Tetranitrobenzene

[knowledgehungry]

Here is a synthesis I have developed for Tetranitrobenzene(if someone else has published this or posted this elsewhere my apologies):

Precursors: Aniline, Nitric Acid(concentrated), H2SO4(concentrated), pyridine, Alkanoyl Chloride(formed by Acetic acid and thionyl chloride reacting), Methyl hydroperoxide,Zr(OCH3CH2CH23)4,

Synthesis:
Preparation of Trinitroaniline:
Aniline +Alkanoyl Chloride(in pyridine)-->Acetenalide
Acetenalide +HNO3+H2SO4--> Trinitroaniline

Synthesis of Tetranitrobenzene:

TrinitroAniline is oxidized to tetranitrobenzene, The NH2-->NO2 by the following method.

Trinitroaniline+ Methyl hydroperoxide (catalyst Zr(OCH3CH2CH23)4)--> Tetranitrobenzene.

Source for oxidation of Amines http://www.tu-chemnitz.de/chemie/biophysanorg/forsch4_e.html


Comments are appreciated.

[cutefix]

The synthesis looks nice in theory….
Complicated for home experimenters..
Have you performed the synthesis successfully and were you able to do some explosive testing with these material?
:)

[knowledgehungry]

No I have not attempted this yet, and yes it is merely theory, but theory comes first does it not? Before attempting this (which would require very expensive and hard to obtain chemicals), I wanted to have some peoples opinions, so I don't waste my time. I agree it is complicated for the home experimenter, in fact I have not seen any mention of tetranitrobenzene, let alone a synthesis. I have no idea the stability of this compound nor it's properties. The first step is making this compound, then comes working on making an OTC version of it, if anyone has any other ways of oxidizing an NH2 to NO2 I'd be very glad to hear it.

[Mr Cool]

Well, the middle NO2 (the one in the "wrong" place) is going to be very reactive... that compound would just LOVE to turn itself into TNP or something...

Just a few minutes ago I realised that NH2's can be converted into NO2's by the Sandmeyer reaction. Maybe not in all cases, but it can with 5-aminotetrazole... would be worth looking into. Much more OTC than methylhydroperoxide with zirconium propoxide!!

[knowledgehungry]

I have found several things of note, I have found something that should work instead of the Zirconium propoxide and methylhydroperoxy acid, this isn't much easier to get but it *might* be easier to synthesize.
** O
* *||
CF3COOH is used instead of the previously mentioned chemicals.

Mr. Cool I do not know what you mean by talking about the sandmeyer reaction, the sandmeyer reaction is used to get halides onto a benzene ring with an azide group on it, its a substitution. I dont understand how that would allow another nitro on?

[knowledgehungry]

Hexanitrobenzene is prepared by oxidizing the amine group of pentanitroaniline with H2O2 in H2SO4. The compound is a high density explosive.
http://www.nawcwpns.navy.mil/474G00D/patents/0202.html

We could use Caro's acid instead of the previously mentioned exotic oxidizers! According to the navy it works, at least for converting pentanitroaniline to hexanitrobenzene. This is looking better and better, I might actually try this experiment myself in a little while. Please let me hear your opinions, this could be big folks...

[Mr Cool]

In the Sandmeyer reaction, an amine is diazotised, and then the diazo group is kicked off an replaced with an anion - commonly, but not exclusively, a halide.
So if you use double (+ excess) the amount of nitrite required for diazotisation, and chuck in your copper catalyst, then the anion that gets attached is nitrite, and you end up with a nitro group.

Yes, peroxyacids will do it, also permanganate oxidation will work in some cases, eg oxidation of aminoadamantanes. Caro's would be a good one to try if you can get strong enough peroxide. Personally, I hate that stuff!

