keto-RDX peroxide?

[CodeMason]

I think this explosive would be a devillishly sensitive but powerful primary. Probably would be the most powerful primary known. The ring structure of keto-RDX is already trimeric, so this wouldn't be much of a problem, although the carbonyl C=O radical is only present on one monomer in the cycle (IIRC). Here's a very rough structural diagram (more like a sketch) I thought up:<font face="fixedsys">
&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;NO2
&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;|
&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;N
&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;/&nbsp;\
&nbsp;&nbsp;&nbsp;&nbsp;|&nbsp;&nbsp;&nbsp;|
NO2-N&nbsp;&nbsp;&nbsp;N-NO2
&nbsp;&nbsp;&nbsp;&nbsp;\&nbsp;&nbsp;&nbsp;/
&nbsp;&nbsp;&nbsp;&nbsp;C=O-O</font>
Thus with a formula of C₃H₄N₆O₈.
Any problems with this idea? Would the acid/peroxide mix oxidize the keto-RDX into something else entirely? I thought about this, but I believe the only thing it really can oxidize it to is diketo-RDX or triketo-RDX peroxides. Thus also satisfying the need for a trimeric peroxide. This explosive would be extremely unstable and have a positive or neutral oxygen balance (mixing it with various fuels would make it even -more- powerful). Any thoughts?

[mark]

Why would you want to make it if its extremley sensitive? Do you realy need the extra power.

[CodeMason]

Because of the power, it could be used in very small amounts in blasting caps, thus increasing safety, and making it more cost effective for most people.

[mark]

quote
thus increasing safety

But you just said it would be horribly unstable! And ap can be made by the pound for under $20.

[CodeMason]

But AP has relatively meek initiation qualities as compared to say mercury fulminate, thus you need a large amount of it in caps which is very risky. On the other hand you would need a tiny amount of this theoretical explosive in your detonators, thus making it overall more safe. I can't see it being -that- much more unstable than AP, and in a stoichiometric mix with a fuel it would be less sensitive and even more powerful.

[cutefix]

I suggest that you read the US Patent #6,139,054 about keto-RDX which is called2-oxo-1,3,5-trinitro-1,3,5-triazacyclohexane for more details about its synthesis,properties and application.

[CodeMason]

Thanks cutefix, that patent was very informative. It reveals that there is indeed a triketo-RDX, the proper nomenclature being 2,4,6-trioxo-1,3,5-trinitro-1,3,5-triazacyclohexane. A peroxide of this would be very interesting.

[Mr Cool]

So you're suggesting that an extra oxygen atom would be added between the carbonyl group and a nitramine group? What about forming a dimmer/trimmer like Acetone peroxide, with oxygens joining the monomers? i.e. with a formula like this: (C3H4N6O8)n, where n is two or three?
One problem that I can see is that IIRC K-RDX is insoluble in water, so when you added the H2O2/acid(aq) to the solution of K-RDX in whatever solvent you have it in (MeOH? Not acetone, since this would be peroxidised), it might just ppte. the K-RDX from solution, thus meaning that it wouldn't react very well...
Also K-RDX isn't all that easy to make, and I wouldn't want to make it into a peroxide that I was too scared to go near!
I thought that having three C=O's on the RDX ring stressed it so much that it just decomposed? Perhaps I was wrong...

Does anyone know if you could condense an equimolar ratio of nitrourea and formaldehye to make Diketodinitro-HMX, perhaps with MeOH as a solvent? Could be interesting, and very easy to do if it works...

[Hex]

Here we go...I always seem to find myself pouring cold water on peoples ideas on this forum! Sorry!
k-RDX is a very different beast from acetone. N-nitro is a reasonable leaving group, so even if hydroperoxide anion is a good enough nuc to hit the carbonyl (doubtful, you need to use NaOMe to do the hydrolysis at reasonable speed), I think it's probably going to lead to ring opening
And H-O-O-C(=O)-N(NO2)- has got decomposition to CO2 written all over it, so I can't see any plausible route to reclosure.
If I've got your structure right, you've got 4 heteroatoms all in row, in a non-aromatic system - not likely. But you never know...

Quote - "Does anyone know if you could condense an equimolar ratio of nitrourea and formaldehye to make Diketodinitro-HMX, perhaps with MeOH as a solvent? Could be interesting, and very easy to do if it works..."

