Sciencemadness Discussion Board - Nitromethane -> Fulminates

Nitromethane -> Fulminates

Axt - 10-11-2003 at 08:08

With reference to here

"A laboratory method is to mix solutions of sodium nitromethane, CH2: NO(ONa), and mercuric chloride, a yellow basic salt being formed at the same time."

I havnt been able to find any other references to this process other then that sentence.

Sooo..

CH3NO2 + NaOH --> NaCH2NO2

Hg + H2O2 + HCl --> HgCl2

Thats easy enough, but under what conditions will these two react to form the fulminate, and could this process be used as a shortcut to copper fulminate by simply substituting Hg with Cu?

Marvin - 11-11-2003 at 00:20

Both of those are flawwed.

The sodium nitronate might need to be anhydrous, and if the anhydrous salt gets wet, it tends to detonate by itself. Oh, I remeber something about using a solution of sodium ethoxide in alcohol to form the salt, and when this gets wet, the heat/water turns it yellow and it detonates. Sodium fulminate being distinctly unstable chemically, to heat and to shock. The aci-nitro salts of higher nitroalkanes dont do this, and so are rather safer to play with.

Ive posted this info in one of the forums allready, but I dont rember which one.

From memory, you do a double decomposition to form mercury nitronate, which precipitates, and then digest this with dilute HCl to convert it into mercury fulminate.

On balence, you are much better sticking to the nitric acid/ethanol method. Not that I like mercury fulminate particulaly becuase of the toxicity of the mercury metal and much more so its salts.

Axt - 11-11-2003 at 02:01

"Both of those are flawwed."

In which way? Ive done them both, the NM/SH will give a brown precipitate that burns very simularly to blackpowder, Though ive never been able to ignite it with water (doesnt mean it wont!) it does seem to decompose (hydrate?) into a darker brown powder that will just smoulder and spit. Is your statement due to the formation of water during the reaction? as far as I can tell, water has only effected the amount that has dissolved into it, therefore can be filtered out. If it is hydrous, are there any tests to confirm this? colour? it will burst into flame on contact with H2SO4.

There is a movie of its ignition here if interested. (Ive changed the movie to show ignition of the dry salt, rather then damp as before)

Is the reaction to form mercuric chloride wrong? I know it works for cupric chloride, it was assumed Hg would act simularly. Since this is hydrated, heating would remove the H2O.

My main interest was to use it as a possible copper fulminate synth. therefore bypassing mercury and its toxicity problems.

"From memory, you do a double decomposition to form mercury nitronate, which precipitates, and then digest this with dilute HCl to convert it into mercury fulminate. "

Double decomposition in solution with what?

[Edited on 9-12-2005 by Axt]

madscientist - 11-11-2003 at 08:13

See my post at the top of this page: http://www.sciencemadness.org/talk/viewthread.php?tid=706&am...

HgCl2 from Hg, H2O2, and HCl does work.

Marvin - 12-11-2003 at 06:54

I'm prepaired to be wrong about HgCl2, though I was under the impression that would stop at calomel. I'm unhappy with the long term toxicity problems with using mercury salts, so I wont be trying this myself.

Sodium (methylene)nitronate is undoubtedly what forms _initially_ when sodium hydroxide and nitromethane are mixed, but its very doubtful this is what is precipitated or that this can be recovered in any amount from the aq solution afterwards. More likley a salt of nitroacetaldoxime, or nitroacetic acid, or possibly some sort of polymer caused by self condensation of some of these products.

The mercury salt will go to fulminate, but the silver salt doesnt, and Ive no info as to what the copper salt would produce. Fulminate chemistry is full of unexpected double salt formations, complex salt formations, polymer formations and available information is somewhat lacking.

ppting mercury methylenenitronate from a solution of sodium methylene nitronate and a mercury (II) salt, followed by digesting with HCl is how sidgewick describes one production of mercury fulminate. Available information suggests this is unavoidably done anhydrously.

Axt - 16-11-2003 at 14:54

Thanks for the replys, im now prepared to give this thought a rest.

The NM/SH reaction evolves no gasses if that helps narrowing down the products, other then what ive already said ive no other properties to add.

Heres something to try, pour a pile of NaOH and pour some NM until its damp and get back ..... FWOOMP!

