detonation pressure = P = 15.58 ρ ² ( N √ M √ Q )
P = 270 Kilobar

Velocity of Detonation = V = 1.01 ( 1 + 1.3 ρ ) √( N √ M √ Q )
VOD = 7880 Meters/sec

Complete procedure detailed in this post
http://www.sciencemadness.org/talk/viewthread.php?tid=11195#...
Please observe subsequent correction noted here
http://www.sciencemadness.org/talk/viewthread.php?tid=11195&...

------------------------------------------------------------------------------------------

C-H Bond Dissociation Energy of Malononitrile
http://www.chem.arizona.edu/sanov/pdf/jz900379treprint.pdf

On the Non-Additivity of pK Values of Polynitromethanes
http://abulafia.ciencias.uchile.cl/publicaciones/pdf/12-Tetr...

A Comparative ab initio Study of the Dicyanomethanide, Cyanonitromethanide, Dicyanamide and Cyannitramide Anions
http://actachemscand.dk/pdf/acta_vol_31a_p0151-0154.pdf

------------------------------------------------------------------------------------------

Curiously the anticipated elevated performance one might expect of a cyano - nitro compound
is not realized upon analysis by Kamlett / Jacobs. This excercise demonstrates the value of
ab initio projection of performance. Interestingly by comparison the detonation utility of forum
member ' Engager ' estimates this much higher.
http://www.sciencemadness.org/talk/files.php?pid=169218&...

- * Please cite any apparent error which may account for this wide discrepancy.

Detonation Utility by Engager.gif - 14kB

HE calc by ' enhzflep ' similarly , although this tends to overstate levels of performance
http://www.sciencemadness.org/talk/files.php?pid=64852&a...

HE calc by enhzflep.gif - 9kB

------------------------------------------------------------------------------------------

Formation of this hypothetical structure might be realized by displacing the Chlorine
of Dicyanonitrochlormethane C(CN)2(NO2)Cl, possibly by solvation in DMSO with
Sodium Nitrite. C(CN)2(NO2)Cl + NaNO2 => NaCl + C(CN)2(NO2)2

Dicyanonitrochlormethane C(CN)2(NO2)Cl itself is made from Potassium Cyanide and Chloropicrin
( KCN + CCl3NO2 ) as described here :

A Dictionary of Chemistry and the Allied Branches of Other Sciences Vol 6 1872
Dicyanonitrochloromethane , page 446

http://books.google.com/books?id=sKktAAAAYAAJ&pg=PA446&a...

Chloropicrin heated with potassium cyanide, alcohol, and water, is converted
into dicyano-nitro-chloromethane, C(NO2)Cl(CN)2 This compound is soluble in
water, alcohol, ether, and chloroform, very easily decomposible, and has not
been obtained in the separate state, but only in combination with water, and
with metallic oxides and salts. Lead acetate added to its aqueous solution
forms a prescipitate obtaining C(NO2)Cl(CN)2 • 3PbO ; with silver nitrate a
precipitate is formed consisting of 3C(NO2)Cl(CN)2 • 4NO3Ag • 8H2O
For the details of the preparation, which requires particular precautions
we must refer to the original paper. On a Cyanogen Derivative of Marsh Gas
( Bassett, Chem. Soc. J. [2] iv. 352 ). Journal of the Chemical Society ( J. Chem. Soc.)
Many thanks to forum member ' gsd ' for providing this paper. - Attachment: Dicyano nitrochloro methane.pdf (110kB)
This file has been downloaded 756 times


Chloropicrin may readily made in at least two ways described below.

http://www.sciencemadness.org/talk/viewthread.php?tid=3214&a...
http://www.youtube.com/watch?v=OxPoWZJW20o
http://www.sciencemadness.org/talk/viewthread.php?tid=710

A Bibliography of Chloropicrin 1848-1932
http://books.google.com/books?id=sq4oAAAAYAAJ&lpg=PA19&a...
Chloropicrin by Aqua regia on Acetone

Chloropicrin by Aqua regia on Acetone.jpg - 48kB

--------------------------------------------------------------------------------

http://history.amedd.army.mil/booksdocs/wwi/VolXIV/VolXIVhtm...

CHLOROPICRIN

Chloropicrin, CCl3NO2, is a colorless liquid, boiling at 112 °C, and having a vapor pressure of 5.8 mm.
at 0 °C, 14.0 mm. at 15 °C, and 23.8 mm. at 25 °C. The vapor is nearly six times as dense as air. The
density of the liquid is 1.6924 at 4 °C and 1.6539 at 20 °C, the two determinations not being made by
the same man. The melting point is - 69.2 °C. Chloropicrin is not sufficiently volatile for use by itself in
cloud attacks. While it has been used mixed with 75 percent chlorine, it was usually fired in shell. It is
moderately toxic, 0.8 mg. per liter (110 p.p.m.); somewhat lacrymatory, 0.016 mg. per liter, and liable
to cause vomiting, thus forcing removal of the mask. It was not stopped satisfactorily by the charcoal
first used in the masks. The laboratory charcoal eventually employed was about one thousand times as
effective as the earlier material. Chloropicrin is practically nonmiscible with water, and a mixture of the
two boils at about 84 °C. It is miscible in all proportions with many organic solvents. There is a marked
evolution of heat when it is mixed with methyl alcohol, ether, or acetophenone; a slight evolution of
heat when mixed with isobutyl alcohol, isoamyl alcohol, or carbon bisulphide.

Chloropicrin is not hydrolyzed by water, nor by cold hydrochloric, sulphuric, or nitric acid. When heated
with these acids it is said to distill unchanged. Dilute aqueous sodium hydroxide does not attack it; but
alcoholic sodium hydroxide decomposes it slowly, and sodium ethylate attacks it fairly readily, forming
the orthocarbonic ether, CCl3NO2 + 4C2H5ONa = C(OC2H5)4 + 3NaCl + NaNO2. Chloropicrin can be
heated for several days with aqueous ammonium hydroxide at 100 ºC without undergoing any
appreciable change. At 150 ºC, or when heated with alcoholic ammonia, a reaction takes place in a few
hours, guanidine being formed, HN:C: (NH2)2. Alcoholic potassium acetate decomposes chloropicrin
completely at 100 ºC and alcoholic potassium cyanide reacts at a lower temperature, the product in
this last case having the formula (CN)2C(NO2)-Cl.
. Though chloropicrin is attacked very slowly by dilute
aqueous sodium hydroxide, it unites readily with neutral potassium sulphite,
CCl3NO2 + 3K2SO3 + H2O = CH(NO2)(S03K)2 + 3KCl+KHSO4.


http://cameochemicals.noaa.gov/chemical/387
http://www.cdc.gov/NIOSH/ershdb/EmergencyResponseCard_297500...
http://www.cdc.gov/niosh/idlh/76062.html
http://www.cdc.gov/niosh/npg/npgd0132.html
http://pmep.cce.cornell.edu/profiles/extoxnet/carbaryl-dicro...
http://en.wikipedia.org/wiki/Chloropicrin
Attachment: Chloropicrin MSDS.pdf (113kB)
This file has been downloaded 1096 times
Attachment: Chloropicrin label use.pdf (21kB)
This file has been downloaded 778 times

.

franklyn - 25-6-2011 at 17:05

A closely related compound Ammonium dinitroacetonitrile NH4C(NO2)2CN has crystal density about 1.8 g/cc

Clipboard1.gif - 44kB

Clipboard2.gif - 22kB

Clipboard3.gif - 22kB

Clipboard4.gif - 18kB

Chemistry of dinitroacetonitrile I
http://www.sciencedirect.com/science/article/pii/S0040402001...
Chemistry of dinitroacetonitrile II
http://www.sciencedirect.com/science/article/pii/S0040402001...
Chemistry of dinitroacetonitrile III
http://www.sciencedirect.com/science/article/pii/S0040402001...
Chemistry of dinitroacetonitrile IV
http://www.sciencedirect.com/science/article/pii/S0040402001...

