Sciencemadness Discussion Board

Tetranitromethane

Blaster - 4-12-2003 at 01:58

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!

Microtek - 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".....

Blaster - 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!

BromicAcid - 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."

chemoleo - 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)

Blaster - 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!;)

Be careful with tetranitromethane

FloridaAlchemist - 8-1-2004 at 19:54

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

Theoretic - 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.

sylla - 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...

garage chemist - 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...

Polverone - 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

BromicAcid - 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

JohnWW - 7-10-2004 at 23:06

Can the book "Nitrocarbons" be downloaded anywhere?

John W.

Theoretic - 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...

BromicAcid - 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.

Blaster - 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!

chemoleo - 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.

Rosco Bodine - 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]

Blaster - 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]

hinz - 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]

chemoleo - 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).

Boomer - 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.

hinz - 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]

CH(NO2)4

chemrox - 18-1-2007 at 23:53

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.

photoguy - 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...

Microtek - 21-1-2007 at 07:45

I have prepared a small amount of TeNM via the Ac2O/HNO3 method. I tried mixing a small amount of it with the calculated amount of toluene for oxygen balance, then absorbed a drop of it in tissue paper and hit it with a hammer. It detonated much like NG from this treatment.

I wore a gas mask which didn't cover my eyes and the vapours from the TeNM stung quite a lot. I quickly determined the evaporation rate to find out how much could be hanging around the lab ( which was very little; much less than the permitted concentration level when diluted to lab volume ). In the end I got so paranoid about poisoning hazards that I took all of it outside and let it evaporate on its own.

Engager - 20-3-2009 at 20:23

Quote:
Originally posted by Microtek
I have prepared a small amount of TeNM via the Ac2O/HNO3 method. I tried mixing a small amount of it with the calculated amount of toluene for oxygen balance, then absorbed a drop of it in tissue paper and hit it with a hammer. It detonated much like NG from this treatment.

I wore a gas mask which didn't cover my eyes and the vapours from the TeNM stung quite a lot. I quickly determined the evaporation rate to find out how much could be hanging around the lab ( which was very little; much less than the permitted concentration level when diluted to lab volume ). In the end I got so paranoid about poisoning hazards that I took all of it outside and let it evaporate on its own.


How much of TNM did you made, and what is found evaporation rate? Today i've prepared HNO3/Ac2O mixture witch will produce TNM on standing, but i'm seriously worried about high toxicity, so actual evaporation rate digits can help me to make it more safe.

Microtek - 23-3-2009 at 08:16

I made maybe 20 ml. I can't remember what the actual numbers were, but I had removed a sample and kept it in a small vial for testing. When it started stinging, I placed the vial with contents on my laboratory scale and monitored weight loss over 60 seconds, then computed possible concentration levels based on the period I had it open. IIRC just a few milligrams evaporated over the course of one minute, but obviously that will vary depending on temp and surface area, etc. I would estimate (I'm working from memory here) that the vial I used was about 1.5-2 cm in diameter.

Incidentally, I didn't suffer any ill effects at all (except the stinging eyes), but I have such an active imagination that the suspicion of poisoning is enough to make me physically ill. That's why I discarded the rest without doing anything with it, even though I was going to convert it to trinitromethane and then experiment with all sorts of nitroform condensates.

Engager - 27-3-2009 at 09:04

Preparation of tetranitromethane from acetic anhydride & nitric acid



Procedure:

Flat bottom flask with 500 ml capacity is filled with 63g (1 mol) of 99% nitric acid and placed on ice bath, then 102g (1 mol) of acetic anhydride is added by small portions with efficient stirring, not allowing temperature to rise above 10C (#1). After all nitric acid is added, neck of the flask is thoroughly dried with bath towel and flask is capped with small glass turned upside down. Mixture is allowed to stand in ice bath until it will heat up to room temperature, then reaction flask is removed from water bath and allowed to stand at room temperature for 7 days (#2). Mixture is poured to 600 ml of cold water, carefully stirred and heavy oily layer of tetranitromethane is separated in separation funnel. Crude product is washed with pure water until acid-free, with 15 ml of 40% sulfuric acid and then dried by careful washing with 10 ml of concentrated H2SO4 (#3), to get about 18 ml (29g) of pure tetranitromethane with melting point at 13.9C. Yield is ~60% from theory (#4).