Axt - 8-1-2004 at 20:36

Since PATR 2700 gives reference to an explosive K salt produced in aq. solution, so I gave it a shot with Na.

Nitromethane was reacted with sodium hydroxide to produce what I gather was a mix of sodium nitronate / sodium nitroacetate. This was then disolved in water converting it all to sodium nitroacetate(?).

To the SN solution was added an unmeasured amount of cupric chloride (via Cu + H2O2 + HCl) a reaction took place and a whitish precipitate seemed to form around the chloride "rocks" but once filtered nothing remained in the paper.

The solution was allowed to evaporate, this resulted in a dark green sludge which was spread out and allowed to dry.

The dark powder left after drying deflagrates fast when exposed to a flame, and since the sodium nitroacetate(?) itself doesnt burn there must be some explosive copper salts in there somewhere, any ideas on how to isolate it?.

Not only does it show a bit of promise as an explosive it has a very amusing product ..... PURPLE SMOKE! who wanted copper fulminate anyway

. I cant see any reason why it would be purple, perhaps some weird reflection off a copper cloud, but definately purple.

[Edited on 9-1-2004 by Axt]

Marvin - 9-1-2004 at 01:35

Good to see you posting again Axt, I hope we will see a return to form on this forum.

I didnt check Fedoroff, becuase I can usually never find anything in the few volumes we have, good searching.

What little info I have on nitroacetic acid suggests that in the free state its relativly stable to decarboxylation provided its not heated. It makes me wonder if you added dilute HCl to the sodium salt, if youd get a ppt of the free acid. If you dont get a ppt an extraction is possible with ether, toluene, benzene, hot chloroform. Insoluable in pet ether but very soluable in ethanol. Making the copper salt from the hydroxide might then be possible.

The purple smoke is very curious!

Axt - 9-1-2004 at 05:06

Heres the two references to the salts you have already suggested as possibilities Marvin, thats how I found them. I think it also confirms your thoughts on extracting the nitroacetic acid via HCl, though it seems dry HCl is needed.

______________________________

Mononitroacataldoxime or Methazonic Acid

(O2N) CH2. CH(:NOH), mw 104.07, N 26.92%, crysts, mp 79-80°; sol in w, alc, eth, acet and warm benz or chlf. Can be prepared by treating nitromethane in aq. NaOH or by other methods. Its ammonium salt, C2H3N2O3.NH4 obtained by the action of ammonia on nitromethane, dec on heating with evoln of poisonous hydrogen cyanide. Its K salt C2H3N2O3K, yel ppt expl on heating with evoln of lt blue flame (Ref 2) and its Ag salt, C2H3N2O3Ag, pale yel. ppt, expl ca 100°.

Nitroacetaldoxime, Anhydride, C4H4N4O4, mw 172.10, N 32.56%. Two isomers, a-, mp 168-172° (dec)& B-, mp 121-2° are described in the literature. Ag & Na salts of a-isomer were reported to be mild expls.

Nitroacetic Acid

O2N.CH2.COOH, mw 105.05, N 13.33%. Ndls, expl on heating; sol in chlf, benz & toluene;insol in petr eth; decompd by w; yields nitromethane when heated with w. Was prepd from the dipotassium salt and dry HCl in ether.

Its dipotassium salt, C2HK2NO4, ndls, sol in w and insol in ethyl & methyl alcs, can explode on contact with w. Can best be prepared by treating nitromethane with KOH. Other methods of prepn are given in refs 1&2. It is a powerful expl.
The aq soln of the salt yields with Pb acetate a white ppt and with Ag nitrate and mercurous chloride yel ppts. These salts dewflagrate in a flame (the Ag salt the strongest). Approx 3lb dipotassium nitroacetate in a 10 gal stainless steel can, moistened with w and covered with about 7lb dry K nitroacetate exploded after 30 mins at RT.

______________________________

So you can see why its confusing, the first reference gives the precipitate of NM/SH as methazonic acid, but the precipitate I recieve is not soluble in acetone/alcohol, thats why I believed it to be the sodium salt of nitroacetic acid, but now Ive found a reference that says Na nitroacetate cannot exist in aq solution. "The sodium nitroacetate is very unstable, and upon contact with water hydrolyzes to nitromethane" from <a href="http://members.shaw.ca/ThreeW/Business/newsbusiness/archivesbusiness.htm">here</a>. Really annoying!

