madscientist
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Dinitroacetone peroxide
I was thinking that nitrating acetone, and then preparing the cyclic peroxide of that, should yield a primary explosive of unprecedented power. I
believe PHILOU Zrealone may have mentioned such an idea in the past, and if so, that's probably why that idea was lurking in my mind.
I prepared a solution of 9mL concentrated HNO3 and 11mL concentrated H2SO4. I cooled it down to 0C, and proceeded to
slowly (and often sloppily) add 5mL of acetone with a separation funnel (I need to get a pipette...). I kept the temperature between 0C and 5C with a
NaCl/ice bath, except for one occassion, where I added acetone a tad too quickly, causing the temperature to rise to 8C. After adding all of the
acetone, I was becoming very cold due to the freezing wind outside, and went inside, thinking nothing of my mostly-molten ice bath. I had been inside
for about five minutes, staring through the window at my experiment, when it began billowing NO2. Obviously, the temperature had risen out
of control, resulting in a runaway nitration. The plume of NO2 disappeared after approximately ten seconds. I waited half an hour, and then
looked at the thermometer with binoculars - it had cooled down (I'm not willing to venture near to a glass reaction vessel containing concentrated,
oxidizing acids, unless it's clear that it's not about to detonate). I approached the beaker, added a few pieces of ice, and then poured in around
100mL of icy water. An orangish oil precipitated; it soon turned greenish, and then disappeared altogether. A slow fizzling began. This is my
hypothesis for what had happened up to that point: the acetone had been nitrated, forming dinitroacetone. The temperature had then risen out of
control, causing the extra nitric acid to oxidize the dinitroacetone, yielding nitroformic and nitroacetic acid. The nitroformic acid was probably
stabilized by being in concentrated strong acids. When diluted, the nitroformic acid was no longer stable, and began to decompose via the following
equation:
2O2NCOOH ----> 2CO2 + H2O + NO + NO2
An equamolar mix of NO and NO2 is, of course, an anhydride of nitrous acid, which reportedly is a greenish/bluish liquid.
Back to the experiment: I added 10mL of 27.5% H2O2 to the solution, hoping (but not expecting) to get a precipitate. No
precipitate ever formed. Just before I dumped the solution in disgust on the waste disposal site located on my lawn, I noticed that it possessed a
strong acetic odor.
I weep at the sight of flaming acetic anhydride.
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Polverone
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I do not think that you can nitrate acetone with mixed acid as you are attempting.
ALIPHATIC NITRO KETONES
CHARLES D. HURD, MAY E. NILSON;
J. Org. Chem.; 1955; 20(7); 927-936.
I can give this article to you. It includes a description of how nitroacetone can be prepared. It also indicates that nitroacetone is very prone to
decomposition after preparation.
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BASF
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I WANT to believe that such a compound could exist, maybe it wouldn´t be very stable(not a difficult guess hehe).....
Below a patent i came across some time ago, which is about the nitration of acetone with dilute and conc. nitric acid.
It seems to be fairly simple although it also lines out that the resulting product consists of a mixture of different nitrates and maybe also other
(degradation/oxidation)-by-products.
Therefor they refer to different grades of nitrogen content in their product, very similar to nitrocellulose.
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BASF
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damn.....forgot to add what i was talking about
United States Patent 5,043,488
Schulz , et al. August 27, 1991
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BASF
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Recently i was playing around with chemsketch, trying to get some output regarding a hypothetical trimeric dinitro acetone peroxide.
My hope was that chemsketch could also give some valuable data on bonding lengths (>stability), but it seems that the program is limited to the
known standard bonding lengths for di/tri-atomar compounds and the like.
Definitely, it does not give a shit about ring-strain......a hypothetically fully nitrated cyclo-propane ring has the same C-C bonding lengths as any
alkane 
Ok. It is a simple non-profit program.
*sigh*
On the other side, the predictions for substance´s densities have turned out to be accurate.......draw any energetic material you know, and
chemsketch will not be far off reality with the density
For a hypothetical 3,5,8,10,13,15-hexanitro-1,2,6,7,11,12-hexaoxacyclopentadecane-4,9,14-trione, which is actually our trimeric nitro-peroxide:
Density = 2.04 ± 0.1 g/cm3
(After all, this would be an amazing density for an organic peroxide...)
Index of Refraction = 1.594 ± 0.03
Molecular Formula = C9 H6 N6 O21
Formula Weight = 534.172 g/mol
Composition = C(20.24%) H(1.13%) N(15.73%) O(62.90%)
HLR
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Microtek
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If I draw inositol hexanitrate ( inositol is a cyclohexane ring with OH-groups on all carbons ) and tell chemsketch to calculate density, it claims
2.57 +-0.1 g/cc which is quite a bit over the top. RDX gives 1.89 ( 1.82 experimental ) and HMX gives 1.95 which is right on target.