Notes:

1. Temperature of reaction mixture must be kept below 10C at all times (above this temperature reaction speed up greatly). Reaction at the beginning of addition is strongly exothermic and acetic anhydride must be added by small portions (0.5 ml). Then about 10 ml of acetic anhydride is added, exotherm is reduced and portions can be slowly increased from 1 to 10 ml. After addition is complete mixture must be allowed to sit in ice/water bath, slowly heating up to room temperature. If cooling during first several hours is removed, violent exothermic process can start and at 30-35C mixture must be immediately poured to emergency drain with large amount of cold water.

2. On mixture aging slow reactions takes place, at first trinitroacetic acid is formed and is decarboxylated to nitroform evolving carbon dioxide, then nitroform is slowly nitrated to form tetranitromethane. Contamination by nitroform can be clearly evidented by intense yellow coloration of water layer, then tetranitromethane is separated from reacted mixture. Different sources mention different aging periods, but 7 days at room temperature found to be most common in references.

3. Occasional batches of tetranitromethane were found to evolve considerable heat and turn black if allowed to stand over concentrated sulfuric acid for longer then 10-15 minutes. So actual contact time must be minimized, and tetranitromethane must be separated on separation funnel as soon as possible.

4. Some literature sources mention higher yields on other aging time and temperatures. Some sources mention use of catalysts and chipped glass to improve yield of this reaction, however those statements are unconfirmed in later publications.


Photos:





[Edited on 27-3-2009 by Engager]

Anders Hoveland - 20-6-2010 at 00:21

Quote: Originally posted by photoguy  
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...

Trinitromethane is acidic, and forms powerful, but very stable nitroformate salts with NH4OH or amines. I am unsure what "Isopropanone" is. Do you mean acetone?
Could someone characterize hydroxylamine nitroformate? It should be better than NH4ClO4 for solid rocket oxidizer.

The WiZard is In - 20-6-2010 at 09:20

Quote: Originally posted by BromicAcid  
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.) "



In 1920 at the University of Münster a massive iron gas
burner containing a residue of 10 grams of tetranitromethane
and toluene mixture decomposed suddenly. The detonation
splintered the container, and of 300 students in the area,
10 were killed and 20 injured!

Several secondary references. Primary reference not seen
by me:

Zeitschrift für das Gesamte Schiess- und Sprengstoffwesen
25:439 1930


Weird - this discussion has gone of for 7-years, yet — no one
noted that Urban'ski has all that you need to know 'bout TNM.

For more recent methods of synthesis see Köhler and Meyer.

Chattaway's method (Patented by Farbenfabriken vorm. F. Bayer
and Company), J. Chem Soc. CCXX 2101 (1910) is described in detail
in good old —Capt. E. de W. S. Colver, High Explosives, Crosby
Lockwood and Son. London 1918. A somewhat hard to find book,
I do not remember where I purchased my copy. It maybe easier
to look up the J Chem. Soc. And ... if I was working on energetic
materials I would want to read the original reference, and check
following volumes for additions/corrections!




franklyn - 20-6-2010 at 09:25

Trinitromethane thread is here _
http://www.sciencemadness.org/talk/viewthread.php?tid=3061

attached references for both


Attachment: Nitroform Tetranitromethane & derivitive compounds .txt (11kB)
This file has been downloaded 1415 times

AndersHoveland - 24-5-2011 at 13:37

Tetranitromethane has been obtained from iodopicrin I3CNO2 and silver nitrite AgNO2.
Hantzsh, Chemische Berichte, 39, p2478, (year 1906)

From Köhler and Meyer

The WiZard is In - 24-5-2011 at 15:32

Tetranitromethane
Tetranitromethan; t´ etranitrom´ethane; TNM
colorless liquid with a pungent smell
empirical formula: CN4O8
molecular weight: 196.0
energy of formation: +65.0 kcal/kg = +272.1 kJ/kg
enthalpy of formation: +46.9 kcal/kg = +196.4 kJ/kg
oxygen balance: +49.0%
nitrogen content: 28.59%
volume of explosion gases: 685 l/kg
heat of explosion*): 526 kcal/kg = 2200 kJ/kg
specific energy: 69.1 mt/kg = 677 kJ/kg
density: 1.6377 g/cm3
solidification point: 13.75 °C = 56.75 °F
boiling point: 126 °C = 259 °F vapor pressure
Pressure Temperature
millibar °C °F
12 20 68
57 50 122
420 100 212
1010 126 259 (boiling
point)
detonation velocity, confined:
6360 m/s = 20 900 ft/s at r = 1.637 g/cm3

* The presence of small amounts of impurities may easily increase the experimental value to above 1000 kcal/kg.

