Sciencemadness Discussion Board

Nitration of Tris????

chemoleo - 28-8-2003 at 18:18

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 :)

Madog - 28-8-2003 at 18:35



chemoleo - 28-8-2003 at 18:45

hehe .... ur enthusiasm is appreciated :)

Blind Angel - 28-8-2003 at 19:12

Will it make (O<sub>2</sub>NOCH<sub>2</sub>;)<sub>3</sub>CNH<sub>2</sub> or (O<sub>2</sub>NCH<sub>2</sub>;)<sub>3</sub>CNH<sub>2</sub> ?

chemoleo - 28-8-2003 at 19:18

ok, assuming that the NH2 group doesnt get oxidised/whatever, you should get (just like NG/PETN/ETN) [(O2NOCH2)3CNH3]+ [NO3]- i.e. the nitrate salt of the nitrated version of Tris.

btw blindangel how do u do the subscript?

Blind Angel - 28-8-2003 at 19:28

< sub > xxxx < /sub >
Withouth the space

Basement Chemist - 29-8-2003 at 03:58


Madog - 29-8-2003 at 06:26

i have a PDF somehwere where it describes the nitration of urea to nitrourea with mixed acids.(whee)

i would think that it wouldnt oxidise real easily.

where is this stuff available?

chemoleo - 29-8-2003 at 06:34

'that stuff' is one of the most commonly used buffers anywhere... next to phosphate buffer maybe. So I imagine any lab will have it, and ordering it via someone who works in a lab won't ever raise eyebrows. I dont know whether you can get it as a household item or whatever - personally there is no need for it for me as I happen to get hold of it easily out of a lab...
I guess any chemistry supplier/pharmacy will have it, in bulk.

AngelEyes - 29-8-2003 at 07:04

Given that it's not easy to acquire pentaerythritol (in the UK, anyway), and one of the precursors, acetaldehyde, is a watched chemical, is it possible to prepare pentaerythritol from this Tris stuff? If the only difference is that one has an amine and the other a methoxy group, can't you 'swap the amine for a methoxy'? (over simplification, I know, but you get the idea). Maybe with formic acid or something?

Sorry if I am well off base was just a thought.

chemoleo - 29-8-2003 at 07:23

doubt it will be easy. you are talking of creating a new C-C bond. Also, the remaining CH2OH are fairly reactive themselves, so they would need to be protected to work on the NH2 specifically.
Anyway, thats why I thought Tris-trinitrate might make a nice compound if it works, and possibly a nice replacement for it is easy to get hold of Tris

Nick F - 29-8-2003 at 07:23

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(CH<sub>2</sub>ONO<sub>2</sub>;)<sub>3</sub>NHNO<sub>2</sub>. Good OB...

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

chemoleo - 29-8-2003 at 07:31

good point.
thats what I tought, too, to nitrate it as with PETN.
wow, that final compound should indeed be quite interesting!

Nick F - 29-8-2003 at 09:04

Hey, just think - oxidise it (like ammonia to hydrazine) and then nitrate it to (O<sub>2</sub>NOCH<sub>2</sub>;)<sub>3</sub>C-N(NO<sub>2</sub>;)-N(NO<sub>2</sub>;)-C(CH<sub>2</sub>ONO<sub>2</sub>;)<sub>3</sub>

Probably not possible though...

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

chemoleo - 29-8-2003 at 16:46

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? :D

Basement Chemist - 29-8-2003 at 18:07

lol dont send it to anyone in america because thanks to these new security measures to keep us safe from the evil terrorists, all powder is taken out of the mail... there go my coke shipments

chemoleo - 1-9-2003 at 07:24

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 :)

chemoleo - 1-9-2003 at 10:32

sorry, not as far as I am aware. It is a very common laboratory reagent (especially in biological/biochemical labs), used as a buffer.
It is nontoxic, and not a regulated chemical. Chemical supplies should ship it without questions asked, and I am sure pharmacies would stock it (alternatively you could order it).
The IS name is Tris(hydroxymethyl)aminomethane, or TRIS Buffer.

nitration of triethanolamine

chemoleo - 1-9-2003 at 13:45

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 :D

d g joshi - 2-9-2003 at 03:48

hi i doubt it willbe that easy

Please refrain from posting crap like this.

