Nitrocarbons

About time there was a thread devoted to nitrocarbons

On a speculative note I propose an unknown one derived from :



Hexamethylenecyclohexane also known as Radialene , CAS 3227-93-8
www.chemspider.com/Chemical-Structure.14476692.html
Reaction scheme :
C- nitration of all 12 hydrogen sites might be done under extreme conditions.
The stoichiometric amount of SO3 gas introduced steadily at some pressure
into a closed vessel , dissolves into a chilled mixture under it of fuming nitric
acid and radialene. As the water is abstracted the HNO3 in the mixture will be
consumed and replaced entirely with H2SO4 mixed with the end product
Dodecanitroradialene.

C6(CH2)6 + 12 HNO3 + 12 SO3 => 12 H2SO4 + C6(C{NO2}2)6

C6(C{NO2}2)6 => 12 CO2 + 6 N2

- comments ?

Related thread elsewhere
www.sciencemadness.org/talk/viewthread.php?tid=1226#pid17906...


An empirical method to estimate detonation velocity described
on page 6 here -> Explosive Properties of Polynitroaromatics
http://handle.dtic.mil/100.2/ADA229627 , gives a value of 5.17
for factor F which works out to ~ 8930 m/s. The utility created by
forum member engager , utilizing the methodology of Keshavarz
obtains near to the same value ( 8940 ) and 386 kbar at a nominal density
of 1.89. The method I explained in these other posts
http://www.sciencemadness.org/talk/viewthread.php?tid=11195#...
http://www.sciencemadness.org/talk/viewthread.php?tid=11195&...
is in close agreement with detonation velocity of 8905 and 363 Kbar
at the supposed density of 1.9.



.

[Edited on 15-12-2011 by franklyn]

Quote: Originally posted by PHILOU Zrealone

An even better variant of the reaction would be the condensation product between CH2(NO2)2 and 1,2,3,4,5,6-cyclohexanhexone...

Cyclohexanehexone Triquinoyl references

An interesting caged molecule reminiscent of Cubane



C10Cl12 Mirex CAS-2385-85-5 - Now banned as a persistent environmental
contaminant formerly used as an insecticide especially against fire ants, applied
under the original name Dechlorane of the defunct Hooker chemical co. as a
fire retardant for plastics, rubber, paint, paper, electric goods. Produced by the
dimerization of hexachlorocyclopentadiene in the presence of AlCl3. Known as
Hexachlorocyclopentadiene dimer , http://en.wikipedia.org/wiki/Hexachlorocyclopentadiene
http://www.chemicalbook.com/ChemicalProductProperty_EN_CB343...
also as Perchloropentacyclodecane , Dodecachloropentacyclodecane , IUPAC _
1,2,3,4,5,5,6,7,8,9,10,10-Dodecachloropentacyclo[5.3.0.02,6.03,9.04,8]decane

Density : 2.25 g/cm3
Sublimes : 421 °C at 1 atm.
Melts Decomposing above 485 °C
Insoluble in water , 0.085g/100ml at 20 ºC
Solubility : Chloroform 17g/100ml , Dioxane 15g/100ml , Xylene 14g/100ml
Benzene 12g/100ml , CCl4 7g/100ml , MEK 6g/100ml


http://en.wikipedia.org/wiki/Mirex
http://chemeo.com/cid/21-111-4
http://sitem.herts.ac.uk/aeru/iupac/1294.htm
http://www.chemspider.com/Chemical-Structure.16054.html

Now only available as a laboratory reagent it is very expensive. ~ $ 25 gm
http://www.carbosynth.com/carbosynth/website.nsf/(w-productdisplay)/47CC86BCE4D50450802579CF0063B54A
http://www.ebiochem.com/product/mirex-dechlorane-4070-10mg-vial-109359#morespecification

The precursor Hexachlorocyclopentadiene as well as Aluminum Chloride
are available as industrial staple chemicals. According to Skylighter
www.skylighter.com/fireworks/making-fireworks-projects/chlor...
it still finds use as a chlorine donor in pyrotechnics.

________________________________________________


The possibility of substituting the chlorine with nitro groups cannot be lightly
dismissed , given the prospective density for the target and positive oxygen
balance.

Nitration with nitrates was pioneered by Menke , although done in solution.
Threads related to a possible reaction scheme.
http://www.sciencemadness.org/talk/viewthread.php?tid=1226#p...
http://www.sciencemadness.org/talk/viewthread.php?tid=1226#p...
http://www.sciencemadness.org/talk/viewthread.php?tid=1226#p...

Sodium nitrite ( NaNO2 ) melts at 271 ºC decomposing above 320 ºC.
If a lewis acid catalyst needs to be applied , anhydrous Aluminum Chloride
melts at 192 ~ 193 ºC but actually begins to sublime at 180. It is soluble
in organic chlorides.

.

[Edited on 15-10-2012 by franklyn]

Some tinker toy creations of unknown Nitrocarbon target molecules
which exhibit zero oxygen balance.
This illustrates the problem of choosing a destination , you then have
to figure how to get there. The Benzene variant below left , having two
sets of adjacent Nitroso groups , these would additionally condense
into two Furoxan groups , enhancing density. The Napthalene variant
below right has no adjacent Nitroso groups which can reform into
Furoxan as as this would incur steric hindrance between adjacent
Trinitromethane groupings.
P.S.
They look as if they will be rather toxic too.



