Sciencemadness Discussion Board

Energetic derivatives of cyanuric acid?

killswitch - 30-3-2012 at 10:40

I was toying with the idea of an HNO3 generator that functioned via pyrolysis of urea and came across the interesting connection between that process and the production of cyanuric acid, which is widely available in pool supply shops. As an aromatic nitrogen heterocycle, it strikes me as an excellent precursor for interesting energetics. I remember one of the senior members being engaged in the planning of a particular synthesis of a certain energetic compound starting from cyanuric acid, and was wondering if there were any relatively simple procedures for producing an energetic derivative of this compound that doesn't require things like three-necked flasks, fractional distillation, chlorocarbon solvents or DMSO, etc.

[Edited on 31-3-2012 by killswitch]

Pulverulescent - 31-3-2012 at 04:44

There's cyanuric triazide (see COPAE), a sensitive primary.

PHILOU Zrealone - 31-3-2012 at 06:05

Let me share a bit on that subject...

Trinitrocyanuric ring is more than certainly too unstable to exist because of the electron withdrawing effect of the nitrogen atoms on the aromatic ring...
The nitro-nitrite rearrangement of the nitro groups is apparently favourised by such conformations and are thus leading to a mixed anhydride (cyanuryl-nitrite).
The same kind of behaviour can be seen with nitrocyanide...
Such mixed anhydide compounds are very water sensitive and hydrolyse immediately from the water vapour in the air
N#C-NO2 <-=> N#C-O-N=O =H2O=> HO-C#N + HO-N=O
The reaction can be very exothermic and free a lot of oxydising NxOy fumes aside with oxydation products...in the case of the present molecule, the all batch can turn into a boiling suffocating smog...maybe with explosion.

The nitro-nitrite rearrangement is responsible of the unstability towards water or towards heat of:
-vicinal dinitroaromatic compounds and of vicinal dinitroalkanes.
-hexanitrobenzene that turns into trinitrophloroglucidol (2,4,6-trinitro-1,3,5-rihydroxybenzene) (see hydrolysis of HNB)
-2,3,5,6-tetranitro-p-quinone that turns into 2,5-dihydroxy-3,6-dinitroparaquinone (see synthesis of nitranilate salts)

About tri-nitramino variant of melamine (1,3,5-triamino-2,4,6-triazabenzene), it is also very unstable and sensitive to hydrolysis... In the case of nitraniline, the nitrogroup can migrate to the nucleus and result in a nitro-aniline (ortho or para); here such places are not accessible and so only splitting of NH2-NO2 (nitramide) is possible...
C3N3(NHNO2)3 + 3H2O -->C3N3(OH)3 + 3NH2-NO2 --> C3N3(OH)3 + 3 H2O + 3 N2O
You certainly noticed that the water only enters here as a catalyst of decomposition.

In such an hypothesis you should investigate the putative tri-methylnitramine variant of melamine...the methyl group will enhance the stability of the molecule making it maybe isolable (see tetryl). 1,3,5-Tri-methylnitramino-2,4,5-triazabenzene (N=C(-N(CH3)NO2))3 will be dense and quite sensitive to shock and maybe to heat/friction.

I think someone made cyanuric tri-nitroformide (C3N3(-C(NO2)3)3 ...it is listed on wikipedia...must have been done via metathesis from sodium nitroformiate and cyanuric trihalide in an adequate solvent.

[Edited on 31-3-2012 by PHILOU Zrealone]

Nicodem - 31-3-2012 at 07:00

I always suspected nobody ever UTFSE! Now I see it is indeed so:
https://www.sciencemadness.org/whisper/viewthread.php?tid=18...

neptunium - 31-3-2012 at 07:03

the link is broken Nico...

Nicodem - 31-3-2012 at 07:06

No it is not.
But you can still UTFSE if you are unable to use the direct link! :P

killswitch - 31-3-2012 at 07:32

Quote: Originally posted by Nicodem  
No it is not.
But you can still UTFSE if you are unable to use the direct link! :P


It's broken for me, too. Must be my browser add-ons.