Lead-Free Initiator Materials for Small Electro-Explosive Devices
for Medium Caliber Munitions Final Report 04 June 2003

www.dtic.mil/dtic/tr/fulltext/u2/a438486.pdf

J. B. Christian, Nav. Ord. 3387 N.O.L. (1954) p. 23.

.

franklyn - 9-7-2011 at 09:05

Explosives research has proceeded principally by inspiration of the researchers.
In recent times exhaustive analysis of every conceivable or imaginable molecule
has become feasible with the advent of computers running algorithms to compile
encyclopedic ab initio data identifying promising candidate structures. The problem
with this approach is that once a particular molecule deemed worthy of research
is identified , the way and means of it's synthesis remains to be speculated about ,
since the programs only consider functional groups and moieties not reaction
schemes. In my view it may be more productive to look for precursors that can
readily host explosophore functional groups using well established reaction schemes.
If you 're wondering at the practicality of this approach , this is how Edison developed
his light bulb , literally going to the haystack and sampling every straw until he found
the needle - 17000 experiments later. He was grossly understating the problem
when he quipped " invention is 1 % inspiration and 99 % perspiration ".

In a related post I outlined the range of possible base adducts applicable for addition
compounding here => http://www.sciencemadness.org/talk/viewthread.php?tid=13174#...
Threads in the references section citing papers on investigatory research into new
explosives compounds.
http://www.sciencemadness.org/talk/viewthread.php?tid=7518&a...
http://www.sciencemadness.org/talk/viewthread.php?tid=7518&a...
http://www.sciencemadness.org/talk/viewthread.php?tid=7518&a...

PHILOU Zrealone outlined here candidate functional groups for energetic compounds
http://www.sciencemadness.org/talk/viewthread.php?tid=1778#p...

Cyclizations A.gif - 32kB Cyclizations B.gif - 34kB

Summarized in the chart above is the seven reaction schemes depicted above it. The
varied products highlight the range of possible outcomes from a few precursors. The
order in which reagents are introduced in a reaction scheme affects the result obtained,
what is produced and the yield of product. Exhaustively investigating every conceivable
interaction of selected reagents can yield many new and unexpected results.
What this does is provide a framework for rigorous systematic evaluation.
Of course many schemes will not yield any useful results.

______________________________________________________________

When we are concerned with a group as a set without reference to any order, it is a problem in combination.
A permutation is a combination of objects that has also an order or sequence of arrangement imposed.

There is only one group combination , A, B, C, of that there can be 3 groups A, B, , A, C, , B, C, each in turn can
have 2 permutations ( A, B, or B, A,) ( A, C, or C, A,) ( B, C, or C, B,) adding the missing letter to each we have
A, B, C, , A, C, B, , B, A, C. , B, C, A, , C, A, B, , C, B, A, , note that none repeat an order.


If there are 9 horses in a race and only the first 3 to finish pay off , how many groups of winners can there be ?

9 x 8 x 7 = 84
3 x 2 x 1

How many ways are there in the order those 84 groups can finish ? 9 x 8 x 7 = 504

since the ways to place 1st , 2nd , 3rd of any particular group is 3 x 2 x 1 = 6 , then 6 x 84 = 504

_______________________________________________________________

There is only one combination of the 5 reagents but 120 possible permutations of the
order in which they can be reacted. There are 5 possible combinations of 4 of the reagents
with 24 possible permutations of the order in which each of those can be reacted.
10 possible combinations of any 3 of the listed reagents having 6 permutations each.
10 combinations of any 2 reagents , with some exceptions order matters little at this point.

U - urea , F - formaldehyde , G - glyoxal , S - sulfamate , N - nitromethane

- the combinations of groups of 3 out of the 5 -
UFG , UFS , UFN , UGS , UGN , USN , FGS , FGN , FSN , GSN

- and their permutations -
UFG , UGF , GUF , GFU , FUG , FGU
UFS , USF , SUG , SFU , FUS , FSU
UFN , UNF , NUF , NFU , FUN , FNU
UGS, USG , SUG , SGU , GUS , GSU
UGN, UNG, NUG , NGU, GUN , GNU
USN , UNS, NUS , NSU , SUN , SNU
FGS , FSG , SFG , SGF , .GFS. , GSF
FGN , FNG, NFG , NGF , .GFN , GNE
FSN , FNS , NFS , NSF , .SFN , SNF
GSN, GNS, NGS , NSG , SGN , SNG

__________________________

- the 5 groups of 4 combined reagents out of the 5 -
UFGS , UFGN , UFSN , UGSN , FGSN

- and now their permutations -
UFGS , FUGS , FGUS , FGSU
UFSG , FUSG , FSUG , FSGU
UGFS , GUFS , GFUS , GFSU
UGSF , GUSF , GSUF , GSFU
USFG , SUFG , SFUG , SFGU
USGF , SUGF , SGUF , SGFU

UFGN , FUGN , FGUN , FGNU
UFNG , FUNG , FNUG , FNGU
UGFN , GUFN , GFUN , GFNU
UGNF , GUNF , GNUF , GNFU
UNFG , NUFG , NFUG , NFGU
UNGF , NUGF , NGUF , NGFU

UFSN , FUSN , FSUN , FSNU
UFNS , FUNS , FNUS , FNSU
USFN , SUFN , SFUN , SFNU
USNF , SUNF , SNUF , SNFU
UNFS , NUFS , NFUS , NFSU
UNSF , NUSF , NSUF , NSFU

UGSN, GUSN, GSUN , GSNU
UGNS, GUNS, GNUS , GNSU
USGN, SUGN, SGUN , SGNU
USNG, SUNG, SNUG , SNGU
UNGS, NUGS, NGUS , NGSU
UNSG, NUSG, NSUG , NSGU

FGSN, GFSN , GSFN , GSNF
FGNS, GFNS , GNFS , GNSF
FSGN, SFGN , SGFN , SGNF
FSNG, SFNG , SNFG , SNGF
FNGS, NFGS , NGFS , NGSF
FNSG, NFSG , NSFG , NSGF

Ths only assumes a simple serial addition.
This does not consider the mixing of pairs
of already premixed reagents , for example
NSGF seen immediately above here can
also be arrived at in an altered reaction
scheme by adding to NS , GF.

.

[Edited on 9-7-2011 by franklyn]

AndersHoveland - 9-7-2011 at 10:29

I disagree. While investigating every possible permutation of target molecule and testing the result is productive, though time consuming, researchers do and should save much time and effort by just ignoring combinations that are fairly certain not to yield desirable properties. Trying consider every permutation of reaction order of addition would just be a big waste of time, even with sophisticated computer programing. Knowledged intuition is essential to designing, and synthesizing, new better energetic compounds. While many compound have been discovered by accident, the increasing complexity of molecular structures and synthesis makes it extremely unlikely now that any advances can be made relying on chance. All the low hanging apples have already been plucked from the tree, so to say.

Energetic research could be advancing much more rapidly if there was more research funding to attract talented chemists, but as it is, there are only about 25 energetic researchers in the USA, and half of those do not even do research full time. I have a feeling that often they simply give up on target many molecules because they cannot figure out a workable synthesis, or do not care enough to hire a highly knowledged consultant.

Personally, I would like to see some research done on the target molecules I designed.
http://www.shadowrx.com/forums/showthread.php?t=1505

franklyn - 9-7-2011 at 11:51

@ AndersHoveland

Lonely molecules left unrealized does not comprise useful practice of effort.
You are assuming an omniscience which does not exist nor can it be possible.
Just as the practice of integration in calculus involves the use of references
that detail known integrals - because their derivation is otherwise practically
unrealizable.
The common constituent of most of the now over 50,000,000 identified molecules
is the aromatic carbon ring , yet less than 1000th of one percent would ever
involve benzene as a starting material in their synthesis. As an example if Mesitylene
were a target how would one naively approach this ? The counterintuitive reaction
of acetone and sulfuric acid likely would not spring to mind. Reaction schemes are
what is wanting , not the target molecules.

.

Adas - 16-10-2011 at 11:42

I have found a new N10 molecule.
This is from Wikipedia:

"Chlorine azide is prepared by passing chlorine gas over silver azide or by an addition of acetic acid to a solution of sodium hypochlorite and sodium azide.[3]
When treated with ammonia it is conceivable that one or more of the three possible azinamines, NH2N3, NH(N3)2, and N(N3)3 may be formed."

