Nitrogen trioxide ( NO3 ) charge neutral free radical nitration of an alkene is an
established procedure which by applying the method I outlined here _ http://www.sciencemadness.org/talk/viewthread.php?tid=6717&a...
should be able to produce equivalent nitric esters from benzene ring derivatives
such as xylene. See _ http://en.wikipedia.org/wiki/Xylene
In this case acetone is the prefered solvent being miscible with xylene and
ammonium nitrate. For safety the amount of acetone should be much greater
than what is necessary to solvate a given amount of ammonium nitrate since
in effect one will be subjecting to electrolysis a potentially explosive blend.
The exposure of xylene (CH3)2:C6H4 to NO3 radicals will attach a nitrate group
to each carbon of a cleaved double bond one for each of the six carbons in the
ring , producing dimethylcyclohexylhexanitrate (CH3)2:C6H4(NO3)6 which will
yield upon explosion the products 8CO2 + 2H2O + 3N2 + 3H2
Compared to HMX this is approximately the same size , yet 61.5 % heavier at
478 grams per mole against 296 grams per mole for HMX indicating a greater
density. The carbon of HMX yields 59.5 % dioxide. For this nitric ester ( or is it
a nitric cylcloalkane ? ) derived from xylene it is 73.6 %. This compares favorably
with hexanitrobenzene and octanitrocubane's 75.8 %. Most notably is that HMX
generates 12 moles of gas per mole , same as for octanitrocubane. But this nitric
ester ( or nitrated cycloalkane ) will produce 16 moles of gas in much the same
space as HMX , a 33% improvement.
Given the known properties of nitric esters at best one can only expect this
to be comparable to PETN in sensitivity, or even more so.
I just realized that you could make a lot of malonic acid by cleaving that sucker (i.e. DHA) with a lot of ozone.
I digress...
Timfranklyn - 3-4-2007 at 17:03
Quote:
Originally posted by gregxy
I don't think an aromatic compund like xylene would add NO3, aromatics tend to substitue instead of adding.
Benzene forms a triozonide easy enough, structurally similar
to the Peroxy trimer of Acetone , why should this be different.
Reactive radicals as this only need an Alkene double bond to
cleave. It's an easy enough experiment to do without exotic
reagents, I would try it myself if I wasn't an urban apartment
dweller, which apart from the illegality of it , would be
irresponsible.
.
1,2,4,5-Tetranitratobenzene
franklyn - 22-7-2010 at 06:07
1,2,4,5-Tetrahydroxybenzene (1,2,4,5-Benzenetetrol CAS 636-32-8) , http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=6946... / / http://www.chemspider.com/Chemical-Structure.62671.html
forms leaflets from glacial acetic acid (mp 215–220 ºC). It is easily soluble in water, ethanol, and diethyl ether but is
not quite as soluble in concentrated hydrochloric acid and glacial acetic acid. It is obtained by the reduction of
2,5-dihydroxyl-1,4-benzoquinone - http://sioc-journal.cn/EN/abstract/abstract332005.shtml http://en.wikipedia.org/wiki/2,5-Dihydroxy-1,4-benzoquinone, which is readily made by oxidation of Hydroquinone
(also known as Quinol or Benzene-1,4-diol) - http://en.wikipedia.org/wiki/Hydroquinone , dissolved in strong aqueous
sodium hydroxide with hydrogen peroxide, with stannous chloride and hydrochloric acid or by catalytic hydrogenation , US patent3780114. Etherification with methyl iodide in the presence of base gives the tetramethyl ether of
1,2,4,5-benzenetetrol (mp 103 ºC). Several partial ethers, halo, and amino derivatives of 1,2,4,5-benzenetetrol
are obtained by reduction of the appropriately substituted 1,4-benzoquinones.
Tetrahydroxybenzene Tetraesters US patent 7300604
The closing observation above indicates 1,2,4,5-Tetrahydroxybenzene is readily able to be esterfied conventionally
with Nitric and Sulfuric acid to form 1,2,4,5-Tetranitratobenzene. It will be unique , I am not aware of another
aromatic or aryl nitrate. http://www.springerlink.com/content/x006510m113h66u5 . The oxygen balance is just
slightly negative compared to the nearest similar compound Tetranitrobenzene , and will have greater peformance
with it's higher heat of explosion. Tetranitrobenzene being an aromatic nitro compound does have greater insensitivity
to shock.
The reference for "dissolved in strong aqueous
sodium hydroxide with hydrogen peroxide, with stannous chloride and hydrochloric acid" did not appear in any of the links you provided. Since these
would be the easiest two routes by far to make the desired compound, it would be very valuable if you could provide a reference for this.
A search failed to reveal anything on benzene nitrate, neither on carbolic-nitric anhydride, which strongly suggests that benzene nitrate is not
stable and does not exist in macroscopic quantities (at reast at RT). There is strong reason to believe that a nitrate cannot be put on a benzene
ring, but that is discussed elsewhere on the forum.
2,5-dihydroxy benzoquinone does seem like a very useful precursor to make other compounds. (condensation with hydroxylamine?)
[Edited on 23-7-2010 by Hoveland]franklyn - 22-7-2010 at 23:16
Ortho-form
Meta-form
Para-form