But the information in PHILOU Zrealone's post was extremely valuable to me, so I'm glad I posted the thread.

So nyeah!

[Edited on 31-3-2012 by killswitch]

killswitch - 31-3-2012 at 07:42

I'm interested in how removing one or more of the hydrogen atoms would affect the behavior of the compound. It looks similar to keto-RDX, minus the nitro groups. Could this molecule:

.................O
.................||
............N÷C÷N
.............|:......:|
............C÷N÷C
...........//..........\\
..........O...........O

exist?

I really, really wish I hadn't left my textbooks at my house...

[Edited on 31-3-2012 by killswitch]

stygian - 31-3-2012 at 08:48

The link isn't broken, it's https, Check your browser settings.

PHILOU Zrealone - 31-3-2012 at 10:50

Quote: Originally posted by killswitch  
I'm interested in how removing one or more of the hydrogen atoms would affect the behavior of the compound. It looks similar to keto-RDX, minus the nitro groups. Could this molecule:

.................O
.................||
............N÷C÷N
.............|:......:|
............C÷N÷C
...........//..........\\
..........O...........O

exist?

I really, really wish I hadn't left my textbooks at my house...

[Edited on 31-3-2012 by killswitch]

Of course this structure exist it is isocyanuric acid...which can be interconvertible into cyanuric acid.
(-N=C(-OH)-)3 <==> (-NH-CO-)3

Unfortunately, like parent compound dinitrourea (DNU aka O2N-NH-CO-NH-NO2 which is isolable but rather unstable because of autocatalytic selfdecomposition favourised by water....what is itself a product of the decomposition. DNU can be stabilised as its salts of K or NH4); the trinitro variant of isocyanuric acid (-N(NO2)-CO-)3 (or triketo-RDX) would be even less stable and not able to form salts because of the lack of available protons. Here also electron withdrawing effect arround the nitro group favourise a nitro-nitrite rearrangement and subsequent unstability or hydrolysability.

franklyn - 31-3-2012 at 20:11

Better moieties for attaching explosophore groups are
available than triazine trione. I noted that in the closing
comment on this subject , in the middle of this post _

http://www.sciencemadness.org/talk/viewthread.php?tid=16785#...

" My initial interest waned as the projection of performance is disappointing.
The Trazine Trione skeleton has a high heat of formation which evidently degrades
the heat of explosion of what is essentially three attached Methyl Nitrates."

.

AndersHoveland - 31-3-2012 at 21:31

I do not think there are any explosives that can be made from cyanuric acid, at least not directly. That is just my opinion.

The only explosive I am aware of is, as was previously mentioned in this thread, cyanuric triazide. But I do not think this is a good explosive. It would essentially be a waste of NaN3.

Cyanuric acid might contain three atoms of nitrogen and have its carbon atoms already partially oxidized, but it is also a very stable molecule because it is essentially a triple amide (the amine groups are electron donating to the oxygen atoms in the carobonyl groups). These types of amides cannot form salts, and cannot take nitrations (since there are two carbonyl groups attached to each amine)

Usually nitrogen is much more useful in explosives if it is bonded to another nitrogen atom.

[Edited on 1-4-2012 by AndersHoveland]

PHILOU Zrealone - 8-5-2012 at 09:30

I think that the metathesis between cyanuric trichloride and a nitroformiate do give something worth...cyanuric trinitroformide
(-N=C(Cl)-)3 + 3 Na-C(NO2)3 --> (-N=C(C(NO2)3-)3 + 3 NaCl

Sole problem is the overoxygenation (OB being positive)...

This may be circumvented by the hypothetical similar reaction between cyanuric trichloride and 1,1,2,2-tetranitroethane disalt...this would end up in a 2D or 3D polymeric network with a perfect OB...
2(-N=C(Cl)-)3 + 3 Na-C(NO2)2-C(NO2)2-Na --> ((N3C3)(C(NO2)2-)3)n + 6 NaCl