N(N3)3 is mentioned. But I can't find any other info about it. Any ideas?

AndersHoveland - 27-10-2011 at 18:30

Quote: Originally posted by 12332123  
Or, if one doesn't mind hyperactive sensitivity, aminotetrazolium nitroformate could be synthesised. This has perfect oxygen balance and would likely beat HMX by a fair margin (IIRC the dinitramide salt has a detonation velocity ~9500)


I do not think aminotetrazolium nitroformate would be particularly sensitive. Ammonium nitroformate is very stable, and even hydrazinium nitroformate is stable enough for use as a rocket fuel oxidizer. Hydrazinium nitroformate has a friction sensitivity of 25-36 N, compared to 120 N for RDX. Aminotetrazolium nitrate is also apparently less sensitive than RDX. This information leads me to believe that aminotetrazolium nitroformate would be a relatively insensitive explosive, with a very high detonation velocity (probably >9km/sec).

Adas - 8-11-2011 at 12:06

I have an idea for new explosive. Here is the picture and possible synthesis:


Formatik - 9-11-2011 at 21:56

Just when you thought azidotetrazole couldn't get more energetic somebody (guess who) attaches an oxygen to it making salts which are less sensitive and more powerful (azidotetrazolate 2-oxide):

http://onlinelibrary.wiley.com/doi/10.1002/chem.201102064/ab...

PHILOU Zrealone - 12-11-2011 at 11:17

Quote: Originally posted by Anders Hoveland  
Yes, (NO2)3PhO(-) (+)NH3NH3(+) ClO4(-)

Where there are N2H6 (+2) cations and a mix of picrate and perchlorate.

Picric acid, as I have recently described in another post, likely will be able to react through a tautomeric ketone to condense with NH2OH... or with NH2NH3(+) ! There is a diagram somwhere in "Quinone Explosives" topic.

Thus, may get the salt (NO2)3PhNNH3(+) ClO4(-)
This would be even more powerful, since it is the dehydrated form of the double salt I described.
Ph = phenyl obviously

True that phenol and trinitrophenol are able to transpose a -OH group for a -NH2 or -NH-NH2 group...
You would thus end up with trinitrophenylhydrazine...this would display rather acidic H on the first nitrogen close to the aromatic ring...the second nitrogen will be less acidic and thus more basic allowing a "neutralization" by HOClO3 to provide (trinitrophenylhydrazinium picrate) ((NO2)3C6H2-NHNH3(+)ClO4(-)).

:cool::cool::cool::cool::cool::cool::D:D:D:D:D:D
Thinking one step further is to allow trichlorotrinitrobenzene to react with NH2-NH2 to get 1,3,5-trihydrazino-2,4,6-trinitrobenzene...the later must be a good candidate for making salts of HClO4, HIO4, HC(NO2)3, HC(NO2)CN and HN(NO2)2

PHILOU Zrealone - 12-11-2011 at 11:21

Quote: Originally posted by Adas  
I have an idea for new explosive. Here is the picture and possible synthesis:



Do you really think dinitropyridine (a really deactivated aromatic ring) will react as you suggested with AlCl3 and Cl2?
You should check pyridine (heteroaromatic) chemistry before proposing such a pathway.

Do you really think NH2-NO2 will react so easily with chlorodinitropyridine? Isn't it too acidic for that? Usually such reactions occurs with basic amines.

[Edited on 12-11-2011 by PHILOU Zrealone]

PHILOU Zrealone - 12-11-2011 at 11:25

Quote: Originally posted by Formatik  
Just when you thought azidotetrazole couldn't get more energetic somebody (guess who) attaches an oxygen to it making salts which are less sensitive and more powerful (azidotetrazolate 2-oxide):

http://onlinelibrary.wiley.com/doi/10.1002/chem.201102064/ab...

I wonder what is the structure of azidotetrazolate 2-oxide, by chance do you have an image of it?

Formatik - 12-11-2011 at 23:25

Have a look at the spectra and structures yourself.

Attachment: 13068.pdf (758kB)
This file has been downloaded 1452 times

PHILOU Zrealone - 13-11-2011 at 14:49

Thank you Formatik, nice finding!;)

Adas - 29-11-2011 at 06:47

What do you think about cellulose perchlorate? I wasn't able to find it mentioned anywhere, but I think it would be too unstable.



PHILOU Zrealone - 29-11-2011 at 12:14

Cellulose perchlorate is indeed unstable and is subject to self-combustion-initiation.

When adding paper or cellulose to70% HClO4 you get a transparent gellous like stuff that detonates readily from flame. But being of the perchloric ester familly, it is not something to store or to play with in significant quantities (> 2g).

Adas - 5-12-2011 at 09:19

What about sulfur diazide? SCl2 + 2 NaN3 ----> S(N3)2
Or some explosives derived from urea:

CON2H4 + Cl2 ----> CON2H3Cl + HCl
CON2H3Cl + NaN3 ----> H2N-C(=O)-NH-N3 - Quite interesting I think..

Adas - 27-12-2011 at 02:46

Yesterday I got an idea of making biuret dioxime. I don't think it's impossible, but I can't find any info. Many interesting EM can be derived from it, IMO.

AndersHoveland - 28-12-2011 at 01:20

Quote: Originally posted by Adas  
What about sulfur diazide? SCl2 + 2 NaN3 ----> S(N3)2


found this,

Quote:

Sulfuryl azide, SO2(N3)2 ... was made in 1922 by Curtius and Schmidt by shaking a suspension of sodium azide in sulfuryl chloride for 24 hr.



AndersHoveland - 20-1-2012 at 20:43

Quote: Originally posted by Adas  
I have an idea for new explosive. Here is the picture and possible synthesis:



I want to comment on this idea from Adas. The chlorine will not as readily substitute off because it is it the meta- position with respect to both nitro groups. Probably better to use bromine instead. The resulting compound, if it forms, is also likely to hydrolyse with water and be significantly more sensitive than other typical nitramines because the two nitropyridine functional groups would be much more electron withdrawing than the methylene groups found in RDX. It may also be possible that the dinitrochloropyridine may be able to act as an oxidizer towards the NH2NO2, rather than condensing with it. For example, both trinitrophenol and dinitroimidizole will oxidize hydroxylamine, with one of the nitro groups on the ring being reduced to an amine in both instances.

Nicodem - 27-3-2012 at 08:50

Someone might find this article interesting:

Quote:
Synthesis of Trinitromethyl- and Dinitromethyl-Substituted Azoles Using Nitrate Salts in Sulfuric Acid

Venugopal Thottempudi, Jean'ne M. Shreeve

Synthesis 2012 (in press)
DOI: 10.1055/s-0031-1289736

Abstract

Synthesis of trinitromethyl and dinitromethyl-substituted azoles employing a mild and efficient nitration method has been developed using a mixture of sulfuric acid and an inorganic nitrate salt XNO3, where X = NH4+, Na+, K+. This methodology exhibits clear advantages over the more popular mixed acids nitration approach. Various nitro functionalities such as C-trinitromethyl, N-trinitromethyl, and dinitromethyl ester containing azoles were prepared in moderate to excellent yields with reduced reaction times using this method.


nitrotriazoles.gif - 27kB

Rosco Bodine - 1-4-2012 at 21:54

Synthesis of Trinitromethyl- and Dinitromethyl-Substituted Azoles Using Nitrate Salts in Sulfuric Acid

article attached thanks to ayush


Attachment: Synthesis of Trinitromethyl- and Dinitromethyl-Substituted Azoles Using Nitrate Salts in Sulfuric Aciid.pdf (107kB)
This file has been downloaded 1828 times


PHILOU Zrealone - 2-4-2012 at 14:15

A big THANK to Nicodem and Rosco Bodine :) for this little golden nugget!
:D:P
I especially like the comparison and effect of extra groups or heteroatoms (nitrogen) onto the yield...
Introducing electrowithdrawing groups increases the yield...