[Edited on 2-9-2003 by vulture]

chemoleo - 3-9-2003 at 17:37

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!!! :P
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]

vulture - 4-9-2003 at 06:40

I don't like people who say stuff just to say something without backing it up.
That's all.

No problems with your question Chemoleo.

BTW, does someone know a character called "froot" from south africa. I still have something to settle with this person.

[Edited on 4-9-2003 by vulture]

chemoleo - 4-9-2003 at 19:44

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! :P

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

[Edited on 8-9-2003 by chemoleo]

KABOOOM(pyrojustforfun) - 10-9-2003 at 14:07


what happens to tertiary amines upon nitration?

tris(methylol)methylamine isn't a tertiary amine. it's not related to the kind of C attached to it but is related to number of carbons attached. it's a primary amine and you can't get its nitramine by adding it to nitric acid. I suggest making its aqueous solution,then adding acetic acid filter the acetate salt then distill, hoping to get it's amide. dissolve the amide in CH2Cl2. add to mixed H2SO4 & HNO3/nitrate salt. separate the upper layer after reaction stops. let the CH2Cl2 evaporate away, to the left crystals add warm water. after hydrolysis, you have tris(nitratomethyl)methylnitramine crystals settling in dilute actic acid. filter. wash with water, let dry.

trinitratoethylamine isn't very powerful (due to its low OB), there are many ester nitrates easier to make while being more powerful.

chemoleo - 10-9-2003 at 19:17

hmm, good point, sorry. obviously I meant an amine attached to a tertiary carbon atom - is that the correct definition? Anyway - I don't see why an amide would be formed once mixed with with acetic acid.
Also, a nitro-ester would be formed most definitely, not the nitro form. just like with PETN.
You sound like you got this synthesis suggestion from somehwere - where? In other words, is
(O2NOCH2)3CC2H5NH2 a well known substance? it is somewhat different to the one I imagined to obtain from Tris, so bear that in mind (i.e. in terms of low OB)

KABOOOM(pyrojustforfun) - 12-9-2003 at 16:01

obviously I meant an amine attached to a tertiary carbon atom - is that the correct definition?

No, primary: RNH<sub>2</sub>, secondary: R(R' )NH, tertiary: R(R' )(R'' )N

I don't see why an amide would be formed once mixed with acetic acid.

I didn't say it forms amide after mixing. I said distilling (destructive distillation of course, I expect u to know amine carboxilates yeald amides when dehydrated) and when I say <i>hoping to get it's amide</i> I state that I'm not sure about it. It's because tris(methylol)methylamine behaves like both amine and alcohol thus it may esterify when heated but it's very unlikely to happen, especially if it decomposes before melting.

Also, a nitro-ester would be formed most definitely, not the nitro form. just like with PETN.

press Ctrl_F on this page type <i>nitro</i> and see this word doesn't exist in my previous post !!:shocked:

You sound like you got this synthesis suggestion from somehwere - where?

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' + HNO<sub>3</sub> ==(H<sub>2</sub>SO<sub>4</sub> + CH<sub>2</sub>Cl<sub>2</sub>;)=> RN(NO<sub>2</sub>;)COR' + H<sub>2</sub>O
2. RN(NO<sub>2</sub>;)COR' + H<sub>2</sub>O => RN(NO<sub>2</sub>;)H + R'COOH
if the amide is dissolved in a solvent that doesn't react with mixed acids and HNO<sub>3</sub> is solouble in it but H<sub>2</sub>SO<sub>4</sub> isn't, yeald will increase because in some cases the nitroamide is destroyed by H<sub>2</sub>SO<sub>4</sub>. best solvent for this purpose is CH<sub>2</sub>Cl<sub>2</sub>.

