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[*] posted on 4-12-2003 at 01:58
Tetranitromethane


Does anyone have any experience with tetranitromethane? Its not an easy prep it must be said, but I've done it at home from anhydrous nitric acid and acetic anhydride.

Its a white solid melting at 13'C to a straw coloured liquid. If heated it decomposes forming NO2. The literature says it forms explosive mixtures with many organics but in my experience mixtures with petrol, turpentine, acetone etc just burnt when ignited (I did not try detonating them). I was quite disappointed!
I did however manage to get a powerful explosion upon adding a few drops to unsymmetrical dimethyl hydrazine, but then again UDMH is a very reactive substance and was used in the Apollo space missions as a rocket fuel!
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[*] posted on 4-12-2003 at 04:15


With those hazardous preparations of yours, have you tried benzene triozonide ? It is produced by passing ozone into pure benzene at 5-10 C and is, according to PATR 2700, incredibly destructive ( 25 % more energy than NG and much higher VoD than "ordinary" explosives ). It is also detonated by warm water "and even in ice-cold water it explodes at the slightest touch".....
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[*] posted on 4-12-2003 at 07:58


That I haven't tried! I'd love to give it a go but I am unable to obtain Ozone. I think it can be made in small quantities in a garage but you'd need a substantial amount for saturation of the benzene.

I try to push the boundaries as far as I can in terms of making exotic explosives in a domestic environment, but I have to draw the line with low temperatures, vacuum equipment or gases in large volumes!!! I just don't have the apparatus, although I can obtain a fairly wide range of chemicals.

I am working on trying to obtain a small air liquefaction compressor but they don't come cheap! Plenty of fun and games can be had with liquid oxygen as I fondly recall from my student days when I had access to it. I will post another thread about it!
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[*] posted on 4-12-2003 at 13:03


I've read that it forms quite explosive mixtures with toluene as this quote illustrates "When mixed with hydrocarbons in approximately stoicheiometric proportion a sensitive highly explosive mixture is formed.... Explosion of only 10 g of a mixture with toluene caused 10 deaths and severe injuries..." (Stettbacher, A., Tech. Ind, Schwetz. Chem.) It seems disappointing that mixtures with acetone, etc., only burned, maybe the dangers of this chemical are severely overrated, I would have at least expected deflagration.

Looking it up in the Reactive Chemical Hazards book I get:

"Mixtures with nitrobenzene, 1- or 4-nitrotoluene, 1,3-dinitrobenzene or 1-nitronaphthalene were found to be explosives of high senstivitiy and detonation velocities. Those of nitrobenzene are spark-detonable."

"A demonstration mixture,to show combustion of cellulose by combination with oxygen, exploded with great violence soon after ignition."




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[*] posted on 15-12-2003 at 15:03


Let's not forget though that C(NO2)4 is produced as a SIDE PRODUCT from any aromatic nitrations, at high temperatures! This is what's evaporating from your phenol/toluene/etc nitrations... and did anyone ever see an aromatic nitration exploding???

(See Rudolph&Meyer for details)




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[*] posted on 15-12-2003 at 15:48


Well put! I'm convinced this substance is overrated and exaggerated.
Quite how 10g managed to cause 10 fatalities is beyond me - did they hold hands in a circle around it!!! Sorry - being a bit cynical there!;)
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[*] posted on 8-1-2004 at 19:54
Be careful with tetranitromethane


Tetranitromethane is very toxic and can explode on its own.
It should be prepared in situ when needed in a fume hood or somewhere with good ventilation.
:o
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[*] posted on 7-10-2004 at 05:00


Tetranitromethane is in fact 25 times more toxic than HCN... yes, kids, 25 times. Although its much lower volatility makes it less dangerous to handle (vapour pressure at 20 C = 8mm), never let it hit air. Keep it under a layer of water or something.
It's made from acetic anhydryde and nitric/sulfuric acid ("nitrating acid", as I say, an equimolar mix of HNO3 and H2SO4, because for every HNO3 molecule used, approximately one molecule of water is made to make the stablest hydrate of H2SO4, H2SO4*H2O). If one can have SO3, I would suggest putting that and your 100% HNO3 together to get NO2HSO4 - nitryl hydrogensulfate (NHS :D), it would nitrate much faster and more efficiently.




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[*] posted on 7-10-2004 at 14:06


it releases too much oxygens, it would be a good idea (well understand what you want but it's barely not a good idea after all) to mix it with aluminium powder.