Special attention can be set on the Ethyl 5-Tetrazolyldinitroacetate over 95% yield in less than 2 hours!

This opens me a lot of new ways of investigation....

AndersHoveland - 2-4-2012 at 21:44

Trinitromethyl groups can add good oxygen balance, but the problem is significant increase in sensitivity, and thermal stability problems. My opinion is that the trinitromethyl in its anion form (nitroformate) has much better stability, and thus would be much more practical.

franklyn - 3-4-2012 at 00:00

That is a gem of a paper.

The essential reaction scheme irrespective of the *azole , is the oxidation of the
acetic acid functional group into trinitroformate in a rather fascile manner. It begs
the question if this will work generally on any R-CH2COOH. A likely candidate to
investigate would be aromatic derivatives such as ,1,3,5- benzene triacetic acid.

Benzene triacetic acid.gif - 720B

www.chemspider.com/Chemical-Structure.309530.html
www.guidechem.com/products/4435-67-0-p1.html
http://datasheets.scbt.com/sc-252412.pdf
a bit expensive at ~ $130 per 500 gm.
http://www.scientificlabs.co.uk/product/17383-500MG

The intended result of this would be
1,3,5-Tris (trinitromethyl)- Benzene , CAS 210053-27-3
oxygen balance is , - 4.6
2 C6H3{C(NO2)3}3 => 15 CO2 + 3 CO + 3 H20 + 9 N2

1,3,5-Tris (trinitromethy)-Benzene.gif - 5kB

Apart from Arylacetic acids other candidates are Alkyl Dicarboxylic acids.
http://en.wikipedia.org/wiki/Dicarboxylic_acid
By this process Succinic Acid would yield Hexanitroethane.

Succinic Acid (Butanedioic Acid) HOOC.(CH2)2.COOH
http://en.wikipedia.org/wiki/Succinic_Acid
Glutaric Acid (Pentanedioic Acid) HOOC.(CH2)3.COOH
http://en.wikipedia.org/wiki/Glutaric_acid
Adipic Acid (Hexanedioic Acid) HOOC.(CH2)4.COOH
http://en.wikipedia.org/wiki/Adipic_acid
Pimelic Acid (Heptanedioic Acid) HOOC.(CH2)5.COOH
http://en.wikipedia.org/wiki/Pimelic_acid
Pimelic can be synthesized from salicylic acid
http://www.orgsyn.org/orgsyn/pdfs/CV2P0531.pdf

Carboxylic acids can be made by oxidizing an alcohol group.
A typical reaction is:
Carboxilic acid from alchohol oxidation.bmp - 3kB

Syntheses of Tetracarboxylic Acids
Boris I Zapadinskii et al 1973 Russ. Chem. Rev. 42 939
http://iopscience.iop.org/0036-021X/42/11/R04

Ethylene Diamine Tetraacetic acid (EDTA) is available over the counter
from your health food store around $ 15 for 125 grams in capsules.
http://en.wikipedia.org/wiki/EDTA

.

[Edited on 3-4-2012 by franklyn]

Nicodem - 3-4-2012 at 07:14

Quote: Originally posted by franklyn  
That is a gem of a paper.

The essential reaction scheme irrespective of the *azole , is the oxidation of the
acetic acid functional group into trinitroformate in a rather fascile manner. It begs
the question if this will work generally on any R-CH2COOH. A likely candidate to
investigate would be aromatic derivatives such as ,1,3,5- benzene triacetic acid.

The electrophilic nitration of fairly active methylene groups is quite general, but the alpha-position of carboxylic acids is not generally considered as particularly "active". That kind of triazole rings activate the methylene group more than a phenyl group does, so the nitration of phenylacetic acids would not necessarily lead to the nitration of the benzylic position, at least not without first achieving the ortho and/or para ring nitration which activates the benzylic position (an exception would be the radical nitration which should proceed readily on phenylacetic acid to give the corresponding oxidation products).

The alpha-position of carboxylic acids can be activated also from the other (carbonyl) side - carboxylic acid anhydrides and halides enolize much more easily and are thus way more activated than the corresponding acids. This is how acetic anhydride can be nitrated under relatively mild conditions: http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv3...

The nitration of active methylene groups can be achieved with HNO3 like in the discussed article or the Org. Synth. example above. It can also be achieved by the nitration of the preformed enolate by using certain nitrating reagents such as Me2C(CN)ONO2, alkyl nitrates, tetranitromethane, or FC(NO2)3 like in the example of alpha,2,4,6-tetranitrotoluene synthesis described in the 1.8.1.3 chapter of Organic Chemistry of Explosives (Agrawal & Hodgson, 2007). See its chapter 1.8 for a review of the nitration of active C-H groups.

PS: Those interested in the nitromethyl substituted triazoles might also want to check another article (DOI: 10.1007/s11172-009-0285-y) where another ingenious methylene group activation strategy is used.

AndersHoveland - 3-4-2012 at 09:32

Quote: Originally posted by Nicodem  
The electrophilic nitration of fairly active methylene groups is quite general, but the alpha-position of carboxylic acids is not generally considered as particularly "active". That kind of triazole rings activate the methylene group more than a phenyl group does,


Although a methyl group on a tetrazole ring appears to be inert towards nitration, the addition of a carboxyl group [to the now methylene group] seems to activate it to nitration.

Quote: Originally posted by AndersHoveland  

Nitration of 5-methyltetrazole
various starting materials such as 2-methylimidazole, 2-methoxy-2-methyl-imidazolidine-4,5-dione,and2-methylpyrimidine-4,6-dione(4,5-dihydroxy-2-methylpyrimidine) were nitrated and then hydrolyzed to give FOX-7 by somewhat different process. Since the methyl group was converted to dinitromethylidene moiety in all methods, nitration of 5-methyltetrazole was attempted to afford 5-dinitromethylidene-1,4-dihydrotetrazole. But this reaction failed to proceed, and most of the starting material was recovered.

Quote:

With the necessary intermediates in hand, we sought to construct the N2FOX-7 using decarboxylation and elimination. Thus, various conditions were tried. When ethyl 5-tetrazolyldinitro-acetate was treated with water, 5-dinitromethyltetrazole was readily given. Hydrolysis followed by decarboxylation took place completely within 2 h at 50 °C.
Synthesis and Characterization of High EnergeticTetrazole and Furoxan Derivatives, (Korea)

ethyltetrazolylacetate
N4HC-CH2-C(=O)-O-CH2CH3

The reason that the nitration of 5-methyltetrazole failed to proceed is probably the same reason that nitration of plain 1,2,3-triazole is essentially impossible.* I suspect that the electron-withdrawing tetrazole ring pulls away electric charge from the methyl group, giving it a partial positive charge and effectively shielding it from interaction with nitronium ions, which is the mechanism of reaction in most nitrations.

*In contrast, 4-nitro-1,2,3-triazole is easily both nitrated, and oxidized interestingly, by normal mixed HNO3/H2SO4 acids to 4,5-dinitro-1,2,3-triazole-N-oxide. The addition of one nitro group appears to activate the other CH to nitration.


[Edited on 3-4-2012 by AndersHoveland]

franklyn - 4-4-2012 at 00:23

@ Nicodem

" That kind of triazole rings activate the methylene group more than a phenyl group does "

As it does with triazine www.sciencemadness.org/talk/viewthread.php?tid=11195&pag...

Thanks for outlining the complexities involved. There is always more to this than
first appears to my unpracticed notions.

This is that other article cited by you.
www.springerlink.com/content/b451460133120472

.

Adas - 8-5-2012 at 09:36

Possible route to sulfuric diperoxide (S2O8)?

2 SO<sub>2</sub>Cl<sub>2</sub> + 2 BaO<sub>2</sub> ----> O<sub>2</sub>S-(O-O)<sub>2</sub>-SO<sub>2</sub> + BaCl<sub>2</sub>

Adas - 11-5-2012 at 12:53

And what about organodinitramides?