In other words, is
(O2NOCH2)3CC2H5NH2 a well known substance?

what r u talking about? no one disscussed such compound here. actually it can't exist because one of the carbons has 5 valence! even if you meant (O2NOCH2)3CCH2CH2NH2 it is far away from what we were talking about

it is somewhat different to the one I imagined to obtain from Tris, so bear that in mind (i.e. in terms of low OB)
someone spoke about

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 (O<sub>2</sub>NOCH<sub>2</sub>;)<sub>3</sub>CN(NO<sub>2</sub>;)H which is predicted to be very powerful, I was refering to (O<sub>2</sub>NOCH<sub>2</sub>CH<sub>2</sub>;)<sub>3</sub>N

I'm surprised, my post was apparent. btw it is the tri(nitatomethyl)methylnitramine route I offered:
(HOCH<sub>2</sub>;)<sub>3</sub>CNH<sub>2</sub> + CH<sub>3</sub>COOH => (HOCH<sub>2</sub>;)<sub>3</sub>CNH<sub>3</sub><sup>+</sup>OOCCH<sub>3</sub><sup>-</sup>
(HOCH<sub>2</sub>;)<sub>3</sub>CNH<sub>3</sub><sup>+</sup>OOCCH<sub>3</sub><sup>-</sup> => (HOCH<sub>2</sub>;)<sub>3</sub>CNHCOCH<sub>3</sub> + H<sub>2</sub>O
(HOCH<sub>2</sub>;)<sub>3</sub>CNHCOCH<sub>3</sub> + 4HNO<sub>3</sub> ==(H<sub>2</sub>SO<sub>4</sub> & CH<sub>2</sub>Cl<sub>2</sub>;)==> (O<sub>2</sub>NOCH<sub>2</sub>;)<sub>3</sub>CN(NO<sub>2</sub>;)COCH<sub>3</sub>
(O<sub>2</sub>NOCH<sub>2</sub>;)<sub>3</sub>CN(NO<sub>2</sub>;)COCH<sub>3</sub> + H<sub>2</sub>O => (O<sub>2</sub>NOCH<sub>2</sub>;)<sub>3</sub>CN(NO<sub>2</sub>;)H + CH<sub>3</sub>COOH

chemoleo - 13-9-2003 at 06:37

wow - how did I get there? you make me sound like a complete retard lol :o
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 :)

KABOOOM(pyrojustforfun) - 15-9-2003 at 13:53

With conc HNO3 you get the trinitrate ester. the multi nitrato groups reduces its basic property so much that it can't have a ionic nitrate. but before nitration it doubtlessly can form salt. another idea is to make a ionic nitrate before adding to conc HNO3. It is more economical for a home chemist. first make a saturated aqueous solution of tris x, add calculated amount of cold HNO3 (less concentration than 77.7%) chill the soln and filter. do the addition slowly and without stirring to get larger crystals (easier ,faster and better filteration). do the rest like PETN synth (the HNO3 method I mean, don't use mixed acid for that amine group's sake!). IIRC HNO3-Ac2O can nitrate primary amines, I think it was PH Z who once said MMAN + Ac2O yealds MNA. if this is correct, adding the mentioned trinitrate ester to Ac2O-HNO3 will yield the nitramine compound that is obviously more poweful than PETN!


chemoleo - 18-9-2003 at 15:53

Hi there...
I noticed that thread ' PETN from 'tris buffer'' in the E&W forum ( ), 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 no need to claim patent rights!
Else... anyone needs my precise contact details??? :P Wouldnt mind to have a piece of the Tris Cake :P

PS : what is HED? sounds serious ...

