Nitration of Tris????

Ok, silly question
Its quite easy to get hold of Tris buffer as a solid, which is (HOCH2)3CNH2, so similar to pentaerythritol except one methoxy group substituted with NH2.
Thus I wondered -- would there be any point in nitrating this? theoretically one would obtain the trinitrate, and the nitrate salt of this. surely though, the amine group would get oxidised ?!? Anyway, the point is, do you think its worth trying this? what happens to tertiary amines upon nitration?
If theory holds (which I doubt), I reckon this should make quite an interesting energetic compound

hehe .... ur enthusiasm is appreciated

Will it make (O₂NOCH₂₃CNH₂ or (O₂NCH₂₃CNH₂ ?

I can't see a way to make it into PE, but that doesn't mean it can't be done...

Shouldn't be too hard to make a kinda nitramine version of NIBGTN, I'm quite sure that if you used the common PETN synth (95% HNO3 etc) that you'd end up with the nitramine rather than the nitrate salt.
C(CH₂ONO₂₃NHNO₂. Good OB...

[Edited on 29-8-2003 by Nick F]

Hey, just think - oxidise it (like ammonia to hydrazine) and then nitrate it to (O₂NOCH₂₃C-N(NO₂-N(NO₂-C(CH₂ONO₂₃

Probably not possible though...

[Edited on 29-8-2003 by Nick F]

ok I think due to the scarce number of replies someone got to try it....!
i wont in the near future as I am away from my lab.... although i got tons of Tris buffer around me! anyone requires a little sample?

ok, the offer stands nonetheless
anyone in the UK who wants to try it with a few grams of Tris?? Its not a regulated substance or anything, so you would most definitely not get into trouble even if the police etc did find it

nitration of triethanolamine

yo, another idea.

Triethanolamine is (HOCH2CH2)3N. So three hydroxyls.
Is it possible to nitrate this, so that
(O2NOCH2CH2)3N is produced??
Anyone tried this?

This time it is truly easy to get hold of triethanolamine, photographics suppliers have this.

PS Thought of making another thread, but dont want to clog it with random nitration ideas

tho my gut feeling says u are right, why exactly wouldnt you get it? I bet, if you were able to make triethanolamine trinitrate, people would be quite impressed by its power!!!
the same goes for Tris-trinitrate!

Edit: Oops, didnt see vultures moderating Edit! Still I reckon its a valid question, right?

[Edited on 4-9-2003 by chemoleo]

yeah, anyway... I am surprised that noone can really say for sure what you'd get if you nitrated Tris - I would have thought this is a standard question for all the chemists out there!
Sure, *probably* one'd get the nitramine or something, but has noone got any definitve data/answers on this??? With today's government-funded research, someone's bound to have tried it! Comeon bring it, i would really like to know!

PS sorry if I am too demanding but thats written into my genes

[Edited on 8-9-2003 by chemoleo]

no, I was making a recipe! but I got the idea from other synthesis routes for N-nitro primary amines such as MEDINA, EDNA, MNA, ..
the steps include:
1. RNHCOR' + HNO₃ ==(H₂SO₄ + CH₂Cl₂=> RN(NO₂COR' + H₂O
2. RN(NO₂COR' + H₂O => RN(NO₂H + R'COOH
if the amide is dissolved in a solvent that doesn't react with mixed acids and HNO₃ is solouble in it but H₂SO₄ isn't, yeald will increase because in some cases the nitroamide is destroyed by H₂SO₄. best solvent for this purpose is CH₂Cl₂.

my 2 last sentences were about tri(nitratoethyl)amine (the second topic brought up by <b>you</b> under this thread). in the last sentences I did<b>n't</b> mean (O₂NOCH₂₃CN(NO₂H which is predicted to be very powerful, I was refering to (O₂NOCH₂CH₂₃N

I'm surprised, my post was apparent. btw it is the tri(nitatomethyl)methylnitramine route I offered:
(HOCH₂₃CNH₂ + CH₃COOH => (HOCH₂₃CNH₃⁺OOCCH₃^-
(HOCH₂₃CNH₃⁺OOCCH₃^- => (HOCH₂₃CNHCOCH₃ + H₂O
(HOCH₂₃CNHCOCH₃ + 4HNO₃ ==(H₂SO₄ & CH₂Cl₂==> (O₂NOCH₂₃CN(NO₂COCH₃
(O₂NOCH₂₃CN(NO₂COCH₃ + H₂O => (O₂NOCH₂₃CN(NO₂H + CH₃COOH