It would then release much more energy (but a lower amount of gaz) which means higher temperature and then higher VoD.

My Main Question Is : Does somebody have the enthalpy of tetranitromethane ? I'm too lazy to approximate it...
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[*] posted on 7-10-2004 at 14:49


25 times as toxic as HCN...

Blaster, are you still there? Did you know of this toxicity before?

I always wanted to try the synthesis of TNM, but now I will stay away from it as far as possible.
How is it possible that aromatic nitrations can produce this horrible compound and I never read any warnings about this danger?

What kind of poison is TNM? Are the symptoms delayed, like with phosgene or do you immediately feel the effects?

Blaster, take care, please.

This seems to be a very potent WMD which is easy to make. I hope no potential terrorists are reading this...
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[*] posted on 7-10-2004 at 18:25


I don't see support from Sax's Dangerous Properties of Industrial Materials, the Merck Index, or various MSDS that tetranitromethane is 25 times as toxic as HCN. In fact, the LD50 by injection/ingestion appears to be considerably higher. However, tetranitromethane is described as a proven animal and suspected human carcinogen, so I might prefer chronic low-level HCN exposure to tetranitromethane exposure.

Neither have I seen it recommended before to prepare tetranitromethane from acetic anhydride and mixed acid.

http://www.orgsyn.org/orgsyn/prep.asp?prep=cv3p0803




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[*] posted on 7-10-2004 at 20:04


And if it were 25 times more toxic then HCN many people would be dead from nitration reactions, which produce a small amount of TNM as a side product.

The book "Nitrocarbons" has a good section on tetranitro methane, especially interesting is the section on charge transfer complexes. Could be key to some high energy materials as they are isolateable and form with amines and other compounds, some of which are highly colored or possess ionic character. TNM attacks couble bonds of olefins producing interesting sequences of products though addition across the double bond.

"TNM is one of the most toxic materials to plants." From Nitrocarbons, by Nielsen

The maximum amount of TNM allowed in air during a work day though is incredibly low due to cummulative effects, it's .0001 - .0003 mg/L




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[*] posted on 7-10-2004 at 23:06


Can the book "Nitrocarbons" be downloaded anywhere?

John W.
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[*] posted on 8-10-2004 at 12:34


Here is TNM
And here is HCN
I originally thought it was 25 times, but I looked at the LC50 inhalational for mice and for rats for the two chemicals, it turned out rats were much hardier. TNM is actually 6 times more toxic for rats than HCN, no reliable data on humans as yet...




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[*] posted on 8-10-2004 at 22:29


Nitrocarbons is still pretty new (2002 I think) and I've never seen it online. I can scan in a few specific pages or type them in though if you want. I don't do whole books though.



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[*] posted on 9-10-2004 at 07:56


Only just found this revived post!

Well, I'm still here and I don't have any unusual growths coming out of my hands!!! I think a lot of this COSHH stuff these days is exaggerated personally.

I played with TNM over a year ago now and like I originally said I couldn't get it to explode either on its own or mixing with the solvents I had around at the time.

I didn't try toluene though and I've been meaning to try that mix but the prep of TNM is probably the most difficult I've performed for any explosive and I haven't got around to making any more as yet.
(It requires a double distillation of conc HNO3 with conc H2SO4 to get 100% nitric acid, followed by standing for a week with acetic anhydride and another final distillation to get the product!)

100% Nitric is amazing stuff - add a drop of water and it turns green due to the formation of N2O3. You should see the guncotton that can be made from it!
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[*] posted on 9-10-2004 at 09:30


In the orgsyn method Polverone referred to, the reference section mentions it being prepared from iodopicrin and silver nitrite (Hantzsch, Ber., 39, 2478 (1906)), and from acetylene by the action of nitric acid (Orton, Brit. pat. 125,000; Orton and McKie, J. Chem. Soc., 1920, 283.).
Would anyone have access to these journals? What is 'Ber.'?
From the 11 references quoted, these two seem most feasible to do in an amateur lab.




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[*] posted on 9-10-2004 at 10:13


Quote:
Originally posted by chemoleo
What is 'Ber.'?


probably Chemische Berichte ,
or possibly one other journal

Berichte der Deutschen Chem. Gesellschaft

[Edited on 9-10-2004 by Rosco Bodine]

[Edited on 9-10-2004 by Rosco Bodine]
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[*] posted on 9-10-2004 at 11:26


Interesting. I did not know of these other syntheses until now. The ref I followed was indeed from Liang, Org Synth Vol 3 1955 P.803 and is the most quoted (and recent) one in the textbooks I read on the subject.

