2,2-diaminopropane: can it be nitrated?

[Mr Cool]

OK, I suppose this might be better in misc., move it if you like, but I put it here because it's a possible HE reactant and should be easy to make.

I've heard that ammonia reacts with acetone. I'm presuming that the acetone loses it's oxygen atom, and gains two NH2 groups, forming water in the process. The product, I suppose, would be 2,2-diaminopropane.
I noticed that this was a little similar to urea, but with two methyl groups insted of the oxygen, so I was wondering if this would be compatible with H2SO4? If so, I'm sure it could be nitrated to a HE and I'd guess that it'd be more sensitive and perhaps have a higher VoD than nitrourea.

[the freshmaker]

That is very interresting. A good stable and powerfull HE from easy-avaible chemicals.
I'm looking forward to see how this turns out.

[Cipolla]

The Reaction of ammonia on acetone yields
(CH3)2-C=NH. Which on reaction with chloramine forms (CH3)-C-(NH)2, which is a cyclic compound, having a C-NH-NH ring...
The both compounts may be nitrated to nitramines using chlorides as catalyst.

[Mr Cool]

Thanks for that information Cipolla. But do you know if they are compatible with H2SO4? If not would it work with conc. HNO3 (90%+), or would that just form a nitrate salt?

[Hex]

Gem-diamino compounds are generally unstable, and can usually only be isolated as salts, such as [CH2(NH3)2]2+ [SO4]2-.
Anyway, it's virtually unheard of for a free primary amine group to nitrate successfully (the NH2 groups in urea and guanadine do, but are not "typical" due to the proximity of respectively, C=O and C=NH groups). I also expect that the reaction between ammonia and acetone would be quite slow, and would have to be done at temperatures where a lot of the imine formed would polymerise.
I'm intrigued by the suggested reaction of the propan-2-imine with chloramine - do you mean that a 3 membered C-N-N ring forms? Do you have any references for this reaction?

[Mr Cool]

Damn. http://theforum.virtualave.net/ubb/smilies/frown.gif I was just wondering due to the slight similarity between the structures of it and urea.
I can't work out how a ring of -C-NH-NH- can form from that formula... the carbon only makes three bonds, one with each of the nitrogens and one with the methyl group. Can anyone please explain?
Would I be correct in thinking that chloramine is NH2Cl?

Edit: did you mean (CH3)2-C-(NH)2?

[This message has been edited by Mr Cool (edited August 17, 2001).]

[Cipolla]

In the formula the carbon is linked with both of the nitrogens and they're linked themselves.

Chloramine is NH2Cl and is formed by the action of hypochlorites on ammonia. For nitration the use of acetic acid or acetic anhydride should be employed. For nitramines acetic anhydride gives better results than sulphuric acid.

[Mr Cool]

Yeah, I think you missed out a CH3 in the formula you posted, I didn't realise at first.
I knew H2SO4 didn't often work with amines, but I didn't know about the use of acetic acid. Would just ordinary glacial acetic acid work at all?

[Hex]

I think there's a bit of confusion here. Acetic acid is sometimes used a solvent in nitramine nitrations, but acetic acid/nitric acid is not (as far as I know) used as a nitrating acid. I've never seen acetic acid used in such cases without the presence of acetic anhydride, which reacts with nitric acid to form acetyl nitrate, which is, or at least the precursor of (there's a bit of debate about this in the literature) the nitrating species in these reactions.
I suspect that acetic acid/nitric acid mixtures would be less effective nitrating agents than nitric acid alone.
Not all nitramines are incompatible with sulphuric - nitroguanidine, nitrourea and CL20 can all be made with mixed acids.

[Cipolla]

Acetic anh. also forms N2O5 with nitric acid, the acetyl nitrate is not even the working nitrating agent. Acetic acid is able to form acetylamines in the same way as acetic anhydride does, and then nitration with HNO3 is easier to carry out, but not in every case, sometimes HCL is needed as a catalyst, sometimes not...
By the way may nitric acid which is not pure be better for tricyclic compounds, which seem to be not very stable. I only suggest the use of acetic acid/anh., no reason to employ scientific discussions as the use of perhaps nitrosium tetrafluoroborate may be suggested, we're only hobby-chemists and not the best, the professional blah blah is not our practic business.

[Hex]

I've seen it suggested that NO2(+) or AcONO2 is the nitrating species in acetic anhydride/nitric mixes - but N2O5??? Some
of these reactions (ie the Bachmann) are run at temperatures where the half-life of N2O5 is measured in seconds. I also can't see how acetic acid can form acetylamines in the same way as AcAn - surely you'd be much more likely to get the ammonium acetate? Philou?


[This message has been edited by Hex (edited August 22, 2001).]

[cutefix]

Nitramine explosives like as RDX were made before by direct nitration,with concentrated nitric acid.Acetic acid was for solvent purposes only in these unique amine nitrations.The reasons why acetic anhydride is used for these nitrations is twofold:1) Dehydrating agent 2)formation of acetyl nitrate which is an effective nitrating material in these cases.I think It should work also for these diaminoparaffins.
Sulfuric acid was indeed tested in the preparation of nitramine explosives.check it in USPatent#2,355,770 by Wyler,but he was not able to get any advantage than using P2O5,in RDX synthesis which the yield was dramatically increased from 71% to 90%of theoretical.In fact when he used pure nitric acid(99%+) he got slightly more yield than with nitric acid treated with oleum.
We should not discount exotic nitrating materials like nitronium tetrafluoroborate,they are effective in their own means. New explosives synthesis like HNIW were pioneered by this tetrafluoroborate,as well as the preparation of bicyclo-HMX.
Cipolla We cannot learn more if we close our minds against nontraditional ingredients.That adds spice to the discussion and will encourage us to delve deeper into the mechanism why that certain material work...

[Cipolla]

What a nice speech, let it print on bubble gum papers. The only thing I said is that acetic acid/anhidride should work better than sulphuric acid for the nitration of nitramines, and you take the chance to start a semiprofessional discussion aiming to show off your knowledge accumulated from several books which you are proud to own. In fact it makes no difference (for this forum topic) if the nitrating agent is acetyl nitrate or N2O5 as long as it works. Seems you forgot what you are: no professional chemists, only a few guys who are interested in chemistry.

And a word about my closed mind. My closed mind made a few improvements in the synthesis of unusual explosives which are not taken from the uspto.

[This message has been edited by Cipolla (edited August 23, 2001).]

[cutefix]

Look I didn’t mean to offend you,sorry about that.
But ,you are wrong pal,Frankly,I obtained chemistry training in the university.I own no explosive books, just accumulated knowledge from old experiments and my previous employment in this field and updated with the help of friends who are still employed in it,and last, through reading .Its not my habit to flaunt,I’m not brillant enough to do that,somehow I believe that the forum is a venue for intelligent discussion that expands one’s understanding of the subject you are familiar and as well as what you don’t know...If it happens that one participant cannot cope up with it,why feel jealous,you can watch the works and try learning something from it.I don’t see any competitive spirit in this forum,just the zest for discussion which we are all united to the same cause….