Tetranitromethane is insoluble in water, but soluble in alcohol and ether. The volatile compound strongly attacks the lungs. The oxygen rich derivative is not explosive by itself, but forms highly brisant mixtures with hydrocarbons such as toluene. Tetranitromethane is formed as a by-product during nitration of aromatic hydrocarbons with concentrated acids at high temperatures, following opening of the ring. It can also be prepared by reacting acetylene with nitric acid in the presence of mercury nitrate as a catalyst. According to a more recent method, tetranitromethane is prepared by introducing a slow stream of ketene into cooled 100% nitric acid. When the reaction mixture is poured into ice water, tetranitromethane separates out.

Mixtures of tetranitromethane with organic fuels are very sensitive to impact and friction and may react spontaneously by detonation or fast deflagration.

R. Meyer
J. Köhler
A. Homburg

Explosives
6th Ed

----------
Patented Oct. 13, 1936
2,057,076
UNITED STATES PATENT OFFICE
2,057,076
PREPARATION OF TETRANITROMETHANE

Joseph A. Wyler, Allentown, Pa., assignor to Trojan Powder Company.

AndersHoveland - 19-9-2011 at 17:10

some non-scientific sources on the internet claim that nitromethane transforms into dinitromethane from exposure to UV light, but this could just be a perpetuated myth among the non-scientific community of racers and hobbyists.

AndersHoveland - 26-9-2011 at 06:36

Some people have suggested that tetranitromethane might be easily made through halogen substition. For example,
CCl4 + 4 NaNO2 --> C(NO2)4 + 4 NaCl

Unfortunately, it is not that easy. The above reaction would not work for three reasons.

First, chlorine does not substitute off carbon atoms very readily. Such reactions are very slow, and typically require nearly a whole 30 days to go to completion. (there do however exist certain complexed copper catalysts that can speed up the reaction to only a few hours)
Bromine and iodine substitute off much more easily.

Second, especially in light of the fact that the reaction is so slow, the two reactants would need to be mixed together. That is going to be problematic, because NaNO2 is water soluble, whereas CCl4 is oil soluble. There are not many solvents that can dissolve both. One of the few that can is propylene carbonate, which you would have to prepare yourself. Another idea would be to make lithium nitrite, which is soluble in ethyl ether, and simply mix with CBr4. Yet another idea would be to mix NaNO2 with carbon tetraiodide, CI4, using acetone as a solvent. Unusually, NaI is actually soluble in acetone. So the solid NaNO2 (which would not dissolve) could react with the CI4 dissolved in acetone to form NaI, which would also dissolve in the acetone. It is important that the NaI dissolves, otherwise it would form a protective layer over the solid particles of NaNO2, which would prevent the reaction from happening.

Third, forming nitro groups by substituting nitrites is problematic. It gives low yields, especially when you are trying to put more than one nitro group on a molecule. Such yields would be expected to be low, less than 11%, since nitrite substitution on secondary and tertiary haloalkanes gives successively lower yields than a primary haloalkane because a small proportion of nitrite gets substituted instead of nitro groups, which in this case would lead to degradation of the molecules with such undesirable substitutions. When subsituting only one halogen group, such as iodomethane, a small portion of methyl nitrite results as an undesirable byproduct, but when three or more halogens are being substituted, accidental addition of even one nitrite group will lead to hydrolysis of the unstable molecule, even if the other two halogens have successfully been replaced with nitro groups. Formic acid, or carbon dioxide , will form.

Furthermore, tetranitromethane is somewhat thermally unstable, especially in hydrocarbon solvents. It is also extremely dangerous to heat tetranitromethane, since it forms sensitive explosive mixtures with hydrocarbons. Therefore it is unlikely that tetranitromethane could be directly prepared from any reaction that involves refluxing or heating.


Here is a summary of possible ways to make tetranitromethane through halogen substitution.

CBr4 (or CI4) with AgNO2, using benzene solvent.
AgBr will solidify out.

CBr4 (or CI4) with NaNO2, using propylene carbonate solvent

CBr4 (or CI4) with LiNO2, using ethyl ether solvent

CI4 with NaNO2, using acetone as a solvent.
The solid NaNO2 will slowly react into the solvent, the NaI that forms is soluble.

In the above reactions, yields will likely be less than 8 percent, the remaining CBr4 will be oxidized to CO2.

Bromoform CHBr3 (or CHI3) could be used instead in the above reactions, this would give improved yields (since only 3 nitro groups are being substituted on instead of 4). The trinitromethane that then forms could be dissolved in excess methylene chloride (for safety), and nitrated to tetranitromethane.