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Polverone
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Computational chemistry fascinates me but it seems very difficult to have packages accurately predict properties of substances that they don't
"know" already. Semi-empirical methods are faster than ab initio and, what is more surprising to me, generally more correct, at least in the
domains they are designed for. But I have not been able to try a truly wide variety of packages. I've used ghemical under Linux, Fujitsu CAChe
under Mac OS, and ChemOffice Chem3D under Windows. None of them attempt to make substantial predictions about properties of the substances under
consideration, apart from structure and heats of formation. They all use MOPAC and derivatives thereof for semi-empirical calculations. I haven't
installed any of the extra software I would need to try ab initio methods for myself.
There are a number of experimental packages that can be obtained by request from the research groups developing them, but I have never pursued these
packages because research software - especially that written by scientists instead of software engineers - tends to be quirky and hard to use. The
package I would really like to try is Gaussian, which was once distributed freely and is now priced way out of my reach. It interests
me because it attempts to compute a number of useful things about the substance - IR spectra, density, and water solubility among others, IIRC.
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PHILOU Zrealone
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There is serious risks to make nitroaceton and dinitroaceton from aceton and HNO3/H2SO4!
First off:
aceton polymerises in strong dehydrating acids into mesitylene when heated...and mesitylene (trimethylbenzen has always lead to fire or explosions
while subjected to nitration acid mix!)
When the cold process is used, you get mesityl oxyde and phorone!
In a nitrating matrix they will provide not only (CH3)2C=C(NO2)-CO-C(NO2)=C(CH3)2 and
(CH3)2C=C(NO2)-CO-CH3 but also owing to nitrous fumes to oxydation products!
CH2=CH2 + NOx --> O2N-CH2-CH2-NO2 + ONO-CH2-CH2-ONO + O2NO-CH2-CH2-ONO2 + HO2C-CO2H and all combination of the above half molecules!
The formation of nitrate and nitrite esters is what causes the most troubles
In this case we have even more possible end products knowing that each C=C bond can be oxydised into -CO-CO- and then splited!!
All those process are very exothermic!
Secondly:
If normal reaction of aceton and conc HNO3 are reacted you get
CH3-CO-CH3 <--> CH3-C(OH)=CH2
CH3-C(OH)=CH2 -NO2(+)-> CH3-C(OH)=CH-NO2 and then CH3-C(OH)=C(NO2)2 further oxydation lead to nitroform and TNM (as mentionned Madscientist)!
Thridly:
CH3-CO-CH2-NO2 is very prompt to self condensate into high polymer (exothermic process!!!!
CH3-CO-CH2(NO2) + O=C(CH3)-CH2NO2 --> CH3-CO-C(NO2)=C(CH3)-CH2NO2 + H2O
One of the possible result is trinitromesitylene!!!!
Finally:
Aceton is 100% miscible with 100% HNO3 the resulting mix is a binary explosive as sensitive as nitroglycerin!!!!
So better do nitroacetons via a metathesis way:
Cl-CH2-CO-CH3 or Cl-CH2-CO-CH2-Cl reacted with AgNO2 or NaNO2!
Beware of chloroacetons they are lacrymator, irritating volatile liquids (toxics!) they are unstable and polymerise upon time (what property is
similar with nitroacetons to get high molecular weight HE)!
One possible result of trimerisation of 1,3-dinitroaceton is (O2NCH2)3C6(NO2)3!!!!
Trinitromethyltrinitrobenzen a sensitive HE that must be outstanding!
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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Axt
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Moving on from NIBGTN, I think formaldehyde is the only aldehyde to join with the 3 hydrogens on nitromethane, is this true? If so, acetaldehyde
should condense with 1 hydrogen in nitromethane to form nitro-2-propanol(?), then possibly reduced to nitroacetone.
Critique the following reactions:
<center><img
src="http://ww1.yourtoplist.com/~59594/madscipic.yourtoplist.com/images/nitroacetoneperoxideroute.jpg"></center>
While probably a lot harder then it looks, all the reactants are very common so I think it deserves some going over. If possible, what is the best way
of carrying out the 4 stated reactions? Can it be done one after the other in the same vessel .... why not?<br><br>
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chemoleo
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Just at a quick glance, reaction 1. is actually a lot harder to perform properly as it looks.
Check http://www.sciencemadness.org/talk/viewthread.php?tid=1918 for details.
Reaction 2 - the mechanism sounds plausible, but what is the guarantee that the 1- nitro isopropanol wont react further with additional acetaldehydes?
I guess the bottleneck to this will be to obtain the nitroacetone of course.
I couldnt comment on the next two reactions. As Philou pointed out, why not using 1,3 dinitroacetone? Polymerisation products (similar to the route to
mesitylene) should be very interesting...