[Edited on 9-1-2004 by Axt]

Axt - 9-1-2004 at 18:34

OK, now that ive viewed it in a different light it may be going a bit far to call it purple, maroon maybe, definately a copper tint to it.

Judge for yourself!

<img src="http://ww1.altlist.com/~52497/rogue.altlist.com/images/Cusmoke.jpg">

evildrome - 27-2-2004 at 17:36

Hi Axt,

ref: the purple/maroon smoke... I can tell you that cuprous acetylide produces the same colour smoke.

Axt - 28-2-2004 at 18:54

Evildrome from pulse-jets.com?

So, assuming the same decomposition products form the same coloured smoke, the smoke will be predominantly free copper and carbon, for which the maroon colour does make sence considering the colour of these two. Though I was sure I remembered a copper salt that had a simular colour.... anyone?

Perhaps forming another piece of the puzzle in identifying what the hell it is....?

chemoleo - 28-2-2004 at 21:18

i know it's slightly off topic but... I remember doing the thermite reaction with Cu2O and Al (NOT CuO). Very slow reaction, and HEAPS of orange red smoke... not purple at all.

I am sorry I know this is bound to confuse you... but then... we all know science is a lot about reporting observations!

Sadly theory doesnt always hold. Nonethelss, I wouldnt worry too much, for something to have a colour suggests either the presence of a transition metal, or the presence of a heterocyclic /aromatic/ unsaturated compound. It doesnt look like it's going to be any of the three former - apart from the first one - which is copper.
So here we go - exclusion principle does work

Axt - 3-8-2004 at 06:06

This quote should add some closure to the "what is that brown shit" argument, it should be sodium nitroacetate. This quote is from "The Nitroparaffins" available from polverone-articles folder as nitroalkanes_chemrev.pdf in FTP2.

Quote:

Nitromethane, compared to other nitroparaffins, is uniquely sensitive to the action of alkali. Sodium or potassium hydroxide converts it to salts of methazonic acid by a reaction in which two molecules condense with loss of water. This may be interpreted as an addition of nitromethane to the carbon-nitrogen double bond of the potassium salt, followed by rearrangement and loss of water.
Upon further treatment with strong alkali, methazonic acid is converted to nitroacetic acid.

The crystalline sodium salt of nitroacetic acid can be obtained directly in a single operation by dropping nitromethane into a 50 percent aqueous solution of sodium hydroxide maintained at 50°C, heating the solution to boiling for 10min, and cooling.

Whether it be nitronate/methazonate/nitroacetate, they all should precipitate explosive metal salts.

chemoleo - 3-8-2004 at 09:46

Interesting! I never thought nitroacetic acid could be made so easily !
I had a thought on this. In the other thread, Axt, you mentioned your desire in making some type of nitro acetonperoxide.
Now, I was thinking, if one could condense the nitroacetic acid one would get 1,3 dinitro acetone.
IIRC there is an analogous reaction for the production of acetone: One heats calcium acetate and acetone is distilled off. Could this be done with Calcium nitroacetate, to distill off 1,3 dinitro acetone?
Then of course this owuld have to be peroxidised... in a similar fashion as with AP... - or, using HCl, one could convert 25% at least to the nitro analogue of mesitylene.... lovely

PS admittedly the condensation similar as with Caacetate to acetone is likely not to work well or easily with nitroacetate simply because of the energetic product that results... anyway maybe what could be done is to mix Ca-nitroacetate with Caacetate in 1:1 proportions, then distill (so the overall conc. of dinitroacetone is not soo much!). 1/4 should be acetone, 1/2 nitroacetone and 1/4 dinitroacetone. Surely they could be separated somehow?

[Edited on 3-8-2004 by chemoleo]

[Edited on 3-8-2004 by chemoleo]

Nick F - 3-8-2004 at 10:02

Heating nitroacetates, distilling dinitroacetone... you scare me!
I don't expect nitroacetates to be very stable when heated:
O2N-CH2-COOM --> CH2=NOOM (boom!) + CO2
In fact, isn't that basically a stage which occurs in the production of NM, where M is H and NM adopts its usual structure?

chemoleo - 3-8-2004 at 10:21

Lol, yes, I soon realised the fallacy in my argument

Is there a less thermally dependent way of condensing acetates to acetone, or nitro acetates to nitro acetones?