Hmmm... why stop at tetra? TNT -> TNBenzene -> m-DNAniline -> PNAniline -> HNB

[knowledgehungry]

Hmm... perhaps Hexanitrobenzene would be more worthwhile to try to synthesize. I am planning on attempting a synthesis of either tetranitrobenzene or hexanitrobenzene, however it will take several months to get my lab up to snuff for such a synthesis. I had thought about the synthesis of hexanitrobenzene, would PNaniline be a worthwhile explosive in itself?

[Mr Cool]

Yeah, I reckon PNA might be quite explosive ;). I think I might actually have some figures around here somewhere...

[KABOOOM [pyrojustforfun]]

tetranitroaniline is seemingly easier to make than picramide cause you don't need to acylate the amino group. oxidate this to get pentanitrobenzene which I think can be converted to CL-18 (aminonitrobenzodifuroxan) by 1. 1,3-diazido 2,4,6-trinitrobenzene via reaction of PNB with sodium azide 2. nitrobenzodifuroxan via thermal decomposition of the azide 3. Cl-18 via VNS amination of nitrobenzodifuroxan.

[JoeJablomy]

Speaking of HNB, I was looking at some more NDIA pictures, and came across this:
http://www.dtic.mil/ndia/2002fuze/cope.pdf
which, on p.5 claims these guys were the first to make HNB, "the most powerful explosive known."
Of course, this particular presentation was just the China Lake guys bragging their asses off, but the claim interests me since there doesn't seem to be any other mention of anything called HNB.
Has anyone else heard anything about it? If it hasn't resurfaced since it was patented in 1981, it must be incredibly expensive or unstable, but it might be interesting to know about anyway.
What was that route to PNaniline, Mr Cool?

Otherwise, whose system uses the CL-XX designations?

[Mr Cool]

"What was that route to PNaniline, Mr Cool?"

First make trinitrobenzene (here (http://roguesci.org/megalomania/explo/trinitrotoluene.html), then here (http://roguesci.org/megalomania/explo/trinitrobenzene.html)). Reduce this with Zn or Sn and HCl, using a method similar to this (http://www.rhodium.ws/chemistry/nitrobenzene.aniline.html) to get m-dinitroaniline. Then a normal mixed acid nitration (with conc. acids) should get you PNA.
Another way is reduction of TNT with H2S to make aminodinitrotoluene, then mixed acid nitration will oxidise away the methyl (as it does in making tetryl) and add the nitro's in the same step.

I'm not sure who first came up with the CL-XX system, but it doesn't seem to be used very much...

[Mr Cool]

Just did a quick search (for PNA) on www.espacenet.net, and found these which should be relevant.

US5149818 (http://l2.espacenet.com/espacenet/viewer?PN=US5149818&CY=ch&LG=en&DB=EPD)
US4262148 (http://l2.espacenet.com/espacenet/viewer?PN=US4262148&CY=ch&LG=en&DB=EPD)
US4248798 (http://l2.espacenet.com/espacenet/viewer?PN=US4248798&CY=ch&LG=en&DB=EPD)

[Mr Cool]

I've just realised something that I should have realised a long time ago - I do have a good use for benzoic acid!
Nitration gives m-MNBa in good yield, reduction will give m-aminobenzoic acid, which should nitrate quite nicely to aminotrinitrobenzoic acid, which will easily decarboxylate to trinitroaniline. Then maybe this could pick up another nitro to give TeNA.
TeNA could (if desried) be converted into PNB, DATB, aminoazidoTNB, aminodinitrobenzofuroxan (<- but which one, or both?)...
If it isn't formed, or if the reaction can easily be stopped at TNA, then this could be diazotised, converted into picryl chloride, and then TNB (COPAE, p.134). Then of course this could be reduced and nitrated to PNA, which could be oxidised to HNB.......

Lots of room for experimentation!

[fulminans]

This type of compounds has been investigated in the 70's. A lot of effort was dedicated to the development of new energetic materials based on surplus TNT and other raw materials. I have access to the literature you need :). If there is interest regarding the Article, I'll scan and post it, if the admins give me the authorization to do so ......
My email is not O.K. anymore either, and i'm not able to change my account options because i have no rights to acess my account :(.