[Edited on 18-9-2003 by chemoleo]

a (moronic) tris buffer to pentaerythritol route

KABOOOM(pyrojustforfun) - 2-11-2003 at 18:38

1. reaction of tris buffer with chloroform and KOH in alcohol converts it to a <b>iso</b>nitrle:
(HOCH<sub>2</sub>;)<sub>3</sub>C<font color=red>-NH<sub>2</sub></font> + Cl<sub>3</sub>CH + 3KOH<s>&nbsp;&nbsp;&nbsp;></s> (HOCH<sub>2</sub>;)<sub>3</sub>C<font color=red>-NC</font> + 3KCl + 3H<sub>2</sub>O

2. heating this @ 100-200°C converts it to a nitrile:
(HOCH<sub>2</sub>;)<sub>3</sub>C<font color=red>-NC</font> <s>&nbsp;&nbsp;&nbsp;></s> (HOCH<sub>2</sub>;)<sub>3</sub>C<font color=red>-CN</font>

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

4. diazotation at near neutral conditions with stoichiometric amounts.
(HOCH<sub>2</sub>;)<sub>3</sub>C-CH<sub>2</sub><font color=red>NH<sub>2</sub></font> + HNO<sub>2</sub> <s>&nbsp;&nbsp;&nbsp;></s> (HOCH<sub>2</sub>;)<sub>3</sub>C-CH<sub>2</sub><font color=red>OH</font> + H<sub>2</sub>O + N<sub>2</sub>
&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; :P:P:P
conclusion: acetaldehyde isn't really hard to make!

froot - 18-11-2003 at 08:48

Ok. I tried this;
I used the method of synthesis for sodium picrate but substituted NaOH for tris. The pruduct was an oily liquid that wouldn't dry. I then added formaldehyde solution and a precipitate formed.
Any ideas?

chemoleo - 18-11-2003 at 15:33

I am not sure what you are trying to do there.
What kind of compound did you hope to get when you mix picric acid and tris? Picric acid being an acid, you may just get the salt with TrisH+ being the positive ion.
When you add formaldehyde, I should think you will get some kind of polymerisation and/or acetal reaction, as CH2O reacts with phenol to form bakelite (but I dont know how far this reaction is expandable to trinitrophenol), and CH2O may 1) react with the amine group, while it 2) also may react with the OH via the acetal route....
Anyway, I doubt you will be getting a single product...again, what were u trying to do??

froot - 18-11-2003 at 23:11

I had a somewhat open ended objective with this one. I guess I was hoping for a useful product/precurser for something else useful. I suspected the precipitate I got was from polymerisation.
I'll try the method you suggested-thanks.

froot - 18-11-2003 at 23:13

I had a somewhat open ended objective with this one. I guess I was hoping for a useful product/precurser for something else useful. I suspected the precipitate I got was from polymerisation.
I'll try the method you suggested-thanks.


KABOOOM(pyrojustforfun) - 19-11-2003 at 14:49

it's something like: picryl tris(nitroxymethyl)methyl nitramine.
I read in book that it's made via nitration of 2,4-dinitroanilinotrimethylolmethane and that its power and sensitivity is similar to that of PETN. the only usable info I could find on the net, was <a href=" net&rnum=1">this page on alt.engr.explosives</a>: Specific energy: 1245 mt/kg, volume of detonation gases: 127 l/kg, lead block: 787
I bet the precursor is made from chlorodinitrobenzene and tris buffer!

KABOOOM(pyrojustforfun) - 2-1-2004 at 13:53

acetonitrile reacts with NH<sub>4</sub>Cl 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:
(HOCH<sub>2</sub>;)<sub>3</sub>CCN + NH<sub>4</sub>NO<sub>3</sub> <s>&nbsp;&nbsp;&nbsp;></s> (HOCH<sub>2</sub>;)<sub>3</sub>CC(=NH)NH<sub>2</sub>.HNO<sub>3</sub>
(HOCH<sub>2</sub>;)<sub>3</sub>CC(=NH)NH<sub>2</sub>.HNO<sub>3</sub> + 3HNO<sub>3</sub> <s>&nbsp;&nbsp;</s><u><sup>H2SO4</sup></u><s>&nbsp;&nbsp;></s> (O<sub>2</sub>NOCH<sub>2</sub>;)<sub>3</sub>CC(=NH)NHNO<sub>2</sub> + 4H<sub>2</sub>O

what about an ETN isomer?! add some tris buffer HCl to a previously chilled NaNO<sub>2</sub> sol hoping this reaction take place:
(HOCH<sub>2</sub>;)<sub>3</sub>CNH<sub>3</sub>Cl + NaNO<sub>2</sub> <s>&nbsp;&nbsp;&nbsp;></s> (HOCH<sub>2</sub>;)<sub>3</sub>COH + NaCl + N<sub>2</sub> + H<sub>2</sub>O
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?