Nick F - 3-8-2004 at 12:51

Some sort of crazy claisen reaction, followed by a decarboxylation? Which should, I think, happen quite readily...
I'm just trying to think if I have remembered what a claisen reaction is correctly (!), I'll check...

Edit: I wouldn't be at all surprised if the nitro groups interfered though...
Wait, dinitroacetone has never been prepared, has it?

[Edited on 3-8-2004 by Nick F]

tokat - 21-9-2004 at 00:15

METHYL NITROACETATE
[Acetic acid, nitro-, methyl ester]

Submitted by S. Zen, M. Koyama, and S. Koto1.
Checked by M. Ando and G. Büchi.
1. Procedure
Caution! Benzene has been identified as a carcinogen; OSHA has issued emergency standards on its use. All procedures involving benzene should be carried out in a well-ventilated hood, and glove protection is required.
A. Dipotassium salt of nitroacetic acid. A 3-l., three-necked, round-bottomed flask equipped with a sealed mechanical stirrer, a condenser fitted with a calcium chloride drying tube, and a pressure-equalizing dropping funnel is charged with a fresh solution of 224 g. of potassium hydroxide in 112 g. of water. From the dropping funnel is added, over 30 minutes (Note 1), 61 g. (1.0 mole) of nitromethane. The reaction mixture is heated to reflux for 1 hour in an oil bath maintained at approximately 160° (Note 2). After cooling to room temperature, the precipitated crystalline product is filtered, washed several times with methanol, and dried in a vacuum desiccator under reduced pressure, yielding 71.5–80.0 g. (79–88%) of the dipotassium salt of nitroacetic acid, m.p. 262° (dec.).
B. Methyl nitroacetate. A 2-l., three-necked, round-bottomed flask equipped with a sealed mechanical stirrer, a pressure-equalizing dropping funnel fitted with a calcium chloride drying tube, and a thermometer is charged with 70 g. (0.39 mole) of finely powdered dipotassium salt of nitroacetic acid (Note 4) and 465 ml. (11.6 moles) of methanol.
The reaction mixture is cooled to −15° ± 3° and 116 g. (1.16 moles) of concentrated sulfuric acid is added with vigorous stirring over approximately 1 hour at such a rate that the reaction temperature is maintained at −15°. The reaction mixture is allowed to warm to room temperature over a 4-hour period and stirred for another 4 hours at room temperature. The precipitate is removed by suction filtration, and the filtrate is concentrated on a rotary evaporator at 30–40°. The residual oil is dissolved in benzene and washed with water. The organic layer is dried over anhydrous sodium sulfate, and the benzene is removed by distillation. Further distillation under reduced pressure yields 30–32 g. (66–70%) of methyl nitroacetate, b.p. 80–82° (8 mm.), 111–113° (25 mm.) (Note 5).
2. Notes
1. The reaction mixture heats to 60–80° during the addition of nitromethane. The mixture may require external heating to maintain this temperature. The initial, yellowish color begins to turn red-brown and gradually deepens as ammonia gas is liberated.
2. The reaction mixture should not be stirred mechanically during this period in order to avoid decomposition of the product.
3. This crude product is rather pure. It can and should be employed for the esterification step without further purification. Elemental analyses for C2HO4NK2 were as follows; calculated: C, 13.26; H, 0.56; N, 7.73; K, 43.16%, found: C, 13.27; H, 0.57; N, 7.80; K, 42.68%. This is a hygroscopic crystalline powder and should be used immediately after drying. There is a report2 regarding an explosion of the dry dipotassium salt prepared by another method. There is no evidence that this procedure produces the same unstable impurities.
4. This must be ground into a fine powder with a mortar and pestle immediately prior to use.
5. The spectral properties of the product are as follows; IR (neat) cm.−1: 1776, 1760; 1H NMR (CDCl3), δ (multiplicity, number of protons, assignment): 3.83 (s, 3H, OCH3), 5.20 (s, 2H, CH2); nD20 1.4260.
3. Discussion
Methyl nitroacetate has been prepared from nitromethane via the dipotassium salt of nitroacetic acid by the classical Steinkopf method,3 but in lower yield. The dipotassium salt was obtained in 45% yield. The method has been improved by Matthews and Kubler,4 but the salt must be recrystallized prior to esterification.
This procedure5 is an improvement in that the reaction time is reduced and the yield is improved by increasing the concentration of alkali.
The acid-catalyzed esterification has been accomplished with either hydrochloric acid3 or sulfuric acid;6 an improvement on the Steinkopf method has been reported,7 but the procedure lacks the simplicity of the present method.
Application of sulfuric acid as the catalyst is considered more practical for esterification because of its higher boiling point, its incompatibility with benzene, and the stability of nitroacetic acid in the reaction mixture, which allows omission of the final neutralization step.
The ethyl ester can also be prepared from ethyl acetoacetate (ethyl 3-oxobutanoate) by the method of Rodionov8 as well as via Steinkopf's method.3 Ethyl nitroacetate can be prepared in >70% yield5 from the dipotassium salt, ethanol, and sulfuric acid, using anhydrous magnesium sulfate to avoid the Nef reaction.9 The propyl and 2-propyl esters can also be obtained by this method.

