Sciencemadness Discussion Board

Nitrobutane trinitrate

Chisholm - 6-6-2017 at 10:50

Tris(hydroxymethyl)nitromethane, C4H6N4O11, is a precursor to Tris base, a buffering agent widely used in biochemistry. Tris base is made from tris(hydroxymethyl)nitromethane by reducing the nitro group to the amine:




Tris base


Before the reduction, however, one has a triol with a nitro group attached directly to a tertiary carbon. Unlike glycerin, erythritol, and mannitol, all hydroxyl groups are primary, much like ethylene glycol and pentaerythritol, and thus their nitrate esters are more chemically stable in storage.

The trinitrate ester of the nitro compound would have a perfect oxygen balance, and would probably be more stable in storage than ETN, and may also be melt-castable.

Given the extreme resistance of tertiary nitrocarbons to attack in acid media, the normal mixed acid –> bicarb –> alcohol recrystallization procedure used for ETN production should work here as well.

The real pain, though, is getting the precursor in a pure state.

In a 100mL beaker I mixed 21 mL of 37% formaldehyde (in 85/15 water:MeOH) with 5 mL of nitromethane, and added ~0.2g sodium carbonate. After about a minute, the reaction began, with considerable heating that brought the contents to a boil for a few moments. A slight yellowish tinge slowly appeared.

How would one best recover and purify the tris(hydroxymethyl)nitromethane? Ordinarily I would attempt extraction with diethyl ether, but I'm currently out.

PHILOU Zrealone - 6-6-2017 at 11:23

Already extensively discussed by Axt...
Search onto the forum with the search engine for nitroisobutyltriol (tri)nitrate (NIBTN)and
Nitroisobutylglycerol Trinitrate (NIBG(T/N))

[Edited on 6-6-2017 by PHILOU Zrealone]

NeonPulse - 6-6-2017 at 16:59

When I did this reaction I simply gently heated the solution to drive off excess water and upon cooling the Orange/yellow crystals just grew.

ecos - 6-6-2017 at 17:48

What is the VoD?

PHILOU Zrealone - 7-6-2017 at 02:45

:mad: Oh J.... everybody here must be spoon fed?
Searching with the provided keywords afwords... Nitroisobutylglycerol trinitrate by Axt

Thus VOD better than NG but less than PETN...this due to it being liquid instead of solid...

On the other hand the dinitroethane based brother is solid and outperforms PETN...was discussed into another tread...to be found by using the afworded keywords...

[Edited on 7-6-2017 by PHILOU Zrealone]

Chisholm - 7-6-2017 at 06:58

To be fair, some of us did find the thread. I wish Axt had kept his videos somewhere other than Geocities... they might as well be hieroglyphs on a wall cartouche buried in the Valley of the Kings.

I'm disappointed that it is a liquid.

In the thread they claim that it is less stable in storage than NG. Why is that? The nitrocarbon is tertiary and thus does not undergo tautomerism, thereby cutting off most reaction pathways that involve nitrocarbons. The nitratoxy groups are all attached to primary carbons, like in PETN and EGDN, and unlike in the less stable nitroglycerin, ETN, and nitromannite.

PETN and EGDN are far more stable than the others mentioned, and I was under the impression that this was due to all of their nitratoxy groups being on primary carbons. Decomposition of nitrate esters begins with the formation of free radicals by the loss of NO2. Free radicals are stabilized by hyperconjugation, electron-donating groups, and polarizability. An oxygen atom attached to a primary carbon alpha to a nitro group would seem to have a much higher barrier to formation than those in the breakdown of ETN or NG.

Is the inferior storage stability of NIBTN inherent to the molecule, or is it partially the result of impurities in the starting materials?

PHILOU Zrealone - 7-6-2017 at 13:44

Don't be disappointed that it is a liquid...the (HOCH2)2C(NO2)-C(NO2)(CH2OH)2 tetranitrate brother is a solid...and more powerful..

It is also a matter of electronegativity (Electron withdrawing group effect)

Into NG the central CHONO2 is surrounded by two CH2ONO2 so it is more sensitive to hydrolysis and oxydation to dihydroxyaceton dinitrate.

Into NIBGTN the central atom is holding a NO2 what is a stronger EWG than OH or ONO2.

Same effect is seen into TRIS tetranitrate (O2NO-CH2)3C-NH3ONO2...the -NH2 is not as basic as it should and thus the last HONO2 is not held wel while the external alcohol esters are more hydrolysable.