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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Axt
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Seems like no one received acceptible yield of acetaldehyde? I have chucked the above reactants together, before I knew a slightly basic solution is
necessary for reaction 2, this yielded a very sickly sweet smell, probably paraldehyde due to H2SO4. Condensation wouldnt have happened anyway due to
the acidic solution I had it in.
Ive no answer for reaction 2 stopping at replacing 1 hydrogen, but this was hinted to in another file, which mentions that its hard to condense onto
more then one H in NM with any higher aldehydes then formaldehyde, this is one question I need answered.
#3 should be fine, unless a stronger oxidising agent is needed.
Cant see any practical route to dinitro... so mono will have to do!
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chemoleo
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Regarding the nitroacetone, is there a way of making it via chloro acetone and nitrite? I guess the carbonyl may interfere - but maybe there are some
tricks I don't know of.
Chloroacetone is made easily enough, albeit being a nasty lachrymator.
Edit: Ouch! Looks like Philou had the same thought!
chloroacetone and AgNO2--> NO2-CH2-CO-CH3 + AgCl (precip)
What kind of solvents would this require? Water by the looks of it. Hmm, but making AgNO2 via another metathesis cant be easy, as it should be soluble
itself, and as nearly all sodium salts are soluble too (the main source of nitrite being NaNO2).
But then - the resulting NaCl should hardly interfere with peroxidation.
Looks like we got a route to nitroacetone!
[Edited on 4-8-2004 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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Axt
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Couple more points to add about the NM route. Hysterix seems to have already given this, and it seems to be stated as fact rather then an idea. Search
google for "mononitroacetone" the e&w cached page holds this:
"Mononitroacetone can be produced according to this scheme:
CH3CHO + CH3NO2 -----> CH3-CH(OH)-CH2-NO2 ----(oxidation)---> CH3-CO-CH2-NO2"
And I've found confirmation that only one mole of acetaldehyde will condense with nitromethane, this is shown in Polverones
"nitroalkanes_chemrev.pdf" file in the table titled "Reaction of aldehydes with Nitroparaffins".
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Axt
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Really should have checked this first, but Fedoroff under "acetone":
<center><img src="http://ww1.yourtoplist.com/~59594/madscipic.yourtoplist.com/images/nitroacetone.gif"></center>
Doesnt confirm nor deny, each disputes the other regarding oxidation product of nitroisopropanol. Liquid, solid or not at all ... The evidence seems to suggest that its possible, but as a slightly water soluble solid.
If nitroacetone was to be produced at all, a byproduct that could result is the condensation of 2 moles NM with 1 mole nitroacetone to yield:
<center><img src="http://ww1.yourtoplist.com/~59594/madscipic.yourtoplist.com/images/C5H9N3O6.gif">
Trinitroneopentane.</center>
As a side note, NM/Acetone seems to be a detonatable mixture in itself, I come across the ratios 84/16 & 75/25 but no further info.
[Edited on 5-8-2004 by Axt]
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photoguy
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oh dear! This has been attempted already by myself and the results are disasterous. We had all of the gear ready to make this "theoritical" substance.
We knew that more than likely a fire and or explosion world occur. Let me assure you that mixing any "oxidizing" acid in pure form into Acetone will
cause an insain amount of heat to be released.
-------------------------------
In the forming process a single beaker - 250ml sized was placed in a super cold ice bath for 30 minutes. Ice bath measured -5C.
Added to the beaker was 100 ml of chilled acetone, temperature was -3C. Very slowly I added drop by drop of nitric acid (90%) via glass pipette. As
soon as the nitric acid hit the acetone the color changed and went dark. Ahha! Phoronisation has began... and the temperature kept climbing rather
slowly.
After 10ml of nitric acid had been added the acetone, the temperature was a little below room temperature. I had to chill the mixture further for the
addition of H2O2 - 35% strength - temperature of H202 was 0C. I added the liquid in slowly - but it didn't matter... I recieved a extremely violent
run away which resulted in the ejection of the phoronated solvent into the air into a superheated caustic vapour cloud. I can imagine what would
happen if this reaction took place at high temperature with more acid involved.
Dear GOD!!!!!!
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Ozone
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-5°C is super-cold? Would this (admittedly bad, but interesting idea) be feasible using dry-ice acetone (or N2(l))? This looks like a job for
kinetic-control-man!
Perhaps on the end of a long stick,
O3
-Anyone who never made a mistake never tried anything new.
--Albert Einstein
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photoguy
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In general Mesityl based compounds are incompadable with H202 - it will react rather violently when mixed. However, Mesityl compounds have been able
to form complex organic peroxides though they are difficult to produce due to temperature rise.
humm, maybe a cooler acid like HCl would be better suited for the job- slower phoronization rate with less heat.
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