It would be interesting to know what sort of yield they give. The method I used is stated as giving 57-65%.

[Edited on 9-10-2004 by Blaster]
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[*] posted on 21-9-2006 at 14:18


Today I tried to to nitrate nitromethane further to tetranitromethane. Theoretially it should work with a similar mechanism (step 3 and 6) like the nitration of acetylene to TeNM. I found the mechanism in the Ubanski I p.594:

(1) C2H2 + 2HNO3 ==> (O2N)2CH-C(O)H + H2O

(2) (O2N)2CH-C(O)H + HNO3 ==> (O2N)3C-C(O)H + H2O

(3) (O2N)2CH-C(O)H + HNO3 ==> (O2N)3C-C(O)H + H2O

(4) (O2N)3C-C(O)H + 2HNO3 ==> (O2N)3C-COOH + H2O + 2NO2

(5) (O2N)3C-COOH ==> (O2N)3CH + CO2

(6) (O2N)3CH + HNO3 ==> (O2N)4C + H2O

I didn't found any detailed references about this method, but I hope it's possible to get the stuff by this method.
The pKa value for trinitromethane and 2,2 dinitro-acetaldehyde are definitly lower than those of nitromethane (pKa 10.2) but acetic anhydride shouldn't have a a low pKa and in the AA method I assume the CH3 group gets nitrated first (protonation of C=O makes it more acidic, better nuleophile on NO2+), then the water produced in the nitration hydrolyses the AA to two 2-mono, di or trinitro acetic acid molecules, those decarboxylate to trinitromethane.

I ask this question because I didn't got any inmiscible layers after addition of 40ml nitromethane to a mixture of 180ml yellow (nearly 100%:cool: ) fresh destilled HNO3 and 150ml 96% H2SO4 at 20°C. I thought the reaction would be exothermic so I made it in an ice bath, but the mixture stayed cool even after addition of the whole 40ml of NM.

I don't know whether TeNM is miscible with nitrating acid, but NM was well miscible. The lack of exothermic behavor makes me think that no reaction happened at all. Maybe I have to let it stand in a corner for a week or so like Megalomania writes it in his synthesis from AA.

Has anyone any advices what could be improved or what I thought or made wrong.


[Edited on 21-9-2006 by hinz]
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[*] posted on 21-9-2006 at 15:40


A quick word of caution - NM is heavily sensitised by HNO3 (and known to form a miscible mix), partiuclarly at such high concentrations. I'd rather advice against heating this to speed up any potential reaction (aside from this I haven't heard of such a reaction being possible).



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[*] posted on 22-9-2006 at 00:43


I second that: NM + NA is similat to NG both in power and sensitivity. You don't want to boil it!

And no, you cannot nitrate alipatics with mixed acid in any reasonable yield. What works for nitromethane and -ethane is vapour phase nitration of methane/ethane with HNO3, in an aparatus similar to a ketene reactor, but don't ask me if this goes to the tetra nitro stage before they decompose again.
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[*] posted on 22-9-2006 at 13:00


Thanks for the replys, nothing has happened with the mixture so far, the acid is still fuming, but the NO2 dissolved in it has disappeared, now it's colourless. Maybe I mix a small sample, 40ml or so with some water and destill it under vacuum.

Maybe I store the mixture for some longer till I got my broken quadruple ion trap mass spectrometer and my old GC, both bought for together 400Euro at ebay, I hope I can repair it, only the turbomolecular pump seems to be broken.

Detonating this mixture could be nice too, Axt used 70% HNO3 with NM in his sharped charges, I only have to balance it to CO2 by addition of more NM.




[Edited on 22-9-2006 by hinz]
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[*] posted on 18-1-2007 at 23:53
CH(NO2)4


A friend uses it and keeps it on a shelf where he leaves it alone during the winter. It crystallizes then and the crystals are very unstable. Aldrich will ship it for less than they charge for shipping Br2.
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[*] posted on 19-1-2007 at 23:32


Tetranitromethane - now I've seen this material produced in minute amounts only in a lab. Yes, a white crystalline material with an extremely bad attitude!

-- as an aside---

I know that Isopropanone vapour in direct contact with Nitric Acid fumes can create trinitromethane - so I wonder if trinitromethane can be further nitrated to be Tetranitromethane?? I don't know if this is even remotely possiable...
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