Another butantetrol is not mentionned probably because too unstable to exist (HOCH2)3C-OH thus TRIS where the NH2 is turned into a OH...the central OH is much more acidic due to 3 surrounding C-ONO2 and as a result the ester on that central position is strongly hydrolysable because kind of an anhydride of mixed acids.

From this it can be anticipated that (O2NO-CH2)3C-N(NO2)-CO-N(NO2)-C(CH2-ONO2)3 (bis-TRIS-dinitrourea hexanitrate) would be very unstable and sensitive to hydrolysis, heat and shock...propably decomposing spontaneously. NNO2 is a very strong EWG and here behind you have also a CO what is another strong EWG...

Stability of nitric ester is enhanced when the nitrate ester is external and when there is a CH2, CH or C bridge between two...this is wel seen from the strong difference of impact/shock/heat sensitivity between 1,2-propyleneglycol dinitrate and 1,3-propyleneglycol dinitrate.

PETN belongs to this but 1,3-propandiol dinitrate; 1,3-butandiol dinitrate, 1,4-butandiol dinitrate or polyvinyl nitrate also.


[Edited on 7-6-2017 by PHILOU Zrealone]

NeonPulse - 7-6-2017 at 18:49

Quote: Originally posted by Chisholm  
To be fair, some of us did find the thread. I wish Axt had kept his videos somewhere other than Geocities... they might as well be hieroglyphs on a wall cartouche buried in the Valley of the Kings.

I'm disappointed that it is a liquid.

In the thread they claim that it is less stable in storage than NG. Why is that? The nitrocarbon is tertiary and thus does not undergo tautomerism, thereby cutting off most reaction pathways that involve nitrocarbons. The nitratoxy groups are all attached to primary carbons, like in PETN and EGDN, and unlike in the less stable nitroglycerin, ETN, and nitromannite.

PETN and EGDN are far more stable than the others mentioned, and I was under the impression that this was due to all of their nitratoxy groups being on primary carbons. Decomposition of nitrate esters begins with the formation of free radicals by the loss of NO2. Free radicals are stabilized by hyperconjugation, electron-donating groups, and polarizability. An oxygen atom attached to a primary carbon alpha to a nitro group would seem to have a much higher barrier to formation than those in the breakdown of ETN or NG.

Is the inferior storage stability of NIBTN inherent to the


He is Video Demolitions on YouTube I'm pretty sure. Some of his stuff remains there.

PHILOU Zrealone - 8-6-2017 at 00:53

As said Neonpulse but in one word instead of 2 ;)
Videodemolitions

PHILOU Zrealone - 8-6-2017 at 10:19

Quote: Originally posted by PHILOU Zrealone  
Don't be disappointed that it is a liquid...the (HOCH2)2C(NO2)-C(NO2)(CH2OH)2 tetranitrate brother is a solid...and more powerful..

It is also a matter of electronegativity (Electron withdrawing group effect)

Into NG the central CHONO2 is surrounded by two CH2ONO2 so it is more sensitive to hydrolysis and oxydation to dihydroxyaceton dinitrate.

Into NIBGTN the central atom is holding a NO2 what is a stronger EWG than OH or ONO2.

Same effect is seen into TRIS tetranitrate (O2NO-CH2)3C-NH3ONO2...the -NH2 is not as basic as it should and thus the last HONO2 is not held wel while the external alcohol esters are more hydrolysable.

Another butantetrol is not mentionned probably because too unstable to exist (HOCH2)3C-OH thus TRIS where the NH2 is turned into a OH...the central OH is much more acidic due to 3 surrounding C-ONO2 and as a result the ester on that central position is strongly hydrolysable because kind of an anhydride of mixed acids.

From this it can be anticipated that (O2NO-CH2)3C-N(NO2)-CO-N(NO2)-C(CH2-ONO2)3 (bis-TRIS-dinitrourea hexanitrate) would be very unstable and sensitive to hydrolysis, heat and shock...propably decomposing spontaneously. NNO2 is a very strong EWG and here behind you have also a CO what is another strong EWG...

Stability of nitric ester is enhanced when the nitrate ester is external and when there is a CH2, CH or C bridge between two...this is wel seen from the strong difference of impact/shock/heat sensitivity between 1,2-propyleneglycol dinitrate and 1,3-propyleneglycol dinitrate.

PETN belongs to this but 1,3-propandiol dinitrate; 1,3-butandiol dinitrate, 1,4-butandiol dinitrate or polyvinyl nitrate also.



As a conclusion EW Groups favors hydrolysis but also radicalar breaking into free radicals what induces unstability towards heat/shock/friction by lowering the activation energy barrier...