mercury methazonate

AndersHoveland - 21-4-2011 at 15:21

Mercury methazonate, which is a compound similar to mercury fulminate, is formed from the reaction of solutions of mercuric chloride with the "sodium salt of nitromethane" (actually sodium methazonate)

Nitromethane quickly reacts with a concentrated solution of sodium hydroxide to form the sodium salt of methazonic acid (alternatively named sodium 2-nitroethanaloximate),

(2) CH3NO2 + NaOH HON=CHCH=NO2Na + (2) H2O

The dry sodium methazonate salt is highly shock-sensitive and can explode violently.

When nitromethane is mixed with a concentrated solution of ammonium hydroxide, after several hours the liquid develops a dark brown color and a crystal substance begins to form. The small crystals formed a colored and difficult to purify. In a bottle, 20 cc (cm3) of pure nitromethane is mixed with 8 cc of the ammonia solution, and ammonia gas is then bubbled into the mixture until it is complely saturated (until no more gas can dissolve). A cap is then placed on the bottle and the bottle is kept under 10degC for about a day. The crystals which separate out are then removed and gently crushed into a moist powder. The powder is placed on an unglazed clay tile to draw out the water and allowed to air dry. The residual liquid still in the bottle is again saturated with ammonia gas and the process is repeated as before. This mehod will yield about 12 grams of the crystal substance. The crystals are soluble in methanol, less soluble in ethanol, and nearly insoluble in ether or chloroform. When the crystals are heated, they decompose, producing some poisonous hydrogen cyanide gas.
The crystals are ammonium 2-nitroethanaloximate, with the formula
NH4(+) C2H3N2O3(-). The structure can be written HON=CHCH=NO2(-).
The crystals can be redissolved in water and will react with a solution of silver nitrate to form a pale yellow precipitate. The precipitate is filtered and washed with a mixture of alcohol and water, then air dried. Heating the silver salt near 100degC causes it to explode. The salt easily dissolves in dilute solutions of nitric acid or ammonia. It has the formula AgC2H3N2O3.

If the 2-nitroethanaloximate ion is acidified, methazonic acid is formed with the structure: HON=CHCH2NO2. This is done by dissolving the ammonium salt in a solution with the corresponding ammount of dilute sulfuric acid (just enough to react), then extracting the acid with ether. The ether extraction is dried with calcium chloride and evaporated under vacuum. Methazonic acid crystallizes into crystal plates, and readily changes into a red resinous substance. The acid is soluble in water, alcohol, ether,acetone, warm benzene, and chloroform. Solutions of the acid are colorless, but on standing after a short time, a dark red color develops, and then eventually changes into a red colored resin. The acids melts between 60-70 degC. During the heating there is partial decomposition, and as the heating is continued the clear crystals first turn red, then gradually darken. At 100degC gas is evolved. At 110degC the acid explodes, leaving a black residue.

“Action of the Alkalies on the nitro-compounds of the Paraffin Series” Dunstan and Gouldin

"Mercuric chloride produces in a solution of sodium methazonate a yellow precipitate which is chiefly composed of basic mercuric methazonate. This salt explodes when heated, and is converted by dilute hydrochloric acid into a soluble, crystalline mercuric methazonate. The lead salt is insoluble, and explodes on heating."

