nitromethane

[mercury]

Hi ladies and gentelmen. This is my first mesage.
Are there anyone who tested nitromethane and amonia solution? Can you share your results? Thanks....

[THErAPIST]

sorry man, ive got no experience with that mix. i dont even remember hearing of that mixture before. what kind of compound does the mixture produce? explosive or deflagerating? solid or liquid?

[mercury]

It is liquid and high explosives.

[death11284]

http://www.linkbase.org/high-explosives/ is the only thing I can find on google relating to it being an HE. The ignorance in the statement "20 times more powerful then TNT" makes me think that guy is a fucking idiot. However it seems this would be a VERY unstable mixture, so..be careful..don't make much of it.

If I get ahold of some nitromethane soon I'll try this, personally I won't use more then a few ml of it because this one sounds really, really dangerous, and that's coming from someone who deals with HEs on a regular basis.

[W4RGASM]

Considering that ammonia tends to be a GAS at stp, I'm gonna go ahead and say that this is a mangled urban legend based on most likely kinepak or similars.

NM and anny, now that might be a different matter...

[death11284]

I think he was referring to ammonia, the cleaning product, in low concentrations it's not a gas at STP.This man is an idiot, the only reason this would detonate is the NM. If I ever want to waste a bunch of money I'll put up a video of me attempting this, perhaps soon.

[John Hinckley]

I believe the explosive you are referring to is called PLX. PLX is a mixture of nitromethane and an amine (to sensitize it).

Household ammonia would not do, it's way to low concentration. The curing agent for epoxy works (called "amine curing agent" sometimes), as would any other high concentration amine.

Google PLX explosives, that'll return some ratios to use.

[Anders Hoveland]

Nitromethane can act as an acid, even though it is not acidic, and can form salts.
In a mixture of nitromethane and ammonia, some of the molecules ionize to form a salt.
The "nitromethanate" ion, CH2=NO2(-) is much more sensitive than nitromethane.
Even though a mixture of ammonia and nitromethane is less powerful than pure nitromethane, it is much easier to detonate. It is virtually impossible to detonate pure nitromethane otherwise.

Nitromethane also can form hydroxylamine, if it is heated with 30% H2SO4. This will form hydroxylamine sulfate that can be removed, then reacted with Ca(NO3)2. This will form insoluble CaSO4 and leave hydroxylamine nitrate in solution. Hydroxylamine nitrate is much more powerful than ammonium nitrate, but it is very difficult to dry.

Also, acetic anhydride can react with chlorine gas (and a tiny bit of water added) to form chloro-acetic acid.
This can be distilled with NaNO2, and then CH3NO2 can be distilled out. This happens at only 70degC so a plastic bottle might be able to be used.

[madscientist]

Nitromethane is acidic.

Hydroxylamine alone is dangerous and prone to random explosions in anhydrous form.

Why in gods name would you try to make nitromethane from acetic anhydride?

[digermane]

Off the top of my head I would say the way to do it is to add a mixture of concentrated nitric and sulfuric acids to methanol. It's less stable than nitroglycerin though. Stay away from that shit.

[madscientist]

That's methyl nitrate you have in mind. ;)

[Leshrac]

Off the top of my head I would say the way to do it is to add a mixture of concentrated nitric and sulfuric acids to methanol. It's less stable than nitroglycerin though. Stay away from that shit.

Lol...

Nitromethane is done by nitrating METHANE, not methanol.

Nitration of methanol gives Methyl Nitrate, a liquid explosive. Not only is MN very unstable (it has a little bigger sensitivity than MEKP), it's also highly toxic.
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[digermane]

Ochem isn't my field :oops:

[Anders Hoveland]

Nitromethane can be made by the nitration of methane, but only when there is a big excess methane. This means that the nitration has to be performed at 400C when the nitric acid is vaporized into a gas. The reason that it is difficult to obtain nitromethane is that nitric acid reacts with nitromethane much faster than it does with methane. First, strongly acidic solutions decompose nitromethane into hydroxylamine and formic acid. Hydroxylamine is a reducing agent, and is easily oxidized by concentrated nitric acid. Bubbling Nitrogen dixide into an alkaline solution of nitromethane can make di- and tri-nitro methane.
Trinitromethane is actually a little acidic and can form yellow colored salts with bases. These salts are known as nitroformates, and are almost as energetic as perchlorates.

https://sites.google.com/site/energeticchemical/home

[digermane]

Bubbling Nitrogen dixide into an alkaline solution of nitromethane can make di- and tri-nitro methane.