wow - how did I get there? you make me sound like a complete retard lol
Ok, for one thing I think I wasnt clear about your definition of `nitrato´ (same holds for methylol). Never heard this before, so forgive my ignorance (explaining my confusion with nitrate esters and nitro compounds - was simply assuming the latter).
Secondly, the amine is indeed a primary amine attached to a tertiary carbon.... thats all. No problem there.
Again, I understood ´trinitratoethylamine´ to be a different compound from the one you were talking about (I should have interpreted your substance name more carefully, and would have probably understood correctly). I myself would have called it triethanolamine trinitrate or whatever. Explaining the confusion once again....and yes, this compound wouldnt have as nice an OB as Tris trinitrate (as I call it for now)

Anyway... could you explain though why you´d need the amide (which we ´hopefully´obtain by destructive distillation) for making the nitroamide and then later the nitramine? what would happen to the NH2 group if it was unprotected (i.e. *not* -NHCO-R), upon mixing with strong HNO3? Are you saying that a nitramine wouldnt be formed? - but what would happen instead?

pz

Plagiarising...

Hi there...
I noticed that thread ' PETN from 'tris buffer'' in the E&W forum ( http://www.roguesci.org/theforum/showthread.php?s=&threa... ), and suddenly understood why vulture was looking for someone called froot....
It's quite funny, that guy came up with the Tris nitration idea a few days afta I posted it.... and pretty much placed all the info I posted! At least he didnt copy and paste!
Anyway, although I understand it's not nice to do this, it's not really that important either... as I am sure other people have tried it (like those ever-so-powerful corporations), and probably there are reasons why this putative explosive is not a commercially used one...so no need to claim patent rights!
Else... anyone needs my precise contact details??? Wouldnt mind to have a piece of the Tris Cake


PS : what is HED? sounds serious ...

[Edited on 18-9-2003 by chemoleo]

a (moronic) tris buffer to pentaerythritol route

1. reaction of tris buffer with chloroform and KOH in alcohol converts it to a <b>iso</b>nitrle:
(HOCH₂₃C<font color=red>-NH₂</font> + Cl₃CH + 3KOH<s>&nbsp;&nbsp;&nbsp;></s> (HOCH₂₃C<font color=red>-NC</font> + 3KCl + 3H₂O

2. heating this @ 100-200°C converts it to a nitrile:
(HOCH₂₃C<font color=red>-NC</font> <s>&nbsp;&nbsp;&nbsp;></s> (HOCH₂₃C<font color=red>-CN</font>

3. reduction of the nitrile to aminomethyltrimethylolmethane using aluminum hydride!

4. diazotation at near neutral conditions with stoichiometric amounts.
(HOCH₂₃C-CH₂<font color=red>NH₂</font> + HNO₂ <s>&nbsp;&nbsp;&nbsp;></s> (HOCH₂₃C-CH₂<font color=red>OH</font> + H₂O + N₂
&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
conclusion: acetaldehyde isn't really hard to make!

heptryl!

acetonitrile reacts with NH₄Cl in alcoholic solution to form acetamidine HCl. I think we can generalize it for other aliphatic nitriles. the product of 2nd step in "tris buffer to pentaerythritol route" I posted, very possibly can react with AN to form guanyltrimethylolmethane nitrate which upon nitration should yield <font face=symbol>a</font>-nitroguanyltrinitroxymethylmethane which should be a quite powerful and stable explosive:
(HOCH₂₃CCN + NH₄NO₃ <s>&nbsp;&nbsp;&nbsp;></s> (HOCH₂₃CC(=NH)NH₂.HNO₃
(HOCH₂₃CC(=NH)NH₂.HNO₃ + 3HNO₃ <s>&nbsp;&nbsp;</s><u>^H2SO4</u><s>&nbsp;&nbsp;></s> (O₂NOCH₂₃CC(=NH)NHNO₂ + 4H₂O

what about an ETN isomer?! add some tris buffer HCl to a previously chilled NaNO₂ sol hoping this reaction take place:
(HOCH₂₃CNH₃Cl + NaNO₂ <s>&nbsp;&nbsp;&nbsp;></s> (HOCH₂₃COH + NaCl + N₂ + H₂O
some nitrites (organic obviously ) may form as well. so add some NaOH and get it to boil (to hydrolyze the trisbuffer nitrites) add some urea then HCl (enough to make the sol neutral) boil the water away then pour in alcohol, stir, let stand for some minutes, then filter the undissolved NaCl, let the filtrate stand till all the alcohol evaporates leaving crystals of trimethylolmethanol & urea. add the crystals to conc nitic acid in which anhydrous calcium nitrate has been added (u see the urea impurity is an advantage here) u know the rest...


added to <i>to do list</i>. I'd be bliss to have some piece of (crispy?) crystals of this tris thingy. just dismiss this paragraph I'm just frisky

formaldehyde + nitromethane + HCl and powdered Fe/Sn/Zn ... I assume with these chemicals one can make tris buffer (aint hard to guess how)

Synthesis route to Tris?