But it's a shame that dinitramides are so difficult to prepare...

franklyn - 4-7-2012 at 15:06

Chavez has his patent
Synthesis of Energetic Nitrate Ester US 20120108838
Attachment: US20120108838.pdf (248kB)
This file has been downloaded 798 times

1.gif - 3kB

Recap from an earlier post in this thread

Synthesis of an Energetic Nitrate Ester
http://www.sciencemadness.org/talk/files.php?pid=141343&...
Thanks to 4 9 7 for this

.

PHILOU Zrealone - 20-10-2012 at 08:10

Quote: Originally posted by franklyn  
Chavez has his patent
Synthesis of Energetic Nitrate Ester US 20120108838




Recap from an earlier post in this thread

Synthesis of an Energetic Nitrate Ester
http://www.sciencemadness.org/talk/files.php?pid=141343&...
Thanks to 4 9 7 for this

.

This brings us back to Axt post in 2004 about synthesis of Nitroisobutylglycerol Trinitrate from nitromethane and formaldehyde...
CH3-NO2 + 3 CH2=O --> (HOCH2)3C-NO2
(HOCH2)3C-NO2 + 3HNO3 --> (O2NOCH2)3C-NO2 + 3H2O
A very powerfull OB balanced HE...

I already talked about 1,2-dinitroethane as a possible source of the tetranitrate ester molecule you depicted... 2,3-dinitro-2,3-dimethylol-butan-1,4-diol tetranitrate.
O2N-CH2-CH2-NO2 + 4 CH2=O --> (HOCH2)2C(NO2)-C(NO2)-(CH2OH)2
(HOCH2)2C(NO2)-C(NO2)-(CH2OH)2 + 4HNO3 --> (O2NOCH2)2C(NO2)-C(NO2)-(CH2ONO2)2 + 4H2O
This ester has also a perfect OB like all molecules of the permethylolpolynitroalcane familly derived from polynitroalcanes H-(CH-NO2)x-H (x from 1 to infinite).

As expected the later tetranitrate ester has a higer density, a higher VOD and less or equally sensitive than the former trinitrate ester... this goes the same way as the predictive theory I work on for years now...

I can predict for the following members of that specific familly of perfect OB nitro-nitrate HE:
-that 1,2,3-trinitropropane will provide a pentanitrate ester that will be even denser and powerful than the previous member of the familly (the tetranitrate ester here above)
-that 1,2,3,4-tetranitrobutane will provide a hexanitrate ester that will be even denser and powerful than the pentanitrate member
-etc

So if HMX has already the same VOD as the tetranitrate ester (9,1 km/s) ... can you imagine what would be the power and VOD of the pentanitrate and hexanitrate?I guess > 9,5 km/s

This familly has the low impact and shock sensibility of PETN because each nitrate ester group is not directly vicinal and at least espaced by one carbon atom free of nitrate group...
This effect is seen in 1,3-propanediol dinitrate (where position 2 is free of nitrate), in 1,3-butanediol dinitrate (in which position 2 and 4 are free of nitrate), in 1,4-butandiol dinitrate (where position 2 and 3 are free of NO3), in polyvinylnitrate (where one on each two carbons is exempt of NO3) and in PETN (where the central C atom allows separation of all 4 nitrate groups).

The effect is absent in 1,2 propandiol dinitrate, in 1,2 or 2,3 butandiol dinitrate!

[Edited on 20-10-2012 by PHILOU Zrealone]

PHILOU Zrealone - 20-10-2012 at 08:18

Quote: Originally posted by Adas  
And what about organodinitramides?




But it's a shame that dinitramides are so difficult to prepare...

It is a shame that chlorine atoms on aromatic rings doesn't substitute so easily... the way you wrote it...

Maybe if you add some withdrawing group on the ring...
2,4,6-trichloro-1,3,5-trinitrobenzene would be a much better option ... but the resulting (mono, bis or tris) dinitramide would be very unstable ... a bit for the same reason trinitramide would be...

hissingnoise - 20-10-2012 at 09:14

Quote:
Nitroisobutylglycerol Trinitrate from nitromethane and formaldehyde...
CH3-NO2 + 3 CH2=O --> (HOCH2)3C-NO2
(HOCH2)3C-NO2 + 3HNO3 --> (O2NOCH2)3C-NO2 + 3H2O
A very powerfull OB balanced HE...

Agreed, but the nitro group lowers its stability significantly and although its density exceeds that of nitroglycol, the much lower viscosity of the latter gives it the VoD of a denser material!
And nitroglycol is a very good gelatiniser for NC, working at ordinary temps, unlike nib-glycerine trinitrate which is much slower even than NGL . . .

Nitroglycol's synthesis too, is easier if you have access to the glycol!


PHILOU Zrealone - 21-10-2012 at 10:52

Quote: Originally posted by franklyn  
@ Nicodem

" That kind of triazole rings activate the methylene group more than a phenyl group does "

As it does with triazine www.sciencemadness.org/talk/viewthread.php?tid=11195&pag...

Thanks for outlining the complexities involved. There is always more to this than
first appears to my unpracticed notions.

This is that other article cited by you.
www.springerlink.com/content/b451460133120472

.

Yeah 2,4,6-tricarboxymethyl-1,3,5-triazine would be interesting to test although the resulting tris-nitroformyl triazine can be acheived by easier ways (*).
Cl-CH2-CO2H + Na-C#N --> N#C-CH2-CO2H + NaCl
3 N#C-CH2-CO2H -trimerization-> cyclo(-N=C(-CH2-CO2H)-)3
cyclo(-N=C(-CH2-CO2H)-)3 -nitration-> cyclo(-N=C(-C(NO2)3)-)3
As sugested in http://en.wikipedia.org/wiki/2,4,6-Tris(trinitromethyl)-1,3,5-triazine

(*)By metathesis like it is the case for cyanuric triazide (cyanuric chloride and NaN3)...
cyclo(-N=CCl-)3 + 3NaC(NO2)3 -solvent-> cyclo(-N=C(-C(NO2)3)-)3 + 3 NaCl



PHILOU Zrealone - 12-11-2012 at 03:43

Quote: Originally posted by franklyn  
Chavez has his patent
Synthesis of Energetic Nitrate Ester US 20120108838




Recap from an earlier post in this thread

Synthesis of an Energetic Nitrate Ester
http://www.sciencemadness.org/talk/files.php?pid=141343&...
Thanks to 4 9 7 for this

.


Does someone else here find the following data dubious?
"Compound 1 was characterized spectroscopically and
thermally. The material begins to decompose at 141°C with a
decomposition energy release of 1818 J/g."

I think they made a mistake on the units and that 1818 J/g (or kJ/kg) should rather be 1818 cal/g (or kcal/kg).

[Edited on 12-11-2012 by PHILOU Zrealone]

Nicodem - 3-12-2012 at 11:52

A new article, for those interested in triazoles:

Nitrogen-Rich Bis-1,2,4-triazoles—A Comparative Study of Structural and Energetic Properties
Alexander A. Dippold, Thomas M. Klapötke
Chemistry - A European Journal 2012, early view (page numbers not yet assigned)
DOI: 10.1002/chem.201202483

Davin - 5-12-2012 at 13:43

Everyone knows about aminotetrazole and diaminotetrazole.

What about triaminotetrazolium? :-)
http://onlinelibrary.wiley.com/doi/10.1002/ejic.201200964/ab...

Adas - 29-12-2012 at 02:49

Melam and Melamine could make interesting explosive salts. They are nitrogen-rich :D

Solomon - 26-6-2013 at 17:45

URL is a void link. But to all other scientists on this forum - I agree... we must begin searching for a method of synthesizing this material. If anyone figures out a way to do it then call (805) 279-8556 and post your results.

Boffis - 27-6-2013 at 05:26

Quote: Originally posted by Solomon  
URL is a void link. But to all other scientists on this forum - I agree... we must begin searching for a method of synthesizing this material. If anyone figures out a way to do it then call (805) 279-8556 and post your results.


Which link are you refering to?

LOOKING FOR ADVICE. 4TH GENERATION POLYMER-BONDED THERMOBARIC EXPLOSIVE

SURT Tech. - 28-6-2013 at 06:50

Hello to all members of the forum. Considering the nature of our initiative it will be hard task to explain in details our work and goals in just a single post, but we’ll try. The subject is somewhat touchy and we are more than sure, that we are the first ones who ever tried to do it in such a “delicate” way.

