Nitrocreatine

I have been wondering for a while now whether creatine, the stuff body builders buy in way too big tubs , might not be a good substrate to nitrate and generate EMs.

Creatine has a nice combination of functional groups in terms of EM theory: a guanidine group (can be nitrated at least once comfortibly, see nitroguanidine) and an acetic acid group (can be destructively nitrated to a trinitromethyl group with loss of CO₂, see tetranitromethane) and a methyl amine of sorts (good explosive 'fuel' group, for example see methylammonium nitrate in TOVEX).

A cursory search on 'creatine nitration', however, did not turn up much, but surely somebody somewhere has attempted to nitrate it?

The 'ideal' nitrocreatine compound I'm thinking of would be the tetranitro derivative:



With a formula of C₃H₅N₇O₈

Note the excellent OB.

UPDATE:

Some preliminary computer modelled results have been volunteered to me (see attached files)

The .mol file is the result of a quantum mechanical minimisation without frequency calculation and it gives some idea about bond lengths and angles and such.

Also a basic force field optimisation has been done on a P-1 unit cell to obtain a first guess as to the density of such a hypothetical structure (see .cif file attached).

The determined density was 1.75 g/cc, not half unexpected nor bad for such an unsymmetrical EM.

I would guess that this would be a strongly brissant and sensitive EM, potentially making it a good secondary/booster candidate, e.g. tetryl substitute (yes yes, already a legacy explosive and all that), however, I would also expect it to still be a rather toxic compound because of the trinitromethyl group (analogous to the toxcitity of TNM because of the lability of one of its NO₂ groups... taking note that the QM minimisation did show a significantly longer bond length on one of those trinitro groups!)

Attachment: tetranitrocreatine (TNC).mol (2kB)
This file has been downloaded 874 times

Attachment: Hypothetical P-1 unit cell of TNC for density estimation.cif (3kB)
This file has been downloaded 895 times

[Edited on 24-4-2014 by deltaH]

Yes the availability of creatine is very attractive/frightening.

As for a method... early days, but I was thinking to learn from the tetranitromethane methods developed specifically for acetic acid, as I believe this is similar for at least that half of the molecule. For the other half one could learn from nitroguanidine preparation, but it would probably be a case of whatever affects the destructive nitration on the acetic acid side would easily sort out the guanidine functional group?

The main worry is not have conditions aggressive enough to have the whole thing fall apart, for example, I am trusting the methyl group in that molecule to hang tight



[Edited on 24-4-2014 by deltaH]

Thanks Dornier for that excellent contribution. The predicted detonation pressure is remarkibly high I will look into Avagadro for quick dH estimations then, thanks for the advice!

Motherload, could you ellaborate please?

[Edited on 24-4-2014 by deltaH]

Motherload, if I'm understanding you correctly, the resulting structure would be a four member three nitrogen ring and so no, this is unlikely, probably highly sensitive/unstable.

Ral, no idea about the stability as of yet, so I cannot comment about that definatively, though I am hoping that the guanidine group would lend some stability although this is perhaps nullified by the trinitromethyl monster on the other side... who knows?

The how to make it is yet to be determined, as I mentionioned to Bert above, I know how I would approach a synthesis (based on similar materials and their methods), but what would actually be a good recipe in the end would require experimentation.

As I've mentioned in another thread about collaboration, I am neither legally entiled to nor equiped to safely carry out such an investigation, I hope that somebody, someday, who reads this AND satisfies those criteria may be interested to investigate this further and report the results.

Please guys, leave this to experienced experts, exploratory EM research is very dangerous!

I would also suggest NEVER attempting anything in more than 10's of mg amounts to start out with until the system is well studied and it's behaviour/tendencies understood.

Bert, you mentioned that you were considering gearing up for this kind of work, if you ever get there, I'll come and work for you

Also, you mentioned that creatine is sold as a monohydrate... that would need to be taken into account.

Perhaps a good start in this system is trying to prepare the mononitrocreatine first by [mild] nitroguanidine methods. That product should be rather insensitive and not particularly energetic because of a terrible oxygen balance.

Step two could be a nitration of the mononitrocreatine in strong media (100% HNO3?) to form tetranitrocreatine (TNC).

Those are my hypothetical thoughts on it for the moment.

I believe braking down a multifunctional nitration into two steps would be most prudent in the beginning. One pot methods could be worked on once the foundation has been laid and studied.

****
Wow, apparantly body-builders also use creatine nitrate

I wonder if it's OTC in pure form, doubtful I guess.

Either way, easy enough to prepare the nitrate salt and then affect the dehydration for STEP ONE, namely, to prepare mononitrocreatine in the way one would make nitroguanidine.

The question is can one nitrate it further to TNC afterwards?

[Edited on 25-4-2014 by deltaH]

Can you maybe explain with some drawings please? Are you talking about the resonant structures of creatine nitrate?



If so, I think they are equivalent IMHO

Please elaborate, I'm lost

****

Thanks gregxy, this is very interesting. I did not know about creatinine until now!

For those who have never heard about this, the structure from Wiki is:



This cyclisation might not be a bad thing. For example, the Wiki authors have forgotten one other tautomer possible with creatinine, IMHO:



This kind of tautomerisation can be seen, for example with 2-pyridone.

This might actually activate the β carbon to further nitration because it is ortho to an ar-OH in a possible tautomer?!

[Edited on 29-4-2014 by deltaH]

Quote: Originally posted by deltaH

PHILOU, I am not completely sure I understand what you meant with Quote: This methyl amine group might be more or equaly basic as the formamidine part of the molecule...thus knowing if you will end up with a methylaminium nitrate or with a aminium nitrate form the guanidine is a first step. Can you maybe explain with some drawings please? Are you talking about the resonant structures of creatine nitrate? If so, I think they are equivalent IMHO Please elaborate, I'm lost

Not only about the resonant structure .

In a guanidine, you have 3 nitrogen atoms and each may be subject to an acid-base reaction... pKa1, pKa2 and pKa3 or pKb1, pKb2 and pKb3 are the equilibrium constants of those reactions.

The acidity or the basicity of a nitrogen atom is dependant on its surrounding atoms and groups of atoms...often the electronegativity or attraction-induction plays a big role; but also resonance structures.

CH3-NH2 is more basic than NH3 wich is more basic than NH2-NH2 itself more basic than NH2-OH

Cyclohexylamine is more basic than aniline.

So here you have:
1°)On one side H2N-C(=NH)- formamidine group in resonance what makes those two nitrogen equivalent linked to a nitrogen atom holding an inductive methyl group and an electron withdrawing group CH2-CO2H.
2°)On the other side CH3-N(-CH2-CO2H)- linked to an electron withdrawing group formamidine.

The question is which one will display the highest basicity and be protonated in majority?

Okay, I think I am with you now, thanks for the ellaboration!

I have made this drawing for the one and the other attached below.



What was your thinking as to how this would affect the nitration?

[Edited on 29-4-2014 by deltaH]

Quote: Originally posted by deltaH

Okay, I think I am with you now, thanks for the ellaboration! I have made this drawing for the one and the other attached below. What was your thinking as to how this would affect the nitration? [Edited on 29-4-2014 by deltaH]

Sounds like 'fun'

...and on top of that, as gregxy pointed out, one might actually be affecting a creatinine nitration.

Thanks for your thoughts PHILOU, interesting as always. One can only hope cleavage will occur in the right place, but as always, some bad cleavage is bound to occur even if unfavoured, selectivity will always be an issue with multifunctional exhaustive nitrations.

Quote: Originally posted by Motherload

Can a Triazole ring be formed on the Guanidine end with treatment with HNO2 ?