The NIBGT synthesis route got me the idea:

In this case, CH2O + CH3NO2 and a weak base are mixed to get the NIBG (HOCH2-(HOCH2)C(NO2)-CH2OH).

In the case of Tris (where the NO2 is substituted with NH2), we should use Methylamine, CH3NH2! However, there is a problem I can see - the CH2O will react with the CH3NH2 to form H3CN=CH2 (which would polymerise?) - and I am not sure whether this would still work. From what I remember of the reaction mechanism the CH3 from the CH3NO2/CH3NH2 or even CH3CHO (for pentaerythritol synth) is activated by having those groups adjacent.
Any thoughts?

Also, acetone should react similarly with CH2O and a base, forming a big polyol (and indeed I stumbled across it, it's called anhydroanneaheptite) (HOCH2)3C-CH2OH-C(CH2OH)3.

How about the reaction of CH2O with acetylacetone, or pentane 2,4 dione (CH3-CO-CH2-CO-CH3)?
Would this give
(HOCH2)3C-CH2OH-C(CH2OH)2-CH2OH-C(CH2OH)3 ?

I am not so sure about the central C(CH2OH)2, i.e. whether this would be substituted, or remain -CH2- instead.

Anyway, these certainly are nitratable products..

PS Once again I wished we had a organic chemistry regular helping out... Philou... please help! Else.... guanguanco? He's not been online for a bit .. unionised? There got to be someone! Do I have to study organic chemistry just to solve my own questions? As if biochemistry wasn't enough


[Edited on 28-6-2004 by chemoleo]

Chemoleo, that mention about reacting acetone with CH2O got my attention. That molecule looks amazing! So I gave it a try. I kept the mixture at 50 deg. in order to keep the acetone from boiling out. Over 2 hours I had to keep adding CaOH solution to keep th pH high. Eventually I boiled the solution down and ended up with a very sticky yellow precipitate which is now drying on my oil heater . I used 50ml formaldehyde solution and excess acetone with adding quite alot of CaOH. Sorry about not giving exact quantities but my objective was to ensure all the CH2O was reacted while the excesses can be easily removed.

Could this be the anhydroanneaheptite you spoke about?

If so, any ideas what the correct nitrating process be?

[Edited on 28-6-2004 by froot]

[Edited on 28-6-2004 by froot]

Anhydro-Anneaheptite (an off topic sideshoot)

Well to be honest I think you approached this from the wrong end. What you want is an excess of CH2O, so as to react the acetone to completion! In your case you will probably have a mixture of polyols, all of them with less CH2OH's than they have in the anneaheptite.
I would repeat it, but this time work with moles. Per mole of acetone, you should have at least 7 or 8 moles of CH2O. Surplus CH2O can be evaporated off.
In fact, I'd try to use a procedure similar to that of pentaerythritol (check orgsyn).
React it for several days, even at RT. You can't react it for too long, only too short.
Then boil down the solution, with some charcoal, and filter. Try and crystallise it.
If you get crystals, bingo, you've won.
Then I guess one'd nitrate it as with pentaerythritol...
I think I will try making it at some point too... sounds too easy to ignore! Same for the acetylacetone

Anhydroenneaheptitol does not like to crystalise, it REALLY likes to remain as a sticky mess.
Although that shouldn't have any disadvantages for us, I don't think...
I made some a couple of years ago, but never actually got round to doing anything with it I don't think - it was probably about the time that I got lots of PE, and so I stopped experimenting.

Edit: and yes, it does get hot when you mix up the reactants all at once! Mine went dark brown with horrible polymerisation products etc, and was HOT. I just looked at the thread I started at E&W, apparently the nitrate is slightly more brisant than PETN, and drop height was 30cm, compared to PETN's 16cm. More brisant and less sensitive .

[Edited on 1-7-2004 by Nick F]

As I stated
O2NO-CH2-CH2-NH3NO3
O2NO-CH2-CH2-NH2NO3-CH2-CH2-ONO2
and
(O2NO-CH2-CH2-)3NHNO3
Exist and are wel documented.