Briefly. We are recently founded (private research) company from Bulgaria, engaged mostly in the field of blast enchased explosives. On 30.04.2013, on the testing ground of one of the largest weapon producer in Bulgaria, we made the final tests of our thermobaric compositions (TBX – 2) with the best hardware available in order to extract the maximum data needed to prove our conception. The results from the comparative tests (5 kg. charges with pure A – 9 and standard mash type TB – RDX, IPN, Al) far exceeded our expectations and that’s the main reason for our desire to move it abroad.

As well educated people who have access to the latest research papers and scientific publications, we have closely monitored, studied and tested every promising thermobaric composition or design from the last decade. Based on this our composition is considered to be 4th generation thermobaric, which (as we found) is capable to detonate and burn completely the metal fuel even in 50 gr. quantities. We also want to point that all expenses around the research stages and the tests were paid by the name of our company (SURT Technologies) and considering this and the fact that we are private researchers (and we are not engage with any government structures), we are completely free to sell our products abroad. The big question is how and is this possible at all? With other word is it possible for private company abroad to sell the patent rights for the product or the license for the manufacture to other country?

What are the main advantages of our composition?

1. Cutting edge solid state concept, analogous to the one used in the “Hellfire II AGM-114N”, but completed with the use of much cheaper, safer and ready available materials that release even higher explosive power (16 MJ/kg or 4 times TNT equivalent for the energy of aerobic detonation, Pcj 25-30 GPa for the anaerobic detonation).

2. Lack of any volatile liquid monopropellants (like IPN in the Russian “Shmel” for example), which eases the production, handling and most important - improves the storage stability. Not need of airtight or reinforced containers.

3. Energetically burning polymer binder, which achieves an effect similar to that of additionally introduced metal fuel into the composition. The polymer also acts as catalyst to ensure the complete burning of the metal fuel into the atmosphere. The very first tests were conducted at a temperature of -10 (minus ten) degrees Celsius, which again confirms the high versatility and the excellent performance of our thermobaric compositions. It’s very important to note that our thermobaric compositions detonate completely even in 50 – 100 grams quantities, which is impossible for any other polymer bonded thermobaric explosives. The widely used PBX compositions like PBXH-135 and AFX-757 give satisfactory results only in large amounts, but in quantities less than 10 kilos they suffer from incomplete combustion of the metal fuel, which make them useless in small calibers.

4. Inhibition. The coated with polymer metal particles and oxygen rich salts are protected from external influence during handling and storage, which significantly extends the shelf life and stability of the produced ammunition.

5. Low sensitive to mechanical and thermal impact elements, which in turn puts these products in the category of so-called "insensitive" munitions. Exceptionally high thermal stability, which makes them excellent filler for various supersonic munitions. The composition is stable for short time heating up to 250 °C and its flash point is above 300 °C. The used polymer maintains its mechanical properties from -50 to more than 200 °C.

6. Inert. High resistance to oxidation even at high temperatures without the use of any anti-oxidants or other preserving agents. Zero hygroscopicity and high humidity resistance of the final product. Samples of the described compositions have been stored so far for more than a year (from -15 to +45 °C) without any chemical or mechanical changes to the structure and the properties of the material.

7. Low production cost at about 10-15 USD per kilogram! All ingredients are high-tonnage products of the chemical industry. Our binding system completely eliminate the problems associated with the classical "slurry" method such as high cost, low yield, the use of specialized equipment and most importantly - the oxidation of the used metal fuels. That process can be done even "manually" or with the help of ordinary mechanical mixers. Тhe resulting plastic / semi plastic mass can be charged into munitions using exactly the same methods as the ones used for the composite rocket propellants. This makes the production cycle much simpler and eliminates the need of specialized equipment or the construction of separate production lines. Factors, which shrink the production costs to minimum.

8. High charge density (more than 2 g/cc) in comparison with compositions based on polymers such as hydroxyl-terminated polybutadiene (HTPB). Very good mechanical properties. Easy molding and pressing of the resulting thermobaric composition. Consistency of a solid rubber in polymerized state and a paste in unpolymerized state, which can be extruded even through 1.5 mm opening.

9. Classification and environmental issues. Considering the legal issues around thermobaric weapons in recent years, our explosives can be classified either as “thermobaric” or “enhanced blast”, because they have all the positive characteristics of the classic aluminized explosives (solid state, low sensitivity similar to Tritonal, AFX-757, etc.), but with 2 - 4 times higher blast/pressure capabilities. These new explosives do not contain any toxic products or evolves products (after detonation) with higher toxicity than Tritonal, AFX-757 or PBXH-135.

Furthermore. Right now we worked on another thermobaric composition based on completely new technology concept. Also advanced thermite charges and grenades. Flash bang grenades with improved performance and cheap, non-toxic ingredients (lack of any heavy metal salts, etc.). We are also developing Novel Software for computer simulations of different thermobaric compositions.

Well, that’s it generally. As we stated above, the subject is more than unconventional, but we are well educated, handle freely English and Russian and have the huge willing to continue our development in the field.

We want to apologies in advance if we violate any rules of the forum or the post is made in the wrong thread.

simply RED - 28-6-2013 at 07:02

My friend from the above post could not attach this picture. By the way, I helped him with the theoretical predictions before they did any tests...

TBX2.JPG - 53kB

Solomon - 28-6-2013 at 09:25

I would love to know how you guys at SURT technologies synthesized TBX-2. I realize that you wouldn't want idea theft but I wouldn't do that. If you give me this idea I will give you one of mine about a hydrogen computer concept :D. Not that my idea is too practical, but you might be able to take it somewhere. What is the detonation velocity of TBX-2?

simply RED - 28-6-2013 at 09:41

Oh, it is just a thermobaric composition, not much synthesis is involved. The advantage is that it burns all fuel into the positive pressure phase and yields 3-4 times TNT blast equivalent for 15 dolars/kg. Ammerican compositions have lower yield even by using extremely exotic chemicals like fluorine or other active polymers etc ... and price rises above 50-100 dolars/kg... SURT has patent on this anyway. If you have any connections with the industry, help us and connects us with. As we made it but have no connections and of course we want it to have real use...

Here is a short presentation, if you have problems downloading it tell me:
http://dox.bg/files/dw?a=df6fdacb82

Barely forgot, detonation velocity about 7500-8000 m/s.

[Edited on 28-6-2013 by simply RED]

Solomon - 28-6-2013 at 12:26

Thank you. Could I get the patent number detailing the creation of TBX-2 and the ratios of RDX to TBX-2. Just ask me if you want the idea for the hydrogen computer. Are you the CEO of SURT technologies?

[Edited on 28-6-2013 by Solomon]

[Edited on 28-6-2013 by Solomon]

simply RED - 28-6-2013 at 22:26

I just performed all theoretical predictions before compositions were tested. Engineering enhanced blast/thermobaric/SFAE whatever you call it is extremely difficult. Even using HMX in compositions HMX/Al/HTPB does not help as the energy of detonation gets only 2-3 MJ/kg - less than needed to ignite and burn all Al. American researchers tried to solve this by using active and/or high density polymers like in PBXIH-18. This partially solves the problem but the price of the final product gets too high (it is already too high with HMX). Another attempt to solve the problem was the anular design employed in the Hellfire 2 warhead. Apart from the price problem, a very bad processibility problem arises as the used fluorine polymers tend to be too brittle or generally lack mechanical qualities. No practical sheme for loading the mixture was developed. So Hellfire 2 warhead was the only one completed by this design AFAIK. Russian researchers, countrary, tried to apply low tech solution - adding monopropellant like IPN in the mixture. Same problems with the low energy appeared and as you can see from the pictures in the presentation - IPN mixtures are not even capable of igniting most of the metal powder! In fact RDX/IPN/Al was one of the worst performing in our tests, much worse than all alluminized PBXs, maybe even worse than AN/NM/Al... Another tried method to ignite "those freaking inert" metal particles was adding oxidizer directly into the mix forming RDX/AP/Al/Polymer like material. Good idea, except for the fact that those oxidizers remain inert during the detonation propagation and still the metal particles do not ignite well if the mass of the material is less than 50 kilos.

