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Author: Subject: Peroxide of Acetylacetone (2,4-pentandione) ??
chemoleo
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[*] posted on 8-9-2003 at 14:54
Peroxide of Acetylacetone (2,4-pentandione) ??


Hello all,
I just discovered acetylaceton to be available publicly, at http://www.kremer-pigmente.de (just placed an order :) ).
This is CH3COCH2COCH3, so a diketone!
Considering that MEKP is quite interesting, this should similarily be so.
Anyone tried to make the peroxide? Structure? Synthesis?
At least this time I can point out an OTC source :P

[Edited on 9-9-2003 by chemoleo]
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[*] posted on 8-9-2003 at 18:11


Well for the synthesis it's the same for mostly all ketone (see Megalomania Page) for the schemen, but since it's a di-ketone i dont know if this would apply.



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[*] posted on 8-9-2003 at 19:47


I don't see why both carbonyl groups can't be peroxidized. if so, it'll be more powerful than AP!:)
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chemoleo
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[*] posted on 15-9-2003 at 14:03


cool, the Kremer Pigmente order arrived. This seems like a great source of various chemicals. I highly recommend it, order arrived within 3 days (I_am_a_fish should add it to his readily available chemicals list!)
.
Anyway, as I have never tried a de novo synthesis of putative explosives (where there is no data on it), does anyone have suggestions as to the amount to start off with (I imagine there is a limit as to how far one can downscale an experiment)? What kind of precautions to make (other than doing the whole thing outside, operated remotely :P)? This compound could be by far more sensititve than AP, so it's a tricky experiment! Any comments?

[Edited on 15-9-2003 by chemoleo]
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[*] posted on 18-9-2003 at 22:53


If trying an untested synthesis of an unstable energetic compound, you should always begin with miniscule amounts. This way, any accidents will be much more manageable ( and also less likely to occur as it is much easier to cool small amounts of reactants ) and if the reaction conditions prove to be unfavorable, you will only have lost a very small fraction of your reactants.
I recommend about 0.5-1 mL as a starting point if using concentrated reactants. This amount is sufficient for acetone peroxide but not quite enough for HMTD.
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chemoleo
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[*] posted on 10-1-2004 at 13:11
I tried it :)


Finally I found some time over Christmas to try this!

Ice-cold pentadione and 30% H2O2 were mixed, 1 ml of the former and 1.2 ml of the latter. They did not mix, i.e. the H2O2 sank to the bottom of the test tube. Then, added 120 microliters of 75% H2SO4, in three portions.
An effect could be seen immediately, as the two immiscible liquids mixed and formed a single solution. I am not sure about temperature control here (during the addition of H2SO4), as it is hard to control with small amounts like that (unless I add 1 microliter H2SO4 at a time...).
Anyway, no precipitate occurred, but on the following day (stored overnight at 0 deg C), the solution was remarkably viscous, probably like 30-40% glycerol.
So - what to do at this point? I heated a drop on a spatula, and it burned after a bit with a yellow flame and strange smell. I put a few drops onto a plate, hoping the water would evaporate, and after a few days it did, leaving a very viscous clear sticky mass (which did not smell of acetylacetone anymore) - which burned like benzoylperoxide, i.e. made a slight crackling sound, and left no residue.

Sadly I didnt have time to follow things up :(, but I thought next time I try it, maybe
1. I should definitely neutralise before drying it - as it wont allow the peroxide to dry completely, plus it might degrade it slowly
2. Try to find a solvent in which the putative peroxide precipitates (dilution with water or ethanol didnt yield a precipitate, not surprisingly) - what else could I try? Alternatively, I could hope for a solvent that dissolves the peroxide, but not the water/H2O2...
3. Try slightly larger amounts, where it is easier to check temp. during H2SO4 addition.
4. Do the whole thing at higher temps? such as room temp?
5. See if the residue can be detonated :D

Any more suggestions? I am convinced the reaction worked (!!) to some degree, as the liquids mixed once acid was added, and as it became viscous, and, of course, most importantly, as it left a residue that burned!

PS good thing is, if I get this to work, at least it doesnt seem to be as sensitive as AP! But equally simple!

[Edited on 10-1-2004 by chemoleo]




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[*] posted on 12-1-2004 at 13:15


Damn. pentanedione is such a *nice* synthon, great for making various heterocyclics. To just blow it up is so ... wrong!:cool:
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[*] posted on 12-1-2004 at 17:05


Well in that case, why dont you start a new thread, on making heterocyclics with pentanedione? I am sure a lot of people will appreciate this :), including myself :)

Anyway, the *point* of this thread was to test isolatable peroxides of pentanedione, and to see whether they exist. I am sure some exist (see my previous post), but clearly some more experimenting needs to be done in order to get a pure (precipitating) product.

Sorry, but the argument is silly - you could say the same thing about phenol, toluene, N-ethyl-anilin, etc etc etc. Plus, I DO find it very interesting to test a compound for unknown/undocumented reactions, rather than following the well-trodden path of the known ones!