Carbon tetrachloride (or chloroform CHCl3) can alternatively be used to prepare carbon tetraiodide (or to prepare iodoform) by reaction with sodium iodide. This requires a special catalyst. This catalyst is basically copper(I) iodide complexed to ethylene diamine, or more preferably CH3NHCH2CH2NHCH3. 1,2-diaminobenzene can also be used instead. The reaction needs to be refluxed at 110degC for 8 hours. Butanol, dioxane, or DMF can be used as the solvent.

Bromoform CHBr3 can be prepared similar to chloroform. Either ethanol or acetone is mixed with NaOH, then bromine is slowly added. Unlike with the chloroform reaction, it is better to minimize the percentage of water in the reaction, because bromoform gradually hydrolyses with water (actually chloroform slowly does also but the reaction takes many days)


VladimirLem - 26-9-2011 at 08:07

Hi guys

I've got a question

Pure Tetranitromethane is said to have a VoD of around 6400m/s (at ~1.6g/cm3)

But some sources say that the mixture of TeNM+Toluene got up to 9300m/s (and that with a lower desnity - sure, cause of the Toluene - 0.86g/ml)

Is it "similar" to anfo - where pure Ammoniumnitrate just got a VoD of around 1800m/s and mixed with oil, up to 3500?

How the hell can that be?


AndersHoveland - 26-9-2011 at 08:35

Tetranitromethane mixed with some toluene is more energetic, because the toluene can be burned off by the extra oxygen in the tetranitromethane.

When tetranitromethane explodes, it produces extra oxygen.

C(NO2)4 --> CO2 + (2)N2 + (3)O2

More energy can be produced if the oxygen can be used to burn some other fuel.

VladimirLem - 26-9-2011 at 08:44

Quote: Originally posted by AndersHoveland  
Tetranitromethane mixed with some toluene is more energetic, because the toluene can be burned off by the extra oxygen in the tetranitromethane.

When tetranitromethane explodes, it produces extra oxygen.

C(NO2)4 --> CO2 + (2)N2 + (3)O2

More energy can be produced if the oxygen can be used to burn some other fuel.


interesting stuff...

- I know, TNM got an awsome OB of +72 but does that theoretical work at every (solid) explosive (with +OB) mixed with fuels (like toluene/ethanol/oil) ?


AndersHoveland - 26-9-2011 at 08:55

Tetranitromethane gives off extremely poisonous vapors. It is so poisonous, it was one time considered for use as a chemical weapon. At least trinitromethane is much less poisonous.

Trinitromethane toxicity: 800 mg/m3/2 hour Inhalation Mouse LC50,

Tetranitromethane toxicity: 1230ppm (for 36min, LC50)


Mixtures of tetranitromethane and fuel are very sensitive explosives, and the mixtures are not thermally stable, which means that the tetranitromethane slowly decomposes at room temperature, giving off nitrogen dioxide.

For trinitromethane with hydrocarbon fuels, the mixtures quickly decompose above 100degC, and the decomposition can lead to detonation. No doubt tetranitromethane mixtures are even less stable.

Tetranitromethane REACTS with toluene at room temperature
Tetranitromethane actually reacts with phenol, to form nitrophenol and trinitromethane in 100% yield. (at 30degC in water). At higher pH, nitrite is also results.
"Reaction of Tetranitromethane. I. Kinetics and Mechanism of Nitration of Phenols by Tetranitromethane."
Thomas C. Bruice, Maurics J. Gregory, Saundra L. Walters


So tetranitromethane likely reacts with toluene in similar way also. Therefore, it may likely be somewhat pointless to mix tetranitromethane into toluene. Perhaps better just to mix mononitrotoluene with trinitromethane, because that is what the resulting mix will contain either way.

[Edited on 26-9-2011 by AndersHoveland]

VladimirLem - 26-9-2011 at 09:43

Quote: Originally posted by AndersHoveland  

So tetranitromethane likely reacts with toluene in similar way also. Therefore, it may likely be somewhat pointless to mix tetranitromethane into toluene. Perhaps better just to mix mononitrotoluene with trinitromethane, because that is what the resulting mix will contain either way.

[Edited on 26-9-2011 by AndersHoveland]


hm...ok...

"In actual practice a mixture of 80% ammonium nitrate and 20% TNT by weight yields an oxygen balance of +1%, the best properties of all mixtures, and an increase in strength of 30% over TNT."

Source

No way ! The 80/20 compound will bei 30% more powerfull than pure TNT (at same weight) ?


And dont worry, i'm not going to make T(e/r)NM ;)