So, we solved all those problems and here is the TBX-2 composition using new principle to be able to fully burn the fuel no matter in open, closed space, winther conditions, wind etc. Please no more spam, PM me or the colegue above for further questions. I do not even know if the forum was the right place to post this. Anyway, it was the ONLY place. Jane military and others rejected us and we could not post it anywhere else... So, all test are over and no more evaluation is needed, now we are looking for connections with the industry.

DubaiAmateurRocketry - 28-6-2013 at 22:30

Quote: Originally posted by simply RED  
I just performed all theoretical predictions before compositions were tested. Engineering enhanced blast/thermobaric/SFAE whatever you call it is extremely difficult. Even using HMX in compositions HMX/Al/HTPB does not help as the energy of detonation gets only 2-3 MJ/kg - less than needed to ignite and burn all Al. American researchers tried to solve this by using active and/or high density polymers like in PBXIH-18. This partially solves the problem but the price of the final product gets too high (it is already too high with HMX). Another attempt to solve the problem was the anular design employed in the Hellfire 2 warhead. Apart from the price problem, a very bad processibility problem arises as the used fluorine polymers tend to be too brittle or generally lack mechanical qualities. No practical sheme for loading the mixture was developed. So Hellfire 2 warhead was the only one completed by this design AFAIK. Russian researchers, countrary, tried to apply low tech solution - adding monopropellant like IPN in the mixture. Same problems with the low energy appeared and as you can see from the pictures in the presentation - IPN mixtures are not even capable of igniting most of the metal powder! In fact RDX/IPN/Al was one of the worst performing in our tests, much worse than all alluminized PBXs, maybe even worse than AN/NM/Al... Another tried method to ignite "those freaking inert" metal particles was adding oxidizer directly into the mix forming RDX/AP/Al/Polymer like material. Good idea, except for the fact that those oxidizers remain inert during the detonation propagation and still the metal particles do not ignite well if the mass of the material is less than 50 kilos.

So, we solved all those problems and here is the TBX-2 composition using new principle to be able to fully burn the fuel no matter in open, closed space, winther conditions, wind etc. Please no more spam, PM me or the colegue above for further questions. I do not even know if the forum was the right place to post this. Anyway, it was the ONLY place. Jane military and others rejected us and we could not post it anywhere else... So, all test are over and no more evaluation is needed, now we are looking for connections with the industry.



Explosives with polymers ? cool, i have a small idea to decrease any sensitive explosive to 0 reactivity.

Solomon - 29-6-2013 at 10:27

Simply Red, as far as an industry connection, I do know someone... dr. Robert Cassar of earth shift products. I may be able to get him to work with you. Although earth shift has different types of things that they work on, maybe they would consider you of interest. I will talk to Robert's advisor and see if I can get his attention. If however you accept this offer, you must remember that he lives in Hawaii and if I can get his attention you will almost certainly have to fly out to hawaii. I will try and work out the details now... tell me if you want to go with it. Remember, earth shift products is a multi billion $ company, they will be able to take you places. This will help me as well because if you guys can impress him, he will pay more attention to me. Looking forward to the possibility of working with you!

simply RED - 29-6-2013 at 10:56

Please no more spam in the main topic, address everything regarding TBX-2 as a personal message to SURT Tech. Yes, we are looking for every possible way of cooperation. Solomon, please send personal message to SURT Tech. We can sell the license for production according to the patent to every company that has the valid documents for production and trade of energetic materials or is a LEGAL researcher of energetic materials. Of course we are looking O-N-L-Y for such industry contacts! And please no more spam, PM.

[Edited on 29-6-2013 by simply RED]

[Edited on 29-6-2013 by simply RED]

Solomon - 13-7-2013 at 11:59

New novel energetic materials have been observed. N60 is a new energetic material with a detonation velocity of 17000 m/s :o. I am reading a PDF here: http://www14.atpages.jp/~highenergy/hb_jx/File-hb-005-CESW20... . There is a chart comparing the promise between molecules composed only of nitrogen atoms. The N60 molecule is the graphene of the energetic materials world. I watched the staircase implementation of the big bang theory and in it Leonard is working on a new rocket fuel for the government with over 8,000,000 newtons of thrust. Leonard shows his friends the new fuel in his apartment, however he fails to take into account that his rocket fuel was for a full scale rocket, and he mixes it in a tovex coated with Iridium and exposes far too much of the propellant's surface area to the Iridium resulting in the accident seen on the big bang theory season 3 the staircase implementation. Buy it on itunes and skip to around 17 minutes to see an awesome novel rocket fuel based on a real one developed in 2003.

Solomon - 17-7-2013 at 00:01

Is there even a remote chance that anyone knows the detonation velocity of hydrazinium azide hydrazinate or will I have no choice but to synthesize it and find out as I can't find that information anywhere. Sending out a call of desperation here.

franklyn - 27-7-2013 at 04:12

8100 m/s = HN3
3400 m/s = NH4N3

Hydrazine is detonable on it's own so the Azide is much more energetic than
Ammonium Azide. Guessing ∆Hf to be + 219 kJ/mol , and density of 1.8 g/cc
entering into Engager's Detonation Calculator Utility ( this link )
www.sciencemadness.org/talk/viewthread.php?tid=11195&pag...
obtains 7950 m/s for N2H4•HN3
According to this paper the vod of N2H4•HN3 is comparable to that of RDX at
the same density.
www.chemie.uni-muenchen.de/ac/klapoetke/content/research/pos...

N2H4HN3.gif - 14kB

The Hydrazine adduct will have lower overall energy so the vod must be
substantially less. The density is given as ρ=1.32 g/cc here _
http://onlinelibrary.wiley.com/doi/10.1002/1521-4087(200110)...
Guessing ∆Hf to be + 154 kJ/mol and entering into Engager's Detonation Calculator Utility
obtains 5426 m/s for (N2H4)2•HN3

(N2H4)2HN3.gif - 14kB


AndersHoveland - 27-7-2013 at 22:28

Quote: Originally posted by franklyn  
Hydrazine is detonable on it's own

I do not think it actually is. Perhaps you mistyped?

Hydrazine has a substantial heat of formation, but it was my understanding that, because of the N-H hydrogen bonding, it is not enough to overcome the energy it takes to gasify surrounding molecules, and thus decomposition can only be sustained by a catalyst.

Quote: Originally posted by franklyn  

obtains 7950 m/s for N2H4•HN3

I have seen the detonation velocity listed somewhere before for this compound. It was lower than that. In fact, I remember it being somewhat lower than HN3, though it was still substantially higher than NH4N3. A measurement difference could possibly be due to the velocity being dependent on the diameter of the charge, but you should also be aware that calculation algorithms often tend to overestimate the power of explosives that contain very high proportions of nitrogen.

A quick look at the data plot from one source seems to suggest an observed detonation velocity of around 7.6-7.7 km/s for N2H4•HN3
(G. S. Yakovleva, R. Kh. Kurbangalina, L. N. Stesik, Fiz. Goreniya Vzryva 1974, 10(2), 270-274.)

[Edited on 28-7-2013 by AndersHoveland]

franklyn - 8-8-2013 at 09:21

Quote: Originally posted by AndersHoveland  
Quote: Originally posted by franklyn  
Hydrazine is detonable on it's own

I do not think it actually is. Perhaps you mistyped ?

Hydrazine gas does propagate detonation see page 364 here _
Combustion and Detonation Characteristics of Hydrazine and Its Methyl Derivatives
www.sciencemadness.org/talk/viewthread.php?tid=874#pid254995

According to Encyclopedia of Explosives , Fedoroff , H-192
Liquid anhydrous hydrazine is nonexplosive /
completely insensitive to shock , friction or electric discharge.

• the vapor may be exploded without air

.

franklyn - 9-8-2013 at 23:13

On a similar line as what PHILOU Zrealone proposes here _
www.sciencemadness.org/talk/viewthread.php?tid=1970&page...



