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Sciencemadness Discussion Board Special Topics Energetic Materials
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A uthor: Subject: Preparation of trinitromethane
PHILOU Zrealone posted on 10-12-2012 at 13:01
International Hazard
Mechanisms are quite obscure because many things happens all together:
-Addition of HNO3 and elimination of H2O on double bonds
-Addition of NxOy
-Nitrite hydrolysis
-Nitro-nitrite rearrangements
-Nitrosation and isomerisation into oxime
-Oxydations of carbons and of oximes
-Decarboxylation of nitrocarboxylic acids
-Nitro-keton hydrolysis
-...
If you look at all those reactions individualy and understand fully the principles in action behind; then you might understand
the all story and that sometimes excess carbon is destroyed in the process and degraded.
[Edited on 10-12-2012 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."
(W.Allen)
I dont get it . I mean how is it possible synthesis nitroform from isopropanol. Can anyone wirght
Posts: 1986 the mechanism ?
Registered: 2-3-2011 Shouldn't iso-propyl nitrate form ?
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I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort
itself out.
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and posting of untested
highly dangerous
procedures!
Quote: Originally posted by chemoleo
Well, this was put to the test.
Iodoform (a few spatula tips), made according to the method here, was dissolved in ether (25ml),
Posts: 1986 which formed a pale yellow solution.
Registered: 2-3-2011 To this AgNO2 powder (yellow grey) was added, also a few spatural tips, keeping the solution on
Member Is Offline ice all the while. The AgNO2 didn't dissolve.
The AgI product may have been forming a protective coating over the AgNO2 particles, preventing further reaction. With
these types of reactions, often both reactants have to be first dissolved before they can react together.
Even then, I would expect the yield to be quite low. While the nucleophilic substitution reaction of a haloalkane with silver
nitrite mostly forms the nitroalkane, a lesser portion of the nitrite ester is also formed. As should be self-evident statistically,
the yields become progressively lower as there are more halogens on the same molecule to be replaced by nitro groups. I
remember reading somewhere that the yields of tertiary nitroalkanes from their respective halogen-substituted reactants is
only around 11%. You see, even if only one of the iodine atoms in iodoform becomes substituted by a nitrite group (rather
than nitro), it will open the molecule up to hydrolysis, and all you will get is formic acid.
Something else to mention: Nucleophilic substitution reactions on haloalkanes generally only work when the halogen atom
is bromine or iodine. The rate of reaction with chloroalkanes is generally negligible (the reaction takes 6+ months). (there
are ways to speed this up, but they are not applicable here)
When adding a couple of ml of this to H2O, the yellow colour remained in the etheric fraction ,
which is unfortunate because the TNMe should really dissolve in H2O. No visible reaction of the
etheric extract with 34% formaldehyde either - but again part of the problem could be because the
solutions don't mix.
Trinitromethane is going to be more soluble in ether than water. Similar color concentration in the oil fraction layer can also
be observed with bromine.
I shall add some more AgNO2, to see what happens with it. Lateron I might try the same wtih
NaNO2, and ethanol.
Probably either AgNO2 or NaNO2 could be used. The silver salt is often preferrable for several reasons: Many silver salts
have unusual solubility in benzene (the Ag ion coordinates with the aromatic ring). The formation of AgI/AgBr/AgCl is
favorable and helps drive the reaction. And the silver halide byproduct is insoluble and can be easily filtered out.
I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort
itself out.
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Member Is Offline
I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort
itself out.
I tested Anders isopropanol and 99% nitric acid death wish, or should I say process. I was in the idea that heating 99%
Posts: 1937
nitric acid and adding isopropanol was a bad idea, so I added a drop of isopropanol in room temperature nitric acid, the
Registered: 27-12-2010 reaction was very violent, making a cracking sound and splashing mixture. It was evident the reaction mixture should not be
Member Is Offline heated, but well cooled. While swirling the flask and making the isopropanol running on the side of the flask the reaction
was much moderated, up to the point I got a runaway. I quickly improvised a water bath, and managed to stop the runaway
Mood: Mad as a hatter and add the remaining isopropanol. Because I love my limbs I preferred to lets the mixture set for about 10 hours at room
temperature instead of cranking the heat up for two hours.
Hopefully some yield will be obtained even with the runaway, otherwise the reaction will be re-tried with cooling. Altough
extremely dangerous, the process seams to be working at the point I am.
When the waiting will be done, an extraction with 1-3 dichloropropane wll be made, due to the lack of other chlorinated
solvent. The extract will be reacted with potassium hydroxide dissolved in methanol to precipitate the potassium
nitroformate.
The extraction was tried, it definitely did make some precipitate that was colored yellow, although it was highly contaminated
Posts: 1937
with potassium nitrate, the dried salt smoldered when lighted, but was definitely highly impure. The process show very high
Registered: 27-12-2010 potential, but I need to improve the recovery of the trinitromethane.
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Any idea is welcomed.
Mood: Mad as a hatter
Posts: 22
Sorry for barging in on a thread that hasn't been active for over a year, but does anybody think that it might be possible to
Registered: 9-7-2013 nitrate dinitromethane (or derivatives thereof) into trinitromethane? DNM is pretty easily obtained as one of the products of
Member Is Offline the reaction between nitric acid and hexamethylenetetramine (the other products being water, ammonium nitrate, and RDX),
and the dinitromethanide anion is has been investigated as a component of imidazolium ionic liquids and experimental
shock-insensitive explosives. The fact that the anion exists means that either DNM itself can be deprotonated (doesn't
sound unreasonable), or that derivatives of DNM (particularly halodinitromethanes, which could be obtained by the oxidation
of dinitromethane with the respective halogen) can be reduced (by alkali metals or alkali hydrides?) into halides and
dinitromethanides.