This sort of reraction has been done with NN'-alkylated ureas, with catalytic amounts of acid. It probably goes through the six membered 4-oxodiazine intermediate. The yields are pretty poor, but it's a possibility. Not sure about the stability of nitrourea under the conditions.
All of the keto-HMX's are mentioned in patents for use in airbags, smokeless motors etc, but I don't think the mono-, tri or tetraketo compounds have actually been made (bit of pre-emtive patenting going on I think) The triketoRDX has been under a lot of scrutiny as a possible precursor to new caged compounds.

[CodeMason]

No no Hex any criticism is greatly appreciated, an open forum of theoretical scientific discussion is what sets us apart from the k3wls, and criticism prevents us from doing something stupid and wasting precious reagents. http://theforum.virtualave.net/ubb/smilies/smile.gif
Dinitrourea is formed by reacting urea with anhydrous or close to anhydrous (equal parts) mixed acids for around an hour. Without anhydrous conditions, DNU is rapidly hydrolyzed. I don't see why metal nitrate+super conc. H₂SO₄ (preferably oleum) wouldn't do the trick. It is a very promising precursor to keto-RDX.

[Hex]

DNU may be a way to k-RDX, but I'm troubled by the fact that DNU in aqueous formaldehyde solution doesn't give any k-RDX, just a polymethylene nitramine (P,E,P, 24, 366-70 (1990) - don't know if that's on Mega's PEP site). Even though DNU is hydrolysed by water, it happens slowly enough for salt formation in aqueous solutions in ok yields, so it would appear that at some point there will be DNU and nitramide together in solution - which "should" react to give water-insoluble k-RDX, but doesn't. That said, there's a lot of scope for changing the conditions, especially solvent and temperature. But I have found that getting O2NNH2 to react with HO-CH2-N(NO2)-R, as we require here, isn't all that easy. Let us know how any of your experiments go, including any attempts to get DNU with a metal nitrate.

[CodeMason]

Ok, a more plausable chemical:<font face="fixedsys">
2ON-N-CH2-O-O-CH2-N-NO2
&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;\&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;/
&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;CH2-O-O-CH2</font face>
Which is basically just a nitrated dimer of HMTD, with the possiblity of the CH₂ being oxidized to keto groups, hence forming something closer to my original hypothetical substance. A method could be the action of acid catalyzed H₂O₂ on hexamine dinitrate, or its dehydration product (forgot its name currently.)

[heh, damn structurals]

[This message has been edited by CodeMason (edited October 11, 2001).]

[tvs17]

Hex, do you know if diketo-HMX has been made?

[PHILOU Zrealone]

Don't tell me I'm late to reply, I know!

I must say simply that carbonyl C=O is not equivalent from one compound to another!
So basically:
NH2-CO-NH2 is different than
NH2-CO-CH3 itself different than
NH2-CO-ONH4 i d t
NH4-CO-O-CH3 i d t
CH3-CO-CH3 i d t
CH3-O-CO-O-CH3 i d t
CH3-CO-H i d t
H-CO-H i d t ...

In a previous post there is a mention about urea-formol peroxyde; you see that the peroxyde
is between two CH2
(-NH-CO-NH-CH2-O-O-CH2-NH-CO-NH-CH2-O-O-CH2-)
This implies that the intermediary is
NH2-CO-NH2 + 2 O=CH2 --> CH2=N-CO-N=CH2 + 2 H2O
and --> HO-CH2-NH-CO-NH-CH2-OH
forming some hydroxyperoxyde and condensing to get the ring structure!

The same effect happens with hydrazine/formol and H2O2:
You get
NH2-N=CH2 units and NH2-NH-CH2-OH units that peroxydise and condensate to ring closure into
(-NH-NH-CH2-O-O-CH2-NH-NH-CH2-O-O-CH2-)

You thus see that ceto group from urea is unable to act as peroxyd holder like the ceto group of a formol or aceton molecule.

Now speaking of more powerful explosive than CTAP:
*Formol peroxyde is a good thing to look for:
(-CH2-O-O-)n
*Ethanal peroxyde too:
(-C(CH3)-O-O-)n
*nitroaceton peroxyde also:
(-(CH3)C(CH2NO2)-O-O-)n
*And even better dinitroaceton:
(-C(CH2NO2)2-O-O-)n