Tetrabromoethylene with Lithium Azide should yield an aromatically stable

Br2C=CBr2 + 4 LiN3 => 4 LiBr + (N3)2C=C(N3)2 / / => N6C=CN6

Dodeca aza octalene.gif - 15kB

From what I understand his type direct substitution generally only applies to carbon
single bonded to another carbon , a primary alkyl. Secondary alkyl , those carbons
bonded to two other carbons are much less active for this type reaction. Tertiary
alkyl carbons are not susceptible at all. It is also the case with alkenes , carbon
with a double bond to another carbon. Alkenes are instead susceptible to breaking
a bond to add more atoms or groups. Aryl ( aromatic benzene ring ) carbons have
been demonstrated as alkyl carbons to be labile to substitution induced by catalytic
action of for example copper.
We know diatomic molecular Bromine and Lithium azide react violently on contact.
Bromine substitutes the azide and the bromyl azide formed dissociates. It seems
that minor activation energy would be required to induce a metathetical exchange
with Tetrabromoethylene a Colorless crystal that Melts at 55 ~ 56 °C ,
Boiling point 226 to 227 °C Insoluble in water, soluble in alcohol , ether and other
organic solvents. Bond dissociation energies indicate the reaction to be exothermic.
Approximate values are , C-Br = 80 kcal/mol , LiBr = 100 kcal/mol , LiN3 = 50 kcal/mol
C-N3 = < 80 kcal/mol


.

[Edited on 11-8-2013 by franklyn]

Nicodem - 20-8-2013 at 09:07

A new article that might be of interest:

Energetic N-Trinitroethyl-Substituted Mono-, Di-, and Triaminotetrazoles
Qinghua Zhang, Jiaheng Zhang, Damon A. Parrish, Jean'ne M. Shreeve
Chemistry - A European Journal, 19(33), 2013, 11000–11006.
DOI: 10.1002/chem.201300994

PHILOU Zrealone - 27-8-2013 at 00:08

Quote: Originally posted by franklyn  
On a similar line as what PHILOU Zrealone proposes here _
www.sciencemadness.org/talk/viewthread.php?tid=1970&page...



Tetrabromoethylene with Lithium Azide should yield an aromatically stable

Br2C=CBr2 + 4 LiN3 => 4 LiBr + (N3)2C=C(N3)2 / / => N6C=CN6



From what I understand his type direct substitution generally only applies to carbon
single bonded to another carbon , a primary alkyl. Secondary alkyl , those carbons
bonded to two other carbons are much less active for this type reaction. Tertiary
alkyl carbons are not susceptible at all. It is also the case with alkenes , carbon
with a double bond to another carbon. Alkenes are instead susceptible to breaking
a bond to add more atoms or groups. Aryl ( aromatic benzene ring ) carbons have
been demonstrated as alkyl carbons to be labile to substitution induced by catalytic
action of for example copper.
We know diatomic molecular Bromine and Lithium azide react violently on contact.
Bromine substitutes the azide and the bromyl azide formed dissociates. It seems
that minor activation energy would be required to induce a metathetical exchange
with Tetrabromoethylene a Colorless crystal that Melts at 55 ~ 56 °C ,
Boiling point 226 to 227 °C Insoluble in water, soluble in alcohol , ether and other
organic solvents. Bond dissociation energies indicate the reaction to be exothermic.
Approximate values are , C-Br = 80 kcal/mol , LiBr = 100 kcal/mol , LiN3 = 50 kcal/mol
C-N3 = < 80 kcal/mol


.

[Edited on 11-8-2013 by franklyn]


What I exposed was N4C2N4 with a naphtalene structure or N4C=CN4 with a bistetrazolene structure.
Both are fully aromatic and this means each N-N or N=N is nearly equivalent in bond lenght and in the aromatic plane of the molecule. The aromatic resonance has a stabilizing effect as seen with tetrazoles (heteroaromatic pentaring).

In your N6C2N6 molecule the octacycles are no more really aromatic (bended out of the plane and twisted) and some of the N-N or N=N becomes unequivalent what is the weakest link... This is very detrimental to the stability of high nitrogen content molecules with >3 polynitrogen atom chains.
So a site with -N=N- will more likely expell N2 (N#N) generating a lot of energy probably sufficient to trigger the detonation of the rest of the product...if the molecule survives the decomposition, there would be a chance it rearranges into the putative stabler molecule I thought about.
N6C2N6 --> N4C2N4 + 2 N2

Or the molecule will simply remain uncyclized as tetraazidoethylene. Tetraazidoethen would be (like tetracyanoethene or tetranitroethene) a good scavenger of electrons...electron charge transfer and it can be trapped by dienic structures CH2=CH-CH=CH2 (Diels-Alder reactions).

If tetrahaloethene is not reactive enough for the substitution, alternatively tetrahalo-1,2-dinitroethane will be...leading to a sensitive perfect OB HE...
O2N-CH2-CH2-NO2 --Br2 or Cl2/mild base--> O2N-CBr2-CBr2-NO2 or O2N-CCl2-CCl2-NO2
By vitue of the close relationship to chloropicrine, those nitro-halogenated compounds must be considered highly toxic agents.Their halogen are labiles because of the nitro group vicinity.
O2N-CX2-CX2-NO2 --NaN3/solvent--> O2N-C(N3)2-C(N3)2-NO2 + 4 NaX
Those polyazido-nitro compounds will probably display the same kind of hydrolysability than their halogen cousins leading to toxic HN3 gassing and be hell friction/shock sensitive. Azido group being a pseudohalogen...


[Edited on 27-8-2013 by PHILOU Zrealone]

Davin - 27-8-2013 at 10:24

Quote: Originally posted by franklyn  
On a similar line as what PHILOU Zrealone proposes here _
www.sciencemadness.org/talk/viewthread.php?tid=1970&page...



Tetrabromoethylene with Lithium Azide should yield an aromatically stable

Br2C=CBr2 + 4 LiN3 => 4 LiBr + (N3)2C=C(N3)2 / / => N6C=CN6



From what I understand his type direct substitution generally only applies to carbon
single bonded to another carbon , a primary alkyl. Secondary alkyl , those carbons
bonded to two other carbons are much less active for this type reaction. Tertiary
alkyl carbons are not susceptible at all. It is also the case with alkenes , carbon
with a double bond to another carbon. Alkenes are instead susceptible to breaking
a bond to add more atoms or groups. Aryl ( aromatic benzene ring ) carbons have
been demonstrated as alkyl carbons to be labile to substitution induced by catalytic
action of for example copper.
We know diatomic molecular Bromine and Lithium azide react violently on contact.
Bromine substitutes the azide and the bromyl azide formed dissociates. It seems
that minor activation energy would be required to induce a metathetical exchange
with Tetrabromoethylene a Colorless crystal that Melts at 55 ~ 56 °C ,
Boiling point 226 to 227 °C Insoluble in water, soluble in alcohol , ether and other
organic solvents. Bond dissociation energies indicate the reaction to be exothermic.
Approximate values are , C-Br = 80 kcal/mol , LiBr = 100 kcal/mol , LiN3 = 50 kcal/mol
C-N3 = < 80 kcal/mol


.



Franklyn: Take a look at the introduction of my article here (http://pubs.acs.org/doi/abs/10.1021/ja310384y?journalCode=ja...) for a quick overview of why such a system is unlikely to be stable and for general considerations in the design of long-chained nitrogen species.

The electron-rich nature of such a ring allows the donation of electron density from the N-lone pairs into the N-N sigma antibonding orbitals, destabilizing the ring to the point of (likely) non-existence. This is why unsubstituted 1,2,3,4-tetrazines are so rare (1 example lit). However the key to long-chain nitrogen systems is the removal of LP electron density on alternating N atoms within the chain, increasing the energy difference between these orbitals and stabilizing the system. This is why 1,2,3,4-tetrazine-1,3-dioxides are so much more stable.

Your species is likely analogous, so in the event that 3 oxides can be introduced to each ring, it may be more stable. It would also then have a positive OB.

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