Technical reports and scientific papers By Commonwealth Institute (Great Britain) Scientific and Technical Dept

Production of actual fulminates using nitromethane may be possible. I found these reactions:

Dehydration of nitroethane, using phenyl isocyanate and triethylamine, yields acetonitrile oxide. CH3CNO

Thermal dehydrochlorination of a hydroximoyl chlorides yields nitrile oxides.
RCCl=NOH (heat, minus HCl) -- > RCNO

(phosgene oxime Cl2C=NOH might be a suitable reactant in the above reaction, it can be produced by hypochlorite chlorination of nitromethane to chloropicrin, followed by reduction with Sn/HCl, but I am unsure whether the reaction would work if the R is a hydrogen atom)

Here is a video showing the deflagration of the sodium salt of nitromethane.
Note that it is incorrectly labeled "methylnitrolate". It should actually be "methazonate" or "2-nitroethanaloximate".

sodium methylnitrolate has the structure Na(+) (-)O2N=C(NO)CH3
the extra charge in the anion is delocalized and so the structure could also be shown as (-)ON=C(NO2)CH3,
which is to say that there is not actually any double bond in the charged molecule, it is actually aromatic, with the extra charge resonating between the nitro and nitroso group.

sodium methazonate has the structure Na(+) (-)O2N=CHCH2=NOH
(the anion is probably trimerized, since formaldoxime CH2=NOH exists as a trimer when in solid form)

http://www.youtube.com/watch?v=iscHVlucDfI&feature=relat...

you may want to save this video, as such videos are often removed after several months.

-=PLEASE DON'T MULTI-POST=- This are some good reasons, especially issues with the Search engine why we ask this, thanks - - Moderator

[Edited on 4-5-2011 by quicksilver]

AndersHoveland - 15-8-2011 at 16:45

It should be possible to form lead fulminate simply by mixing lead acetate, nitromethane, and acetic anhydride. Nitromethane can apparently be dehydrated to fulminic acid.

http://www.sciencedirect.com/science/article/pii/S0040403997...

[Edited on 16-8-2011 by AndersHoveland]

AndersHoveland - 14-11-2011 at 17:52

"Potassium nitroacetate, KO2N:CHCO2K, is formed by boiling fulminuric acid, nitroacetonitrile, nitroacetamide, or methazonic acid* with aqueous KOH. It crystallizes from concentrated aqueous alcoholic KOH and gives an intense red color with FeCl3. The lead salt is white, while the mercuric and silver salts are yellow. All three explode when heated, the last most strongly. Dilute H2SO4 converts the salt into nitromethane and CO2. The yield of the potassium salt is, in each case, excellent."
Chemical abstracts, Volume 3, p2439
American Chemical Society

*[methazonic acid is formed by acidifying methazonate salts. Reacting nitromethane with alkaline aqueous solution produces a methazonate salt, whereas in the absence of water, the salt of nitromethane alternatively results. Methazonic acid has the formula HON=CHCH2NO2. There is more information about methazonic acid elsewhere in this forum]

So basically the mercury fulminate is converted into fulminic acid, which can then be converted into nitroacetate, and then finally into nitromethane. So nitromethane can be prepared from fulminates.

More information about Methazonic Acid
"The following improved method for the preparation of methazonic acid has been worked out: To a solution of NaOH (20g) in H2O (40 cc), at 45-50degC, nitromethane (20g) is added gradually, during 15 minutes. Towards the end of the addition the temperature is allowed to rise to 53degC. After remaining until it has cooled to 20degC, the liquid is neutralized with HCl (45cc, density 1.170) the temperature being kept below 10degC. This precipitates the methazonic acid. Yield, 13-15g."

[Edited on 15-11-2011 by AndersHoveland]

PHILOU Zrealone - 16-11-2011 at 13:46

It is funny to see that methazonic acid (2-nitro-acetaldoxime; 2-nitro-ethanaldoxime) is related to furoxane...
O2N-CH2-CH2-N=O <--> O2N-CH2-CH=N-OH <--> HO-N(O)=CH-CH=N-OH <--> H2O + cyclo(-N(O)=CH-CH=N-O-)

From that one can see that 1,2-dinitrosoethane is also glyoxaldioxime and related to furazane...
O=N-CH2-CH2-N=O <--> HO-N=CH-CH=N-OH <--> H2O + cyclo (-N=CH-CH=N-O)

One can suspect that 1,2-dinitroethane may lead after dehydration to a more oxygenated compound (furazan-NN'-dioxide)
O2N-CH2-CH2-NO2 <--> HO-N(O)=CH-CH=N(O)-OH <--> H2O + cyclo (-N(O)=CH-CH=N(O)-O-)