The process of elimination and formation of an alcene only comes at relatively high T°...cf Hoffman degradations occure near calcination of quaternary amines.

On a side note, the same kind of elimination occurs at 170°C with alcools in sulfuric media.

Thus elimination process of relatively simple compounds usually occure >150°C a temperature you don't even want to use for a nitration...except in suiccidal behaviour .

Experiment

I wonder whether P2O5 or H2SO4 could simply be used. Or how about anhydrous MgSO4?

Another thought - perhaps it would be a good idea to derivatise the Tris before the nitration, making the nitration both easier, plus you can add on goodies to the NH2.
However, what chemical groups are available that add well to amine groups, but leave hydroxyls untouched? CH2O would have been my initial choice, but I assume that this reacts with the hydroxyls too. On the other hand, given the supposed prep. route to Tris, I suppose the beta carbon (which is quaternary in Tris) needs to be free, so possibly attack by CH2O would be ok? - leaving the hydroxyls unaffected?
Alternatively, a Sandmeyer could be done, turning i.e. the NH2 to OH. I have a feel that Axt prepared this product, or rather the nitrated form, already. Or was it from the combination of nitromethane and formaldehyde, whose product was nitrated, so slightly different as here we'd get quaternary carbon linked to NO3, not NO2?
I doubt chlorination of the NH2 would work, again for the acidic character. It's bound to be unstable.
What other possibilities are there to play on the amine in simple reactions *before* nitration?

Here are some derivatives of Tris, all more or less common buffers used in the biological sciences. All look interesting, but I fear not all are going to be useful for such purposes

Tris

Bicine

bis (2-hydroxypropyl)amine

Bis-tris propane

Tricine

Thank for downloading the PDF`s. The drawings look
nice. Which drawing program do you use ? Maybe anyone
have a interested link to any useful drawing software. I
have designed a small picture to some new TRIS compounds
bevor nitration.

TRIS(hydroxymethyl)-2-one and TRIS(hydroxymethyl)-2,2-diol
which can prepared from TRIS(hydroxymethyl)ethane with
different chlorinations.
I would guess some other derivates like hydrazinium and
oxime compounds are useful, TRIS(hydroxymethyl)dihydraziniummethane and any ethylene compounds.

Some hints to practical issues may help. I`m not shure but
the sandmeyer reaction within the diazonium salt will form
some various results by a reaction within a amino group.
A example is, aniline in HBr/NaNO2 HBr/CuBr will give first the diazonium salt and then the bromobenzene and not a nitroso compound.

Sandmeyer Reaction

Might i can post a useful process to some of the new
compounds.

Excuse me, i`ve uploaded accidentally the wrong file. The
reviced verion of the picture is now uploaded.

The the correct names of the new mentioned compounds are:
1,1,1,-Tris(hydroxymethyl)ethane-2-one
1,1,1,-Tris(hydroxymethyl)ethane-2,2-diol
1,1,1,-Tris(hydroxymethyl)methanehydrazine
1-tris(hydroxymethyl)-2-aminoethane-2-oxime
1-tris(hydroxymethyl)methane-1-amino-2,2-dihydroxyethene
1-tris(hydroxymethyl)methane-1,2-diamino-2-hydroxyethene
1-tris(hydroxymethyl)-2-hydraziniumethane-2-oxime
1-tris(hydroxymethyl)methane-1-hydrazinium-2,2-dihydroxyethene
1-tris(hydroxymethyl)methane-1,2-dihydrazinium-2-hydroxyethene

BIS TRIS is availaible from chem suppliers (CAS-Nr. 6976-37-0), Tris(hydroxymethyl)methane and Tris(hydroxymethyl)aminomethane too.
(CAS-Nr. 77-85-0 and 77-86-1) The compounds should be easy to nitrate in different ratios with H2SO4 and HNO3.

[Edited on 13-11-2006 by Mason_Grand_ANNdrews]

[Edited on 14-11-2006 by Mason_Grand_ANNdrews]

I have there a nice suggestion at the moment to one of the
new energetic Tris compounds to my last uploaded drawing.
Sorry for the drawing errors within the nitramides, some
problems to convert the picture to a useful compressed
format. I want to produce tris-(hydroxymethy)-aminomethane by the way from tris-(hydroxymethy)-
nitromethane.
Im not shure if the reduction within a the hydroxyde will give
the correct product. Maight somone can test this out.

