Nitration of Acetone

[knowledgehungry]

As i posted earlier i tried to separate HNO₃, which i synthesized, from the ammonium sulfate it was mixed with. I did this by mixing acetone in with the mixture then decanted it off. The first time i tried this it worked and the acetone evaporated off and i was left with relatively pure HNO₃. When i tried to do it in larger quantities i got runaway nitration of the Acetone. I was wondering if anyone had any idea what the resulting compound would be called or look like. I could not test the properties of my nitrated acetone as i had to quickly dump the reacting mixture down the sink to spare myself from NO₂ poisoning.
Also if this compound has any use.
When i get back from visiting my relatives i will try a more controlled synthesis of whtever the hell it was that i created.

[nbk2000]

Maybe it's not a nitration. It could also be an oxidation.

[kingspaz]

wouldn't it just be ethanoic and methanoic (acetic and formic) acids?
like nbk said, its possible the acetone got oxidised. releasing NO2 as a result. i don't know much about oxidation of things using nitric but i'd guess it would be for a similar reason as to why dissolving Ag in nitric releases NO₂. Ag is hard to oxidise and so is acetone because its a secondary aldehyde (known as a ketone :p ).
just my almost random guesswork answer to it.

[simply RED]

Once i tried to mix acetone with HNO3 and H2SO4 (i don't know why) and also a runeway occured.
Theoretically if you make low temperature nitration the next reaction is possible:
CH3COCH3 + 2HNO3 = CH3-C(ONO2)2-CH3 + H2O
CH3-C(ONO2)2-CH3 must have the same properties as nitroglycerine

[megalomania]

I don't think you can nitrate an aldehyde or ketone, but I just mentioned in the FOX-7 thread about reacting acetaldehyde, an aldehyde, into glyoxal, a double aldehyde. There is no reason why a ketone should not work in the same way, probably oxidizing both ends of acetone into something... something quite weird which I have no idea what the name may be. I have my molecular modeler and FTP already open so lets draw a picture:
<img src="http://www.roguesci.org/images/tricarbonyl.gif" alt=" - " />

I found nothing in Merck, Aldrich, Chemfinder, or Organic Synthesis that matches this molecule. It may also become a diol or carboxylic acid, like so:
<img src="http://www.roguesci.org/images/acediol.gif" alt=" - " />

Of course we all wish this would happen:
<img src="http://www.roguesci.org/images/fancypoly.gif" alt=" - " />

[NoltaiR]

Of coarse the priming shockwave itself would have to super-powerful just to get a result even close to the theoretical (which I am not sure how mega came up with the idea of 27k m/s). And I am not too familiar with the idea of how a NO2 would be split to releaste the nitrogen needed to for the pressure blast effect and how the oxygen would then be used to make a complete combustion...

[megalomania]

I was actually joking with this compound. My "wish" is that nitrating acetone would form a super high density explosive more powerful than anything in existance :D

[knowledgehungry]

Well the mixture of Acetone and HNO₃ has been sitting around for about a week, it looks like the attempted phorone(dark red) but that could just be NO₂contamination. I took a small amount of it and lighted it, it burned but it was just the acetone burning. As the mixture started to heat i got more of the runaway nitration/oxidation with large amounts of NO₂fumes coming off there was only a small amount of product left in the beaker, less than 1/2 ml. Im going to heat some more of this mixture today outside, and see what is left in my flask.

[Pu239 Stuchtiger]

Generation of NO₂ gas is evidence that oxidation is occuring.

Mega: Acetone can be nitrated. And I believe that the first compound you drew is very unstable. Two adjacent carbonyl groups are unstable; three adjacent are very unstable. That also rules out the possibility of the carboxylic acid that you diagrammed as being stable. CH₃ groups aren't oxidized as readily as CH₂OH groups, so the diol would only be formed in small amounts. This is probably what is happening:

CH₃--(C=O)--CH₃ ---(oxidation)---&gt; HOCH₂--(C=O)--CH₃

And then lots of relatively complex shit happens, but I'm too fucking lazy to boot in Windows and draw diagrams. Oh well.

Ta-da. *band plays*

[nbk2000]

Knowledgehungry, you say that you evaporated off the acetone and was left with concentrated nitric. How do you know it WAS nitric, and that it wasn't just traces of sulphuric acid and not concentrated nitric?

[knowledgehungry]

The first time i am not sure that it was pure nitric( except that it gave off the choking odor and when heated it decomposed into NO2 gas)
In my second attempt which resulted in the reaction which we are currently discussing I used an excess of NH₄NO₃so i believe that all the sulfuric was reacted. I'm quite sure now that this method will NOT work for obtaining pure nitric(my first attempt was in such a small amount that it was impossible to tell whether all the acetone had evaporated)

[drednort]

Something I have done before to clean particularly dirty glassware is to put conc nitric and a bit of ethanol together. It is pretty exothermic with the evolution of brown fumes. I once swapped the ethanol for THF and nothing happened for a few minutes. Then the whole fumecupboard flashed luckily the visor was down. Anway, the nitric acid / acetone sounds a bit like that. It is probably oxidative degradation that you saw.

[BASF]

Maybe the following patent is of interest.
It describes the formation of an energetic material from acetone and dilute (or concentrated) HNO3.

United States Patent 5,043,488
Schulz , et al. August 27, 1991

Greets to all being curious

[nbk2000]

It would seem, from what I gathered from the patent, that you could make this explosive by mixing sulphuric and potassium nitrate, letting that form nitric in situ, then dump it into a filter and wash the nitric out from the insoluble sulphate using acetone.

Then simply reflux on a hot water bath.

Since there'd be no water in the process (unless it's formed), you wouldn't have to bother with a distillation. Simply use as is as an explosive.

Though it bothers me that they didn't mention anything about detonation velocity. They just compare the nitrogen content to other explosives. That in itself doesn't give any measure of its power.