One step further...1,2-dinitroethane can react with HNO2 (methanol, NaNO2, H2SO4) to form nitronic acids...in this case 1,2-dinitro-1,2-dinitroso-ethane...
O2N-CH2-CH2-NO2 + 2HNO2 --> (CH(-NO2)(-NO))2 + 2 H2O
The later would generate:
HO-N(O)=C(-NO)-C(-NO)=N(O)-OH
or
HO-N(O)=C(-NO)-C(-NO2)=N-OH
or
HO-N=C(-NO2)-C(-NO2)=N-OH
and be precursor after dehydration of dinitrofurazan, nitrofuroxan, or dinitrosofurazan-NN'-dioxide.

It is interesting to note that no mather the enantiomers of 1,2-dinitro-1,2-dinitroso-ethane, they will all lead to the same terminal molecule because of the equilibrium due to proton-jump between the carbon and the oxygen and conversion of the carbons into sp2...

[Edited on 16-11-2011 by PHILOU Zrealone]

AndersHoveland - 17-11-2011 at 21:12

Quote: Originally posted by PHILOU Zrealone

It is funny to see that methazonic acid (2-nitro-acetaldoxime; 2-nitro-ethanaldoxime) is related to furoxane...
O2N-CH2-CH2-N=O <--> O2N-CH2-CH=N-OH <--> HO-N(O)=CH-CH=N-OH <--> H2O + cyclo(-N(O)=CH-CH=N-O-)

From that one can see that 1,2-dinitrosoethane is also glyoxaldioxime and related to furazane...
O=N-CH2-CH2-N=O <--> HO-N=CH-CH=N-OH <--> H2O + cyclo (-N=CH-CH=N-O)

Interesting perspective; of course the molecule of water would only dehydrate out from pressure cooking with KOH. There would not be any equilibrium with furazan under ordinary conditions. One exception however- 1,2-dinitrosoethylene may likely [?] tautomerize with the furazan. There was a paper about this somewhere, I think it said this was much less favorable if the two nitroso groups were not both on another aromatic ring, for exaple 1,2-dinitrosobenzene.

There was another thread in this forum where we speculated that methazonic acid may likely be aromatic (with delocalized bonding). It was somewhere in this thread:
http://www.sciencemadness.org/talk/viewthread.php?tid=16118

There are all sorts of interesting tautomerizations involving adjacent nitro groups and furoxans on an aromatic ring. Essentially, the nitro group can essentially exchange places with the furazan!

[Edited on 18-11-2011 by AndersHoveland]

Rhodanide - 15-12-2016 at 14:20

Hi all, doubt anyone will see this, but it's worth a try. I did the same thing as you all, but subbed the water with Methanol. I got a yellow soln with yellow granular crystals at this bottom, in considerable amount. I soaked up the MeOH w/ a napkin and stored it damp with Methanol in a plastic chem bottle. Not sure, but it looks to be about twenty grams. Since it isn't dry, (and soaked with Methanol) it burns off the Methanol and then sputters, like it wants to self sustain. I haven't tried any other tests, but I'll update when I get around to it. Any thoughts, pointers, or suggestions are appreciated.

-T / AzideN3

PHILOU Zrealone - 15-12-2016 at 15:41

Quote: Originally posted by Tetra

Hi all, doubt anyone will see this, but it's worth a try. I did the same thing as you all, but subbed the water with Methanol. I got a yellow soln with yellow granular crystals at this bottom, in considerable amount. I soaked up the MeOH w/ a napkin and stored it damp with Methanol in a plastic chem bottle. Not sure, but it looks to be about twenty grams. Since it isn't dry, (and soaked with Methanol) it burns off the Methanol and then sputters, like it wants to self sustain. I haven't tried any other tests, but I'll update when I get around to it. Any thoughts, pointers, or suggestions are appreciated.

-T / AzideN3

What did you do precisely?...there are a lot of experiments exposed above
--> NaOH, methanol and NM?
The white precipitate is more likely sodium methazonate or nitronate (or a mix of the two).
When dry and submitted to a flame it explodes. IIRC the experiment was performed by "Explosions-and-Fire" on YouTube but video has probably been banned owing to last YT regulations.