Tris-(hydroxymethy)-nitromethane: (C4H9NO5, 151,118
g/mol)
Prepare mixture of 61 g of nitromethane and 91 g of
paraformaldehyde in a 1000 mL flask. Place the flask to a
cold water bad and in samll portions add around 62 g of
dryed calcium hydroxide powder with rapid stirring. Hold the
temperature below 55 °C during the addition and continue
the stirring for an hour at 55 - 60 °C. Use a stirrer or a
hotplate if necessary. After that, stirring is continued for 2 or
3 hours, pour the mixture over a coarse filter or a sieve
to remove impurities and add enougt 5 - 10% hydrochloric
acid until the solution will become slight acidic. The water is
careful removed by vacuum concentration much as possible
and then the flask with filtered solution is placed in a salt ice
bad, around 500 mL of 95-98% sulfuric acid is added in
small portions and the product is separated and extracted
with several portions of methylene chloride and anhydrous
magnesium sulfate.

Tris-(hydroxymethy)-aminomethane: (C4H11NO3, 121,135 g/mol)
Have anyone a prcical idea to make this stuff by a useful
way. I don``t know the reduction of a alcohol will work
correct and do not form the tri-sodium salt, maybe the salt
can be neutralized with a dilute acid. I would advice that the
industrial manufacturing process is more than complex. One
of the chemical names of the compound is Aminomethylidine-
trimethanol. Maight the obtained product from synthesis 1 is
combined with 270g of tin powder, over a peroid of one hour
510 mL 25% HCl is stirred in, the temperature is hold below
60 °C and the mixture is than refluxed for one hour. After
that, a solution of 450 g sodium hydroxide in 600 mL water
in combined with the first, stirred a while until all is reacted
and the product is then obtained by vaporizing the water
and distilled above 173 °C. Maight a separation exactly as synthesis 1
will work. I`m not shure, but it is possible the obtained
product is tris-(hydroxymethylsodium)-aminomethane.
Does someone have a idea to converte the sodium salt back
into the hydroxymethyl ?


[Edited on 8-12-2006 by Mason_Grand_ANNdrews]

A very interesting possibility concerning TRIS has been noted by Axt in the pentryl thread

http://www.sciencemadness.org/talk/viewthread.php?tid=8027&a...

I haven't reread the PEP articles above to see if this may already have been attempted , to condense TRIS with
dinitrochlorobenzene , and then to further nitrate the
product of that condensation .

Something tells me Axt may be looking into this possible
route for a " heptryl "

[Edited on 25-4-2007 by Rosco Bodine]

Actually the ring gets one more aromatic nitro during the
side chain nitration , and becomes a trinitrobenzene ring
along with the side chain you show there . So just change that first D to a T and you got it

Basically the end nitration product " heptryl " would have
the same structure as pentryl , with an extra pair of
nitroester groups in the side chain .

There's probably a series of aminopolyols which would
react accordingly with the DNCB so this could be a general reaction .

Concerning the possible condensation occuring with both of the ring chlorines on opposite sides in the case of para-DCB ,
yeah that same idea was discussed for ethanolamine earlier in the thread , and Nicodem didn't seem to be optimistic
about that reaction . However , it might or might not work .
I am not sure that Nicodem is the last word on this , even though I do value his input . These theoretical structures
are definitely in the realm of " test it and see what happens "
since theory is not perfect for predicting surprising results .

And what could be the eventuality is that the third ring nitro
entering may not occur. But this may not be significant , given
the addition of a second side chain which brings 3 nitroester
plus 1 nitroamino groups . If such a condensation of TRIS with both chlorines of para-DCB
did produce a symmetrical
aromatic di-alcohol of that sort which could be nitrated fully ,
it would have ten , 10 nitro groups ! ,
even in the absence of one TNB ring nitro which would have made it 11 ,
so there isn't much of a loss of energy there to be of concern .

Update :

I found an old post by Polverone where he tested paradichlorobenzene for reactivity of its chlorines ,
and it appears certain that nothing is going react
under any ordinary conditions , and that would include condensation reactions . So I have pretty well given
up on paradichlorobenzene , with regards to any reactivity
involving the chlorines anyway , for any lab syntheses .

Of course the discussion speculating about reactions for
para is something separate from the proven reactivity of dinitrochlorobenzene .

The proposition of condensing TRIS with DNCB still seems
to have validity .

I would say that the possiblity of alternate substitution
on both the hydrogens of the amino of TRIS does exist ,
to form a bis-dinitrophenyl condensate , similarly as occurs for ethanolamine condensing with DNCB .
But I have no idea what is the percentage probability
or distribution of either of the two possible products .


[Edited on 26-4-2007 by Rosco Bodine]