madscientist
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Preparation of dinitroacetone
Since the direct nitration of acetone is too risky, I have begun considering alternate routes of preparation. Right now, the best idea in my mind is
nitrating polymerized acetone, then hydrolyzing the nitrated acetone polymer, forming dinitroacetone.
2CH3COCH3 --(NaOH)--> CH3C(CHCOCH3)CH3 + H2O
CH3C(CHCOCH3)CH3 + CH3COCH3 --(NaOH)--> CH3C(CHC(CHCOCH3)CH3)CH3 + H2O
And so on...
Hydrolysis of this polymerized acetone reforms acetone. Therefore, I am theorizing that hydrolysis of nitrated polymerized acetone would form
dinitroacetone. Any thoughts on this?
I weep at the sight of flaming acetic anhydride.
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PHILOU Zrealone
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Sorry to be the black bird of your dreams 
Polymerisation of aceton is irreversible and is called cetocondensation or crotonisation!
Boiling aceton under reflux with H2SO4 conc lead to a good yield of 1,3,5 trimethyl benzene.
(CH3)2C=O + CH3-CO-CH3 --> (CH3)2C=CH-CO-CH3 + H2O
(CH3)2C=CH-CO-CH3 + O=C(CH3)2 --> (CH3)2C=CH-CO-CH=C(CH3)2 + H2O
Another possibility is higher polymers since the above is stil a ceton!
Trimethylbenzene is formed almost like above but:
(CH3)2C=O + (CH3)2C=CH-CO-CH3 --> (CH3)2C=CH-(CH3)C=CH-CO-CH3 + H2O
(CH3°)2C=CH-(CH3)C=CH-CO°-CH3 -->(CH3)3C6H3 + H2O (cyclisation via condensation of the ° atoms).
To depolymerise the aceton is not possible afterwards even with a lot of heat, you only get cracking and no ceton, only alcenes!
Nitro aceton is dangerous because it can polymerise on its own (explosively)!
Never attempt to trinitrate trimethyl benzene; it has lead to many batches explosions and the explosive is poor in properties vs TNB and TNT!
PH Z
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PHILOU Zrealone
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Ah yes also crotonisation is possible to make in acidic or basic media!
Dinitroaceton (1-3) is for sure one of the strongest explosive (because it must be dense)!But unstable and prompt to polymerise!
One of its polymer must be over the 9km/s trinitromethyltrinitrobenzene (C6(NO2)3(CH2-NO2)3)!
PH Z
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AndersHoveland
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Nitroacetone
perhaps dinitroacetone could somehow be prepared from nitroacetone?
Ketones can react with nitrous acid (obtained from amyl nitrite and gaseous hydrochloric acid, the ketone being dissolved in acetic acid) to form
isonitroso-ketones,
RC(=O)CH=NOH
(L. Claisen, Ber., 1887, 20, pp. 656, 21 9 4).
This could be reacted with nitrogen dioxide to potentially form dinitroacetone, the intermediate nitrolic acid formed being oxidized by more NO2.
"When silver nitrite is agitated for 24 hours with a dilute ether solution of iodoacetone, the nitroacetone produced remains insoluble, while the
impurities dissolve ... amino acetone is obtained by reducing the nitroacetone, indicating it is not a nitrite."
Journal of the Chemical Society, Volume 78, Part 1, p82
Iodoacetone can be produced by simply reacting iodine with acetone at room temperature.
If you have access to the Journal of Organic Chemistry, you might see
ALIPHATIC NITRO KETONES
CHARLES D. HURD, MAY E. NILSON;
J. Org. Chem.; 1955; 20(7); 927-936,
which has a short description on the preparation of nitroacetone.