It might be possible to nitrate the DNM anion with a nitronium salt or nitric acid. Nitration with a nitronium salt would be a
simple Lewis acid-base reaction, and therefore more straightforward, but I'd be worried about a runaway reaction and the
decomposition of the formed TNM. Nitration with nitric acid would proceed via a condensation reaction, and might, therefore,
be less favorable, as condensation reactions often require heating and additional acid (as catalyst) to occur, again risking
the decomposition of the product.
Halodinitromethanes offer an alternative route to those involving the nitration of the anion. If they're stable (I've seen
reference to bromodinitromethane) they could be reacted with a nitrite salt to displace the halide, rendering TNM and a
halide salt.
I still need to do more research on these ideas, but does any of that sound good?
DNM is quite unstable because part of the -NO2 turns into -ONO (nitro-nitrite rearrangement).
Posts: 2865
It is sensitive to base media and to acidic media.
Registered: 20-5-2002 This effect is also present in TNM but to a lesser extend and into TeNM in an even lower level.
Location: Brussel
The best (and safer) way to nitroform is probably via TeNM and reduction.
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In the above stated reactions:
Mood: Bis-diazo-dinitro- 1°)
hydroquinonic iodoform/AgNO2 may work but one needs a good solvent of both reactants (maybe DMF or DMSO; an alternative may be
aceton/propanon, but with lower yields.)
The main problem with AgNO2-haloalcane way is that each NO2 may introduce into the molecule as 60% nitro and 40%
nitrite.
If one nitrite is included, the molecule will destroy itself via hydrolysis...
First step:
CHI3 + AgNO2 --> CHI2-NO2 (60%) + CHI2-ONO (40%) + AgI (s)
Note that AgI is a pale yellow precipitate turning yellower/ darker upon light exposure...because metallic Ag forms and I2 is
set free...in most organic solvents I2 will turn yellow, orange, brown or black depending on concentration in polar solvants (it
will be violet in some other apolar solvents).
CHI2-ONO will likely be destroyed
Second step:
CHI2-NO2 (activated halide) + AgNO2 --> CHI(NO2)2 (60%) + CHI(NO2)(ONO) (40%) + AgI (s)
Again the nitrite substitued part will be lost in fumes.
Third step:
CHI(NO2)2 + AgNO2 --> CH(NO2)3 (60%) + CH(NO2)2(ONO) (40%) + AgI (s)
Again the nitrite substitued part will be lost in fumes.
The overal yield can only be at best 60% x 60% x 60% = 21,6%
Starting from chloropicrin and AgNO2 one may go slighly to a better yield because one initial nitro group is already present
and thus only two substitutions are critical (last nitro group can be set as a nitrite without much harm in TeNM because in
equilibrium)...maximum yield 36% (60% x 60%).
C(NO2)4 <==--> C(NO2)3(ONO)
2°)
The processus may use KNO2 or for better solubility NaNO2 or even better LiNO2 in an appropriate solvent instead of
AgNO2, but the yield of nitro substitution is lower than 60% and sometimes it goes almost exclusively to nitrite substitution.
3°)
The nitric acid/isopropanol way may be replaced by HNO3/ propanone (aceton)...the first oxydation step of isopropanol
being propanone and thus much of the exothermicity of the reaction is already spared.
Beware that even so Aceton/Nitric acid makes very fast a runnaway after a short induction period; the mix very fast heats up,
boils up and free NxOy nitrous fumes...very long and good cooling condenser is needed!
Such mixes must be in great excess of HNO3 in a way to ensure polynitration but also to temper the heat AND BE FAR
FROM PERFECT OB MIXES which are detonable by heat and shock...such molecular mixes of oxydiser and fuel with conc
HNO3 are as sensitive and powerful as NG!
Aceton probably react by a first addition of HNO3 via its enol form...leading to nitroaceton.
CH3-CO-CH3 <==--> CH3-C(OH)=CH2
CH3-C(OH)=CH2 + HO-NO2 --> CH3-C(OH)2-CH2-NO2
CH3-C(OH)2-CH2-NO2 --> CH3-CO-CH2-NO2 + H2O
The following steps must involve nitrosation of the nitromethyl moeity by NxOy and oxydation to polynitro compounds...finally
splitting of the acetyl part and nitroform liberation.
4°)
The reaction of MNM, DNM with halogens usually ends up in a mix of halonitrocarbons that are dangerous because of their
toxicity (related to chloropicrin, and the halogen is very labile because activated by the nitro group(s)...those are potent
lachrymator and war gases very avid to react with any living moist membrane (lungs, mouth, eyes, nostrils).
MNM forms chloronitromethane, dichloronitromethane and chloropicrin.
DNM will form chlorodinitromethane and dichlorodinitromethane.
The mix is difficult to separate...for the mononitro compounds, this can be done via distillation, but for the dinitro compounds
distillation is unadvisable owing to the very high risk of detonation...keeping in mind the war gas nature of the compound in
the event of a glasware break or explosion....
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."
(W.Allen)
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