Some related compounds
www.sciencemadness.org/talk/viewthread.php?tid=2969#pid93082
www.sciencemadness.org/talk/viewthread.php?tid=11195&pag...
www.sciencemadness.org/talk/viewthread.php?tid=1226#pid17906...
www.sciencemadness.org/talk/viewthread.php?tid=1226#pid18257...

.

Quote: Originally posted by franklyn

The Benzene variant below left , having two sets of adjacent Nitroso groups , these would additionally condense into two Furoxan groups , enhancing density.

AndersHoveland

I guess you mean here ( green arrows )



I have doubts too , why I left it with two nitroso showing

.

hexanitro-hexaradialene revisited

Okay, I had this idea for hexanitro-hexaradialene as well and thanks to Dany, have been redirected here.

I think I have a suggestion for a synthetic methodology that if it could be shown to work, would be pretty neat:

My thoughts revolve around using quinone chemistry actually, mostly because I have experience in it and also because the reagents are simple and cheap.

Firstly there's this little patent about chloranil:

https://www.google.com/patents/US5334735?dq=chloranil+hydrog...

I've performed this reaction several years ago and can confirm it works beautifully. It works so well because HCl can add to the quinone accompanied by a reduction which drives it steeply 'downhill'. So for example, hydroquinone is oxidised to quinone by hot peroxide and then HCl adds to the ring position and simultaneously reduces the quinone to hydroquinone resulting in the monochlorohydroquinone and then this continous on and on until the quinone is saturated by chlorine, ultimately forming chloranil. This all happens in one pot until bam, a mass of choranil crystallises out... a rather impressive synthesis considering it's simplicity.

Anyhow, I've also reacted the subsequently generated chloranil with sodium methoxide in methanol to form a mixture of tetramethoxybenzoquinone and KCl, as well as the hemiacetal derivative thereof.

So..... this got me thinking, perhaps one could use nitromethane to attack the quinone and exhaustivly add to it.

Now the only question is what to use as oxidant... here we could take advantage of the following papers that show that hydroquinone can be oxidised by oxygen rather efficiently using catalytic amounts of NO₂ that is easy enough to introduce.

J. Org. Chem. 59, 2529-2536 (1994),
Tet. Lett. 35(9) 1335-1338 (1994)

Here they used DCM but I beleive nitromethane could work just as well perhaps. The nice thing about using NO2 as catalyst is that it would create acidic conditions which can catalyse the isomerisation of the nitromethane into the reactive ene form.

And yes... I beleive this could be a one pot synthesis. Just like the exhaustive addition of HCl in the pressence of an oxidant. In this case, oxygen or indeed even air is the safest bet as much more oxidation is required to evolve the final product compared to the chloranil case, but I see no reason why this would not be at least plausable.



In another thread, I was trying to find out if anyone would be intrested to collaborate on this since I do not have the means to safely or legally try it out.

[Edited on 22-4-2014 by deltaH]

Interesting thought, thanks PHILOU, I think it is highly likely that what you suggested would also occur with an exhaustive nitromethylation of quinone under oxidising conditions.

Also, in hindsight, the autooxidation which quinones undergo with oxygen may stop whence the the quinone moiety is lost and so one might also not oxidise the side nitromethyl groups. Combining these two thoughts would mean making this structure:



I'm disappointed with it now

It looks like some kind of 'nitro-mite', probably low density, 1.5'ish, with a poor OB to boot

I hate spiders

[Edited on 22-4-2014 by deltaH]

Quote: Originally posted by deltaH

Interesting thought, thanks PHILOU, I think it is highly likely that what you suggested would also occur with an exhaustive nitromethylation of quinone under oxidising conditions. Also, in hindsight, the autooxidation which quinones undergo with oxygen may stop whence the the quinone moiety is lost and so one might also not oxidise the side nitromethyl groups. Combining these two thoughts would mean making this structure: I'm disappointed with it now It looks like some kind of 'nitro-mite', probably low density, 1.5'ish, with a poor OB to boot I hate spiders [Edited on 22-4-2014 by deltaH]

OB can be enhanced by reaction with a nitrite salt in acetic acid or by reaction with a nitrite ester...that way each nitromethyl group becomes a nitroso-nitromethyl one...
R-CH2-NO2 + R'-O-N=O --> O=N-CH(R)-NO2 + R'-OH
R-CH2-NO2 + HO-N=O --> O=N-CH(R)-NO2 + H2O
O=N-CH(R)-NO2 <==> HO-N=C(R)-NO2 <==> O=N-C(R)=N(O)-OH

So
C14H16(NO2)8 (or C14H16N8O16) becomes after per-nitrosation C14H8(NO2)8(NO)8 (or C14H8N16O24)

Due to the acidity of such nitroso-nitromethyl groups...one might assume that it may form interesting amine salts (NH3OH, N2H5, NH4, ...) and primaries metal salts (Li, Na, K, Hg, Ag, Pb, ...)

[Edited on 9-5-2014 by PHILOU Zrealone]