[Edited on 16-12-2016 by PHILOU Zrealone]

Tdep - 15-12-2016 at 19:07

Hey, yeah the Nitromethane got a strike. You can view it here though https://vimeo.com/178184154 The experiment in question is at about 1:15. I use sodium ethoxide in the clip but it also worked with sodium hydroxide.

Also, a side note, things have settled down on youtube. I've put all my explosive videos back up and they've been there for a few weeks without strikes. It just seemed to be a month of a blitz of strikes and then calm. Strange.

S.C. Wack - 24-12-2016 at 09:36

...An aqueous solution of sodic nitromethane (10 grams) is added rapidly to a cold mercuric chloride solution (containing 16 grams HgCl2). After standing 15 minutes, the solution (300-500 c.cm.) is heated to boiling and quickly filtered from the yellow precipitate, which is then boiled out once with hot water. On cooling, a grayish white heavy crystalline precipitate separates out from the filtrate. In order to get rid of traces of adhering mercury, it is dissolved in dilute cyanide of potash and reprecipitated with dilute nitric acid. In this way perfectly pure fulminate of mercury is obtained, which is absolutely identical in every respect with the product made in the ordinary way. The yield is 1 gram to 1.6 grams pure salt from 10 grams sodic nitromethane.

...A yellow compound insoluble in water is, in all cases, the chief product of the action between aqueous solutions of sodic nitromethane and mercuric chloride; in fact only by the above mentioned method is it possible to obtain fulminate of mercury in appreciable amounts. If the corrosive sublimate solution is heated, before adding the sodic nitromethane solution, or if the former solution is added to the latter solution, not a trace of mercuric fulminate can be isolated, and much yellow insoluble mercury salt is formed. The composition of this yellow salt varies also according to whether the mercuric chloride solution is added to a solution of the sodium salt, or vice versa. In the latter case, the salt obtained contains much more carbon and nitrogen.

Basic Mercuric Carbondioxidoxime

On the addition of a solution of mercuric chloride (containing 16 grams HgCl2) to a cold aqueous solution of sodic nitromethane (10 grams), a white precipitate is formed which, after an hour's standing, has become perfectly yellow. The solution is decanted, and the residue is repeatedly treated with boiling water, and then dried on clay plates, and finally at 100°. The latter operation must be carried on with all possible precautions, since it happened several times that the salt exploded, demolishing the air bath and the windows of the hood. The yield from 10 grams sodium salt was regularly from 8 to 10 grams. The salt is, at ordinary temperatures, not quite so dangerous as mercuric fulminate, but it often explodes by friction. It is absolutely free from chlorine and contains no hydrogen : digestion with dilute sulphuric or with dilute nitric acid, in which it is insoluble, does not change the composition of the salt.

The salt is instantly decomposed by dilute hydrochloric acid, forming calomel, carbonic acid, and a substance having a smell like prussic acid, but not a trace of nitrous oxide is formed. Concentrated hydrochloric acid decomposes the salt into carbonic acid and hydroxylaminehydrochloride (proved by conversion into acetoxime). The salt is very soluble in dilute cyanide of potash, and on addition of dilute nitric acid no precipitate is formed. It was at first long suspected that the salt was basic fulminate of mercury, but it is not possible in any way to convert this salt into normal fulminic acid salts...

On the Constitution of the Nitroparaffine Salts
J. U. Nef
Proc. Amer. Acad. 30, 124 (1895)

Rhodanide - 3-1-2017 at 06:43

Quote: Originally posted by PHILOU Zrealone

Quote: Originally posted by Tetra

150 mL MeOH, dissolved 20 mL NM into it, slowly added 10 grams fresh NaOH to it over the period of 10 minutes with stirring. Only a slight clear->yellow color change was noticed. I left the mixture overnight in a cold area (Below 0°C), which formed a yellow granular precipitate (previously mentioned) that deflagrated with a "Poof" and a decent amount of smoke when a flame was applied directly. (This is when it was dry) Another thing which I noticed was not only did the solid stay a deep yellow color, (as opposed to changing to brown, like what Na Nitromethanate/Nitronate is supposedly supposed to do when in air) but it didn't detonate nor have any noticeable reaction with water. (Again, like Na NM-ate is allegedly supposed to do. I'm not sure exactly, but it sounds like PhZ may be right about it being Methazonate)