Citation?

[Anders Hoveland]

You cannot just take me at my word? Now I will have make a boring post explaining this.
Nitromethane has two forms: the regular form, and the "aci-" form.
Reference: http://pubs.acs.org/doi/abs/10.1021/ja00081a072
This acid form has a double bond on the carbon, that leaves the hydrogens more vulnerable to oxidation. This is known as an "unsaturated" molecule.
Now, to quote: "Nitrations can also often be performed by addition reactions using unsaturated hydrocarbons with . . . nitrogen dioxide".
So to summarize, initially nitrating methane is difficult, but after the first nitro group, the others are much easier to add.

According to Love to Know: 1911 Edition, "The hydrogen in the primary and secondary nitro compounds which is attached to the same carbon atom as the nitro group is readily replaced by bromine in alkaline solution." Note that bromine does NOT readily react with regular hydrocarbons (unless left in sunlight). This indicates that nitromethane behaves as an unsaturated hydrocarbon under alkaline conditions.

Nitrogen dioxide reacts at room temperature with unsaturated hydrocarbons.
With ethylene (H2C=CH2) the main reaction (about 95%) is an addition reaction
and so dinitro-ethane is formed. But a smaller reaction is an oxidative nitration reaction where one of the hydrogens get replaced by a nitro group, forming CH2=CH--NO2.
Reference: http://pubs.acs.org/doi/abs/10.1021/ja00388a035
However, with a double bond between a carbon and nitrogen atom, the addition reaction is not possible since the N has a positive charge on it in this resonance state.

Also, at 60 degrees Celsius, pure nitromethane can be detonated by a # 8 blasting cap. Nitroethane can only be detonated if heated near its boiling point under confinement; Nitroethane, by itself, cannot be detonated without confinement.

Hydroxylamine can be made by heating nitromethane with Hydrochloric or sulfuric Acid.
(V. Meyer, Ann. (1876) p.663)
Extremely concentrated sulfuric acid >98% reacts with nitromethane to form hydroxylamine sulfate and carbon monoxide.

Trinitromethane can also be made be reacting (NO2)3C--CN with water.
(NO2)3C--CN can be made in 75% yield by doing a nitration on Methyl cyanide in a carbon tetrachloride solvent. Methyl cyanide can be made by dehydrating acetamide (CH3CONH2)
with P2O5. Acetamide can be made by simply strongly heating ammonia and acetic acid (vinegar) in a sealed tube, this is well known to those that run a meth-lab.
BUT BE WARNED: methyl cyanide is very poisonous, a leak at a factory in India killed hundreds of people.

[digermane]

I never take anyone at their word. I couldn't find anything in the literature mentioning the reaction you mentioned, so I quite reasonably asked for a citation.

Nitrogen dioxide reacts at room temperature with unsaturated hydrocarbons.
With ethylene (H2C=CH2) the main reaction (about 95%) is an addition reaction
and so dinitro-ethane is formed. But a smaller reaction is an oxidative nitration reaction where one of the hydrogens get replaced by a nitro group, forming CH2=CH--NO2.
Reference: http://pubs.acs.org/doi/abs/10.1021/ja00388a035
However, with a double bond between a carbon and nitrogen atom, the addition reaction is not possible since the N has a positive charge on it in this resonance state.

The mechanism is a radical hydrogen abstraction. Something that is highly unlikely to occur in any controlled fashion in nitromethane (unlike a long fatty acid chain.) Especially because any transition state would lose all stability gained from the double bond. I have no idea what you would get but it certainly would not be a high yield of dinitromethane.

