killswitch
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Nitroxylene
Apparently, now that benzene has all but disappeared from consumer products and been relegated to the laboratory and industry, the "Ban It Before It
Gives You CANCER!!" brigade is moving on to toluene. They removed it from nail polish remover, and now I cannot find toluene at my local Home Depot
and will be forced to use xylene (as shipping costs for an online purchase would be nearly as high as the price of the toluene itself), specifically
Kleen-Strip brand:
Now, from what I've come to understand, the additional methyl group will allow trinitration to proceed under less extreme conditions than toluene or
benzene. However, this is complicated by the fact that there are three isomers of xylene, and I have no idea what the % composition of the store-brand
is. I am also about 99% certain that this brand contains at least 1-2% ethylbenzene as a contaminant. I don't have the equipment available for a
fractional distillation. What conditions are best applied for mono-, di-, and trinitration of xylene, and what will be the likely percent breakdown of
nitro groups by position number?
Lastly, is tetranitroxylene achievable without the use of oleum? That would greatly simplify the isomer problem, as I suspect that one of the isomers
of xylene is more amenable to nitration than the others, though my knowledge of organic chemistry is insufficient to predict which one.
[Edited on 14-12-2011 by killswitch]
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Adas
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m-Xylene can be easily trinitrated, and p-Xylene can be easily tetranitrated, IMO. Because -CH3 groups are electron-donors and -NO2 are strong
electron-acceptors. They will cause the -NO2 groups to go either to ortho or para positions. I hope this helps.
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AndersHoveland
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Hexa Nitro Xylene ?
Using xylene, it may also be possible to put additional nitro groups on the methyl groups, rather than only on the ring itself.
| Quote: | "Phenylnitromethane has been prepared by the nitration of toluene with dilute nitric acid in a sealed tube."
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Konowalow, Ber. 28, 1860 (1895).
(the sealed tube probably implies heating)
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"nitration of toluene with nitrogen dioxide at a temperature between 20C to 95C yields a mixture of phenylnitromethane and phenyldinitromethane"
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Further nitration to add nitro groups to the actual ring should probably be done with nitrogen dioxide, using NaNO2 as a buffer, rather than nitric
acid because phenylnitromethane can hydrolyse in acid to benzoic acid and hydroxylamine salts.
"The Meyer Reaction of Phenylnitromethane in Acid", J. T. Edward, P. H. Tremaine, Canadian Journal of Chemistry, 1971
The reaction of benzene with nitrogen dioxide, at 25degC, produces nitrobenzene as essentially the only product.
"Reaction of polycyclic aromatic hydrocarbons with nitrogen dioxide in solution",William A. Pryor, Gerald J. Gleicher, John P. Cosgrove, Daniel F.
Church, Journal Organic Chem., 1984, 49 (26), pp 5189–5194
Phenylnitromethane has the structure,
C6H5-CH2-NO2
It is an isomer of nitrotoluene, but with the nitro group not directly on the ring.
You can read more about my idea and see a structural picture of the proposed "hexanitroxylene" molecule here,
https://sites.google.com/site/energeticscribble/gem-dinitro
If you live in California, you might try visiting another state. On a recent visit to America's "Pacific Northwest", I found a product containing
toluene (and some other unusual and interesting chemicals; butyl acetate, cyclooctanone) that was clearly marked "NOT FOR SALE IN CALIFORNIA".
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killswitch
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Quote: Originally posted by Adas  | | m-Xylene can be easily trinitrated, and p-Xylene can be easily tetranitrated, IMO. Because -CH3 groups are electron-donors and -NO2 are strong
electron-acceptors. They will cause the -NO2 groups to go either to ortho or para positions. I hope this helps. |
It does help indeed. Thank you.
Will the ethylbenzene interfere in the process (by causing unwanted oxidation products, or worse, runaway nitration)? That's one thing I'm
particularly concerned about.
Anders, when you say "buffer," do you mean between nitrous acid and sodium nitrite in aqueous solution? How is this best achieved?
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AndersHoveland
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| Quote: |
Tetranitroxylene (2,4,5,6-Tetranitro-meta-xylene)
C8H6N4O8
According to Blatt and Whitemore, OSRD 1085 (1942), 83, the compound exhibits a Trauzl test value of 106% PA or 115% TNT.