[Edited on 13-1-2004 by chemoleo]




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[*] posted on 13-1-2004 at 21:39


it is known/documented and is in use!
after searching google I came to this:
<i>Acetylacetone peroxides (AAP) are slightly more expensive that MEKP. Significant benefits with AAP are fast cure times and strong heat evolution. This allows thin laminates to cure rapidly. AAPs typically produce half the cure times of most MEKP initiators. Normal gel coats, however, will not work with these initiators. The main benefit of AAP is in shipping and handling due to a lower hazard class rating as compared to MEKP. Where safety is a concern, MEKP is considered corrosive to the eyes, and most AAPs are only considered an eye irritant.</i>
it says "less hazardous than MEKP" which makes me think only one of the carbonyl groups is peroxidized:(
also:
<i>Mixed product containing <font face=symbol>a</font>-hydroxy- and <font face=symbol>a</font>-peroxyhydroperoxides.
Commercial grades have 4% active oxygen.</i>




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[*] posted on 19-11-2005 at 20:21


A few months ago I mixed up some acetylacetone/H2O2/HCl, I didn't seperate so I extracted it with DCM.

I only just found some in the bottom of a beaker so I can guarantee its dry by now! Indeed, it doesn't respond very energetically to ignition, in that it doesnt propagate deflagration but tends to put itself out, flashing with a thump...thump...thump when held in a flame (<a href="http://xmovies.webtop100.net/banners/acetylacetone-diperoxide.mpg">blurry movie</a>;). Though is easily detonated with a hammer.

Its listed in PATR2700 (1, A53) as a polymeric diperoxide, (C<sub>5</sub>H<sub>10</sub>O<sub>4</sub>;)<sub>x</sub> very explosive, non-volatile glassy syrup. The product obtained fits that description.

[Edited on 20-11-2005 by Axt]
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[*] posted on 9-2-2006 at 08:09


I guessing the acetylaceton is quite interesting for a peroxide, more likely as a solvent
or in further reactions.
Maybe the acethylaceton is chlorinated :P to chloroacetylaceton
CH3COCHClCOCH3 when threated with Cl2 or HCL and the product is used
as a solvent or chemical is sidereactions for instance preparing nitrates.
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[*] posted on 10-2-2006 at 10:20


If you take MEK and put it in a NaNO2/HCl mix, the oxime is formed which is then immediatly hydrolized to butanedione.

Butanedione itself is very sensitive toward oxydizing agents. The same reaction could be done with pentanone or pentanedione to give pentanetrione ! This should be very sensitive, perhaps even with air ! Maybe it will yield something like CH3-CO-O-CO-CH3 or CH3-CO-O-O-CO-CH3 which can be somehow interesting...

I've approximated pentanetrione to be about 2600m/s at d=1. So it could be considered itself as a low explosive !
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[*] posted on 10-2-2006 at 15:49


Isn't CH3 CO O CO CH3

Acetic acid anhydride?
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[*] posted on 11-2-2006 at 01:00


Indeed but the two later compounds are theoretical only. It has been proposed by Philou in one of our discussions.

The oxime reaction itself comes from an organic chemistry book : Organic Chemistry by Clayden, Greeves, Warren and Wothers.

On paper it can be cascaded n times but in reality, the compound will become more and more sensitive against oxydation like air but also against the reaction itself because it involves HNO2 !
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[*] posted on 16-2-2006 at 08:35


sylla,

you mean the sodium nitride is reacted with a amin or a amide.
In HCl ?
More the HCl is reakted with NaNO2 to NaCl and nitrogen oxides, the sense of the mix is more theory ;) and the endproduct is not good removed from the NaCl.
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[*] posted on 16-2-2006 at 12:43


NaNO2/HCl -> HO-N=O -> N#O+ "nitrosonium" (as I call it in reference with the nitronium ion NO2+)

H3C-CH2-CO-CH3 + nitrosonium -> H3C-(HC-N#O)-CO-CH3 --[proton]--> H3C-(C=NOH)-CO-CH3 --[proton/hydrolysis of the oxime]--> H3C-CO-CO-CH3
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[*] posted on 4-3-2006 at 21:50


Sylla, could you please post more details on this reaction? Did you try it? Yields? Why is the neighbouring CH2 attacked, rather than the carboxyl itself? This would be an extremely interesting reaction if it worked in good yields, and with ease...



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[*] posted on 5-3-2006 at 04:05


I don't have much infos, the book says it works with good yield...

I guess I could try the synth with butanone but I'm wondering how I could identify the end product. Anyway, I'm quite busy for a couple of weeks with the university so if you have some spare time to try this experiment it would save us the delay :)

But if any of you try it, be careful it could be dangerous... Butanedione seems to be hazardous to handle.
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smile.gif posted on 10-3-2006 at 05:47


CH3-CH2-CO-CH3 <--> CH3-CH=C(OH)-CH3
Enol-cetone equilibrium!

The C holding the OH is more electonegative and so the double link is polarised
CH3-CH(d+)-(d-)COH-CH3

Then looking at HO-N=O it has two ways of splitting!
A)HO(-) + N=O(+)
B)H(+) + O-N=O(-)

Considering A the resulting addition of the alcene will be:
CH3-CHOH-C(OH)(NO)-CH3 the later might be oxydised by the NxOy in the media...and loses its nitroso from nitrosocarbon or rearranges

Considering B the resulting addition will be:
CH3-C(-O-N=O)-CHOH-CH3
Owing to the fast equilibrium of nitrite ester...
CH3-CHOH-CHOH-CH3 is obtained and oxydised by NxOy into CH3-CHOH-CO-CH3 a alfa hydroxyceton.

Such molecules are strong reducers and are readilly oxydised.
Here again enol-ceton may apply to get
CH3-C(OH)=C(OH)-CH3

And so on...for additions and oxydations...

You end up with Butandione...

[Edited on 10-3-2006 by PHILOU Zrealone]




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