This is from CAS: and you know, dont see dont tell otherwise..............

Oxidation of poly(nitro)anilines to poly(nitro)benzenes. Synthesis of hexanitrobenzene and pentanitrobenzene. Nielsen, Arnold T.; Atkins, Ronald L.; Norris, William P. Res. Dep., Nav. Weapons Cent., China Lake, CA, USA. Journal of Organic Chemistry (1979), 44(7), 1181-2. CODEN: JOCEAH ISSN: 0022-3263. Journal written in English. CAN 90:151719 AN 1979:151719 CAPLUS


Hexanitrobenzene was prepd. by oxidn. of pentanitroaniline in H2SO4 with peroxydisulfuric acid (prepd. in situ by addn. of 98% H2O2 to 20% oleum). It reacts readily with aq. NaOH to yield 2,4,6-trinitrophloroglucinol and with NH3 to form 1,3,5-triamino-2,4,6-trinitrobenzene. Picramide is oxidized to 1,2,3,5-tetranitrobenzene and 2,3,4,6-tetranitroaniline to pentanitrobenzene by this new oxidn. procedure. The term "nitrocarbon" is proposed for zero-hydrogen compds. composed only of nitro groups attached to carbon.

For sure there are plenty of pathways leading to this type of energetic materials, but the major problem is still the lack of stability. The stuff ist easily hydrolyzed in most cases. Pentanitroaniline was used by the Germans to some extent as far as I know, but is was given up due to stability problems.
You will get easily TNP from 1,2,3,5-TNB through hydrolysis, as stated above.
The method of oxydation with Peroxodisulfate is for sure better than the more "academic" pathway of catalytic oxidation. Salts of peroxodisulfuric acid are used for etching printed circuit boards, so its not very problematic to get them. If you have cc H2SO4 I would dissolve the starting compound and add the Peroxosalt slowly and carefully to the mixture, then drown the whole shit in a lot of ice/water and filter off the product. If you are not cool enough during the last step you will hydrolyze your stuff and get TNP........

[knowledgehungry]

Do you think you'll give it a go? It shouldn't be too hard. If you do I'd be very anxious to hear the results.

[fulminans]

Do you think you'll give it a go? It shouldn't be too hard. If you do I'd be very anxious to hear the results.

Go for it, but the stuff isn't of high stability, and will easily hydrolyze!!! I would like to upload Literature regarding polynitrocompounds, but so far I have no access to the ftp. I would scan the papers from JOC.
You can oxydize amino groups with peroxodisulfate easily.

Oxidation of poly(nitro)anilines to poly(nitro)benzenes. Synthesis of hexanitrobenzene and pentanitrobenzene. Nielsen, Arnold T.; Atkins, Ronald L.; Norris, William P. Res. Dep., Nav. Weapons Cent., China Lake, CA, USA. Journal of Organic Chemistry (1979), 44(7), 1181-2. CODEN: JOCEAH ISSN: 0022-3263. Journal written in English. CAN 90:151719 AN 1979:151719 CAPLUS

Abstract

Hexanitrobenzene was prepd. by oxidn. of pentanitroaniline in H2SO4 with peroxydisulfuric acid (prepd. in situ by addn. of 98% H2O2 to 20% oleum). It reacts readily with aq. NaOH to yield 2,4,6-trinitrophloroglucinol and with NH3 to form 1,3,5-triamino-2,4,6-trinitrobenzene. Picramide is oxidized to 1,2,3,5-tetranitrobenzene and 2,3,4,6-tetranitroaniline to pentanitrobenzene by this new oxidn. procedure. The term "nitrocarbon" is proposed for zero-hydrogen compds. composed only of nitro groups attached to carbon.

[Mr Cool]

Not for a while I'm afraid - I go back to Uni on the 18th for 9 weeks, and I should do a bit of revision before then...
But I intend to have a go sometime. I'll probably try TNB, PNA, TATB - I don't think I'll be able to make HNB.