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There just does not seem to be any information on "tetranitroxylene", which makes me suspect that further nitration of trinitro-para-xylene would
oxidize the methyl groups before an additional nitro group is added to the ring.
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The mononitration of p-xylene canbe easily carried out at 30°C. Nitro-p-xylene is easily nitrated to dinitro-p-xylene at a temperature of 80°C. The
trinitro-p-xylene can be obtained at 120°C
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Trinitro-p-xylene melts at 137°
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4:5:6-trinitro-m-xylene. An attempt to convert this into tetranitro-m-xylene by action of nitric and sulphuric acids at 150°, leads to the formation
of a small quantity of an acid oxidation product, forming colourless crystals and melting at 190°.
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Another isomer of "tetranitroxylene", 1,4-Bis(dinitromethyl)benzene, has also been prepared. But in this instance all four nitro groups are on the
methyl groups rather than directly on the ring.
[Edited on 16-12-2011 by AndersHoveland]
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AndersHoveland
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Another option would be convert an amine group to a nitro group through a Sandemeyer reaction. For example, trinitroaniline can be converted to
1,2,3,5-tetranitrobenzene by first reacting with NaNO2/dilute HNO3, then reacting with copper sulfate, and adding more NaNO2. The conversion yield is
69%. This is a commonly used procedure.
This reaction was also mentioned on the "Explosive and Weapons Forum",
| Quote: |
Synthesis of Tetranitrobenzene: TrinitroAniline is oxidized to tetranitrobenzene, The NH2-->NO2
...
that NH2's can be converted into NO2's by the Sandmeyer reaction.
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There are several different options to include an amine group onto xylene, depending on the isomer. 4-nitro-m-xylene could be reduced (with Zn/HCl) to
4-amino-m-xylene, preferrably protected by addition of an acetyl group (using Ac2O, acetyl group can be removed after nitration with NH4OH), then
(probably) nitrated to 2,5,6-trinitro-4-amino-m-xylene.
Nitration of N-acetyl aniline, for example, gives the ortho and para products on nitration, as the nitrogen here is less basic and is only partially
protonated under the reaction. Nitration of unprotected aniline gives mostly the meta nitro isomer, although in this case some "charring" of the
aniline can be problematic.
The 2,5,6-trinitro-4-amino-m-xylene could then be converted to tetranitro-m-xylene through the Sandemeyer reaction, assuming the methyl group are not
attacked.
An alternative option would be to clorinate xylene by passing in chlorine gas in the presence of sunlight for several hours. The mono-chlorinated
xylene could then be nitrated, then the chlorine substituted for an amine group.
Nitration of chlorobenzene typically yields 2,4-dinitrochlorobenzene, although other isomers can be obtained under specific reaction conditions.
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"Both 2- and 4-chloronitrobenzene react with anhydrous ammonia at 200degC to form the corresponding nitroaniline, whereas 3-chloronitrobenzene did not
react under these conditions."
V. A. Tarasevich, M. F. Rusak, A. B. Tereshko, and N. G. Kozlov, Zh. Obshch. Khim. 67, 671 (1997); Chem. Abstr. 128, 2701275r (1998)
In the presence of the iodide ion, dry NH3, dissolved in pure alcohol, reacts rapidly with 2- and 4-chloronitrobenzene at 100degC.
1-chloro-2,4-dinitrobenzene reacted with alcoholic ammonia at room temperature.
V. A. Tarasevich, M. F. Rusak, A. B. Tereshko, and N. G. Kozlov, Zh. Obshch. Khim, 67, 457 (1997); Chem. Abstr., 128, 270275r (1998)
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Here is a diagram showing both of these possible routes,
Unfortunately, I have no idea how 4-chloro-m-xylene could be practically prepared and isolated. Chlorination of m-xylene would no doubt give a mix of
5 different monochloro- isomers alone, only one of which would be useful. The fact that commercial xylene itself is a mix of three different isomers
only complicates things.
[Edited on 16-12-2011 by AndersHoveland]
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