chemoleo
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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 
[Edited on 9-9-2003 by chemoleo]
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Blind Angel
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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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KABOOOM(pyrojustforfun)
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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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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 )? 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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Microtek
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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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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 
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]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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guaguanco
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Damn. pentanedione is such a *nice* synthon, great for making various heterocyclics. To just blow it up is so ... wrong!
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chemoleo
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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]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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KABOOOM(pyrojustforfun)
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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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Axt
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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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Madandcrazy
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I guessing the acetylaceton is quite interesting for a peroxide, more likely as a solvent
or in further reactions.
Maybe the acethylaceton is chlorinated 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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sylla
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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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DeAdFX
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Isn't CH3 CO O CO CH3
Acetic acid anhydride?
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sylla
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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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Madandcrazy
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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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sylla
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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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chemoleo
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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...
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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sylla
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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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PHILOU Zrealone
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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]
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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