Nitramide reactions

Some ideas occured to me recently, about using nitramide to prepare interesting and powerful energetic materials.

I haven't been able to find much information to confirm whether my ideas would or would not work however, except the abstract of a journal (see below).

The first idea was to synthesis HANA (hexaazahexanitroadamantine), C4H4N12O12, which has a density of 2.10 g/cc. In this case the reaction would be:
6NH2-NO2 + 4CHI3 -> C4H4N12O12 + 12HI
The HI would most likely have to be absorbed by a base, ie triethylamine, that will not decompose nitramide rapidly. I would think the high reactivity of the C-I bonds would allow this reaction to take place readily. On the other hand the probable strain of the molecule would make the reaction disfavourable. They might also react to form other products, and not form HANA at all.
So, I am not really sure whether that would work, if it did it would be quite easy to do at home and would produce a very interesting energetic material.

The second one would be reacting nitramide with glyoxal, to form a piperidine ring NO2-N(CH(OH)-CH(OH))2N-NO2. This would no doubt lend itself well to the synthesis of some interesting energetics.
The original compound I had in mind that could be made from it was HHTDD, which would be formed by condensing the above compound with dinitrourea, adding a dinitrourea group on each side and eliminating water. Since water would decompose the DNU, would would have to form the tetracetyl of the nitramide product, and react that with the DNU instead as acetic acid would form, and it will not hydrolysis the DNU.
HHTDD has a densitry of 2.07 g/cc, perfect O balance, and is considered to be the most powerful explosive known. However, the nitration conditions require large amounts of 100% HNO3 and N2O5 and so straight synthesis would be difficult.
If nitramide forms the wanted ring, then the only starting materials are acetic anhydride, dinitrourea, glyoxal and the appropriate solvent, and maybe a catalyst.

The evidence I have for nitramide reacting with aldehydes comes from a journal abstract I came across while searching to see if these ideas would work, in which nitramide and formaldehyde formed a stable and powerful polymer.
A Study on the Condensation of Nitramide (NH2NO2) with Formaldehyde and the Characteristics of the Products Formed
Z. Raszewski, M. Syczewski
Propellants, Explosives, Pyrotechnics
Volume 24, Issue 6 , Pages 366 - 370

It would be nice if someone got it, the polymer looks like it would be interesting on it's own.
(CH2N-NO2)n --> nCO + nH2O + nN2

I have attached drawings of HANA, NO2-N(CH(OH)-CH(OH))2N-NO2 (not sure of the name) and HHTDD so it is much clearer what I am talking about.

Thoughts?

That is a massive amount of gass molcules

Nice ideas

Your HANA, do you have a reference on this?
Iodoform and nitramine - sounds simple enough. Do you have decent references on the production of H2N-NO2? I thought it was notoriously unstable.
I imagine getting the final product would be difficult as the proportions have to be gotten exact. How would you avoid getting intermolecular crosslinks, rather than this caged structure?
The reaction of the C-I moiety with H-NR2 would require conditions generally used for N-alkylations (similar to what was asked in the novocaine thread).

On the second one, I guess you got the idea from the tetranitropiperazine, which was described in one of the PEP papers by this Munich group (Klapoetke)?
I suppose this could work, they use formamide as opposed to nitramide.
Nitrating this is gonna be a pain or two, nonetheless (TFAA and such).

Re. these polymers - I had similar ideas like that before. For instance, I condensed CH2O with guanidine BASE, and very soon after, a white plasticky substance formed.
Of course this could now be modified to use nitroguanidine, nitro urea, and so on, and possibly make the nitrate salt of this afterwards. Alternatively one could start playing with semicarbazide, or aminoguanidine, and so on. So many things to do!

Definatly interesting, I think the HANA reaction is pretty likely if the C-I with H-N is able to take place in the standard way. There is actually very little strain in this molecule, after all it is (figurativly) a bunch of cyclohexane rings. Since cyclohexane pretty much has a strain of zero, the strain on this molecule is only slightly greater. I made this molecule with a molecular kit and there was only very mild forcing of the last bond together(unlike cubane which snapped the sp3 carbon when making the molecule).

Compared with what else could theoretically form based on the reaction of just the C-I and H-N, such as cyclobutane rings in the same format as the adamantane structure, and cyclononane based structures, and even larger, ring strain reaallly favours the adamantane structure.

Hehe...use iodopicrin instead of iodoform, ....4 more nitros on the molecule

Unfortunately I don't have readily acces to my books and notes(everything is in cardboard boxes for two years now-new mother's appartement, buildingwork, and now I go live with my girlfriend )...maybe in two weeks I wil be able to answer your question...
Regarding your -CH=O instead NO2...I wonder how do you account for the fact urea doesn't react with -CH=O?

You are misunderstanding what I have in mind. I've attached a diagram of what reaction works, and what I have proposed using DNU. OAc is used because otherwise the water produced by the reaction would destroy the DNU. In the first reaction, the CHO is hydrolysed during the reaction.
It may need other incentives to get the reaction to proceed fully however, ie basic enviroment etc.

The diagram looks fine. I don`t know the reaction works esay with HCL. Rather than with a other solution or the way from a existing nitramide to a nitramin ?
It have likely better attributes (density ad VOD) as TNGU and DNGU.

I have attached a diagram to get a THD (Tetrahedran) nitramin or nitramide derivat maybe with the same way, but diagram not uploadable ?

The formulas here.

(NNO2)3CNO2
(NHNO2)3CNHNO2

[Edited on 26-12-2005 by Madandcrazy]

N2O5 is stable at -10 gegree celsius and very hycroscopic.

Your knowledge are correct, N2O5 was easiest avialable by HNO3 and P2O5 ?

I`ve found a articel, N2O5 was manufactured per distillation.
Fuming white HNO3 is destilled with ozon gas to a beaker with freshly prepared P4O10 which was cooled to -10 gegree celsius and N2O5 should formed in a oxidation process when the ozonylized HNO3 passed to the P4O10.

I belive P4O10 is available as a drying agent for the industrie and is formed by the oxidation of phosphors with a lage excess of oxygen.
P4 + 5 O2 -> P4O10

Quote: Originally posted by BASF

I wonder wether it would be possible to brominate RDX... Mild conditions. The problem is, i know few to nothing about nitramine-chemistry.....

Quote: Originally posted by PHILOU Zrealone

halogenation of RDX might work but as you said the C-N link might not survive the halide. (-CHX-N(NO2)-)3 where X = F, Cl, Br or I Those haloRDX are also interesting because they might be precursor for couplage reactions of other explosophoric groups. Maybe a different way of action must be investigated! CH3-O-CH=O + NH2-NO2 --> CH3-O-CH=N-NO2 3CH3-O-CH=N-NO2 --> (-CH(OCH3)-N(NO2)-)3 (-CH(OCH3)-N(NO2)-)3 +3 HBr(g) --> (-CH(OH)-N(NO2)-)3 + CH3Br(g) or (-CHBr-N(NO2)-)3 + CH3OH