There is also an interesting, but confusingly worded article
"Synthesis ofα-nitrocarbonyl compounds"
K. K. Babievskii, V. M. Belikov and N. A. Tikhonova
http://www.springerlink.com/content/w48107v45086v883/
which I will try to summarize for you:
Complexes of dimethylformamide with dimethyl sulfate react with nitromthane in the presence of sodium ethylate (more commonly known as ethoxide), in
60% yield. The intermediate
(CH3)2NC(CH3)(OC2H5)2 reacts with nitromethane to form
(CH3)2NC(CH3)=CHNO2.
1.5 grams of the 2-[dimethylamino]-1-Nitropropylene,
(CH3)2NC(CH3)=CHNO2, is reacted dropwise with 15mL of 10% KOH. After 5-10 minutes, a white precipitate formed. The precipitate was separated by
filtration, washed on the filter with absolute(pure) alcohol and ether, then dried in a desiccator over KOH. The final product was 1.31g (81% yield)
of the potassium salt of nitroacetone. The potassium salt of nitroacetone decomposed between 190-191degC.
[Edited on 20-9-2011 by AndersHoveland]
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PHILOU Zrealone
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I would do 1,3 dinitroaceton from 1,3 dichloroaceton (lacrymator) and AgNO2 or NaNO2...
The main problem would be the fact that conversion of the chloride into the nitro will not be 100%; but on the other hand alfa halocetons are very
reactive molecules towards subsitutions (lacrymators owing to a very labile halogen atom).
One could expect from Cl-CH2-CO-CH2-Cl,
-25% 1,3-dinitroaceton O2N-CH2-CO-CH2-NO2 (may go up to 44% if diiodoaceton is used aside with urea and LiNO2)
-50% Nitrohydroxyacetone nitrite ONO-CH2-CO-CH2-NO2
-25% dihydroxyacetone dinitrite ONO-CH2-CO-CH2-ONO
To increase the yield one could think to allow chloroacetaldehyde (or derivated iodoacetaldehydre from halide exchange reaction) to react with
nitromethane...in a way to get nearly 100% 1-nitro-3-chloro-2-propanol.
Cl-CH2-CH=O + CH3-NO2 --> Cl-CH2-CHOH-CH2-NO2
The later can be:
1°) oxydised into nearly quantitative yield into chloronitroaceton Cl-CH2-CO-CH2-NO2 (probable lacrymator and precursor upon standing of
1,3,5-trichloromethyl-2,4,6-trinitrobenzene or related linear polymer via crotonisation condensation)
2°) then reacted with AgNO3 to get 100% nitrohydroxyacetone nitrate O2N-CH2-CO-CH2-NO2 (probable precursor upon standing of
1,3,5-trihydroxymethyl-2,4,6-trinitrobenzene trinitrate or related linear polymer)
3°) or reacted with AgNO2 or NaNO2/KNO2/LiNO2 to get between 50 and 66% of 1,3-dinitroaceton (O2N-CH2-CO-CH2-NO2) aside with (50-33%
nitrohydroxyacetone nitrite ONO-CH2-CO-CH2-NO2).
A lot of interesting "nitricacidless" chemistry to very powerfull (and after polymerisation to dense molecules)...
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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AndersHoveland
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The rate of reaction for such chlorine substitutions is so slow as to be negligable. Trying to react chloroacetone with silver nitrite dissolved in
benzene is likely to take several months. Bromo- or Iodoacetone would react much more rapidly.
The reaction should not contain water. Bromoalkanes (such as ethyl bromide) gradually hydrolyse with water. Even chloroform very slowly hydrolyses
with water, either after a few months, or after a few hours if refluxed with aqueous sodium hydroxide.
[Edited on 10-10-2011 by AndersHoveland]
I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort itself out.
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Sedit
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What about Nitrating various other derivatives of acetone such as the Sulfite adducts? I haven't really put any thought into it I'm just throwing this
out there. Would it increase or decrease the stability of the formed Nitroacetone? I'm curious about this myself as a simple, safe route to Mono
nitroacetone would be a golden goose to Nitroethane synthesis.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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