[madscientist]

You cannot just take me at my word?

Your unreliability has previously been established :P References should always be used when claims are made that aren't common knowledge.

However, with a double bond between a carbon and nitrogen atom, the addition reaction is not possible since the N has a positive charge on it in this resonance state.

Do you KNOW this or do you think it MAY be the case? The lower electron density in that pi bond as compared to olefins certainly will destabilize any electrophilic addition transistion state... but it's not a FACT that it won't happen until experimental data is provided. It may just proceed at a very low rate. It may predominate under thermodynamic conditions. We don't know. A pad of paper and pencil is known to suck at predicting the course of untested reactions.

The free radical abstraction mechanism for bromine addition would require the presence of light or an initiator, which you specified wasn't present. This suggests an addition mechanism may be at work. Do you have a reference for the formation of di & trinitromethane from nitromethane and nitrogen dioxide? (Let me point out that nitrogen dioxide is itself a radical, so an initiator would not be needed for an abstraction mechanism for that one.)

Again, with nothing but paper, pencil and theory there's too many possibilities, too many questions. In fact, here's another one: perhaps the transistion state with the addition of bromine is stabilized by the formation of a bromonium ion (cyclic intermediate) but an analogous intermediate for nitrogen dioxide might not form. However, maybe it does form! How do we know? We analyze experimental data.

The Bhopal disaster involved the much stinkier methyl isocyanate, not acetonitrile. X-(

[Anders Hoveland]

It would be preferrable not to reveal certain sources, since this could lead to them being taken down, but you are assured that this is not just conjecture. A relevent link to NO2 reactions with unsaturated hydrocarbons:
http://pubs.acs.org/doi/abs/10.1021/ja00388a035

Another quote, "In spite of . . . addition of two NO2˙ radicals in the reaction of nitrogen dioxide with allylbenzene and some other alkenes, kinetic studies indicate that both NO2˙ and N2O4 are reactive species, each leading only to addition products." However, this is not quite entirely true. Russian researchers have shown that there is a small side reaction.

In the presence of oxygen, nitrogen dioxide reacts with unsaturated hydrocarbons to form
nitro-nitrites, and nitro-nitrates, in addition to plain double nitro compounds.

"alkyl radicals later react with nitric dioxide and nitroalkanes are generated"
Effect of copper and oxygen on the yields of individual nitroalkanes in the vapour phase nitration of paraffin hydrocarbons, Ivan Mladenov, Pepa Toromanova-Petrova
This exert indicates that nitrogen dioxide will not rect with a plain alkane, such as ethane,
an alkyl RADICAL is required. There are also numerous mention in patents to mixtures of hydrocarbons and NO2. However, I will conceed that in some situations, NO2 can react.
It is mentioned in a certain source that, "toluene can be nitrated with nitrogen dioxide at only 20 degrees Celsius into phenyl-nitromethane", with a formula (C6H5)CH2NO2.

There is a reason that the type of information that I post is not widely known of.
Most of the information dispersed in the amateur community deal with very basic reactions, mostly discovered before the year 1900. There was a different culture then, and scientific information was freely printed in encyclopedias found in libraries. If you look at old chemistry books from this time, you will find lots of good information. After the 1950's, chemistry began to advance at an extremely fast pace, and the reactions and measurements became so complicated that non-professionals could not really keep up with most of it. This is when information posted in popular chemistry encyclopedias became "dummed-down" to only very basic levels. The culture started changing after 1960, with the hippies and such, and "revolutionaries" began making explosives. The government, and both the conservative and liberal public developed a fear of chemistry. Chemistry sets no longer contained liquid mercury, cyanide, or nitric acid. Today, it is virtually impossible to find a toy chemistry set that even contains an alcohol burner. The appearance of meth-labs in the 1980's did not help matters, and only made the public even more paranoid.

After the 80's, once the cold war was over, the USA stopped putting emphasis on trying to expose school children in science. There were massive government budget cuts in all scientific research, and today most high schools do not have a chemistry laboratory. With less interest in chemistry, the quality of generally available quality information has fallen.
Compare a science encyclopedia from the 1950's with one today. There is a very noticable difference in terms of content.

Only a few types of new reactions have trickled their way down into the amateur chemistry community in recent times: nitramines and dinitramide, and even then many chemists interested in pyrotechnics have never even heard of dinitramide.

[digermane]

You're not talking about an unsaturated hydrocarbon. You're talking about a hydrocarbon with vastly different properties than a benzene, toluene or lipid.

Oh, BTW, there are a few of us on this forum that ARE professional chemists. I may not be as fluent in organic synthesis as some people but I still have a formal education in the field (I'm more inorganic synthesis and solid state chemistry/condensed matter physics). I'm questioning you based on what's widely known among chemists, not whats widely known among civilians. Cite your fucking sources. Saying that it works but I can't provide the data or proof is bullshit. That's a very good reason not to believe you.

Your citations are not fully relevant and only show your inexperience in synthetic chemistry. Benzene and toluene react entirely differently than dibutene (EAS rather than SN). Cite something showing the reaction occurring in something where the transition structure is as highly unstable and resonance stabilizes towards the reactants rather than the products as what you have proposed and I might believe you.

[Anders Hoveland]

Here is a quote from researchers in St.Petersberg Russia;
"reaction of nitroethane salt with sodium nitrite . . . 1,1-dinitroethane formed in a high yield."
N.A. Petrova, Zhurnal Organicheskoi Khimii Volume 43, # 5, p. 653–656. (2007)
As can be inferred, this is directly relevent to nitrogen dioxide reacting with nitromethane,
because "nitrite" is basically a form of nitrogen dioxide under alkaline conditions.
(2)NO2(-) + (2)H(+) --> NO2 + NO + H2O
(2)NO2 + (2)OH(-) --> NO3(-) + NO2(-)
from wikipedia: "Nitrites of the alkali metals can be synthesized by reacting a mixture of nitrogen monoxide (NO) and nitrogen dioxide (NO2) with a corresponding metal hydroxide solution"

If you have a formal education in the field, perhaps my site would be of some interest to you:
https://sites.google.com/site/energeticchemical/nitro-alkanes.

Nitrous acid (NaNO2 and acid) can be used to nitrate phenol or analine. If concentrated mineral acids are present with the nitrous acid, mostly the para-nitro will be produced (91% yield), but if acetic acid is present with the nitrous acid, yields of 74% ortho-nitro are possible. Ortho means the nitro is in the 2-position, adjacent to whatever other group is on the ring. Para means the nitro is on the opposite end of the ring from the other group.
The theory is that a nitrosyl ion (NO+) initially nitrates the ring, and then the resulting nitroso group gets oxidized to a nitro. ("Aromatic nitration", K. Schofield. 1980)

However, this nitrosyl ion equilibrium with nitrous acid is only present under strongly acidic conditions, certainly not when nitrous acid is in an alkaline envirorment., where it is mostly in the form of nitrite.

[digermane]

I suggest you read the Russian article you cite. They specifically say that any hydroxy containing group on the solvent will react preferentially over the nitrate ion. They also list several Lewis bases that will have the same effect.

That means you get the wrong product.

[Anders Hoveland]

Here is the reference for nitromethane an methyl nitrate reacting in the presence of a nitrite ion to form
methanol and a psuedonitrosole R--CH(NO)(NO2):
R. K. Blackwood, N. Kornblum and D. D. Mooberry, J. Am. Chem. Soc., 1956, 78, 1501.

Just found a very strange, and potentially useful reaction: Picric acid can be reduced with borohydride
(using ether and alcohol solvents) to form 1,3,5-trinitro pentane, which should be as thermally stable as nitromethane, unlike many other poly-nitro alkanes.
M. Adam and T. Severin, Chem. Ber. Volume 96, p448. (1963)

Nitromethane is known to be very energetic, but suffers from a low density, which limits its explosive performance. Making the molecule larger should give good compound, but this area has not been well explored because many such compounds are not thermally stable (see my site).