chemoleo - 27-6-2004 at 09:46

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

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 :(:o

[Edited on 28-6-2004 by chemoleo]

froot - 28-6-2004 at 11:20

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)

chemoleo - 28-6-2004 at 12:54


Sorry about not giving exact quantities but my objective was to ensure all the CH2O was reacted while the excesses can be easily removed.

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 :)

froot - 28-6-2004 at 21:55

Thanks for the help. I tried the synth as you suggested. I placed all the reactants in a conical flask, stoppered it and left it outside for the night, which was a good move! This morning the stopper was gone and the contents have mostly climbed out. That same precipitate as before was at the bottom.
Do you think the product may be 'caramelising' from heating too much?

chemoleo - 29-6-2004 at 18:56

I doubt it (the 'caramelising'.
Maybe, you should try it again, and slowly add the formaldehyde, over the course of several hours - while the Ca(OH)2 is present from the beginning.
The problem is, if it heats up too much, the form. / acetone will evaporate, thus changing reactant concentrations.. so either reflux, and do with a large reagent vessel... or do it VERY slowly with cooling. If you cant help the boiling, just add more CH2O - you want an excess of that, not acetone.
Then, after a few days (and having made sure no substantial amouns have evaporated/spilt), add some charcoal, filter, and reduce the volume. Put in fridge, and hope something will crystallise!

KABOOOM(pyrojustforfun) - 30-6-2004 at 13:14

chemoleo:<blockquote>quote:<hr>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? <hr></blockquote>
from COPAE:
<blockquote>quote:<hr>Formaldehyde enters readily into combination with substances which add to its unsaturated carbonyl group. If a substance containing an active hydrogen adds to formaldehyde or condenses with it, the active hydrogen attaching itself to the oxygen of the formaldehyde and the rest of the molecule attaching itself to the carbon, the result is that the position originally occupied by the active hydrogen is now occupied by a — CH2 — OH or methylol group. Hydrogens which are active in condensation reactions are those which are a- to a carbonyl, a nitro, or a cyano group, etc., that is, they are attached to a carbon atom to which a carbonyl, a nitro, or a cyano group is also attached and are in general the hydrogen atoms which are involved in the phenomena of tautomerism.The condensation of formaldehyde with acetaldehyde, with nitromethane, with cyclopentanone, and with cyclohexanone thus leads to polyhydric primary alcohols the nitric esters of which are useful explosives.<hr></blockquote> thus methylamin doesn't work here. what's wrong about reducting NIGB?

PHILOU Zrealone - 1-7-2004 at 09:36

simply read my U2U and edit it here as proposed.

Nick F - 1-7-2004 at 10:07

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]

froot - 1-7-2004 at 10:16

Nick, what was the colour of your product and do you remember how long you left the reactants before you reduced the volume of the solution? I have a solution made as Chemoleo explained and it has been sitting at RT for 48 hours now. It has a slight hint of yellow to it. I think I'll do the boiling tomorrow afternoon.

chemoleo - 1-7-2004 at 11:09

Reply from Philou:

About the process of tris from CH3-NH2 and formol it wont work since most products are: CH3-NH-CH2OH, CH3-N=CH2, CH3-NH-CH2-NH-CH3 (interesting for dinitramine) and 1.3.5 trimethyl 1.35 triazacyclohexane.

Only way to get tris is from trimethylolnitromethane reduction.

In fact the compound forms a tetranitrate that should be similar to PETN except maybe a little trouble of long term stability owing to the mild acidity of the nitrates of amines (acidity is bad with nitrate esters) anyway ethanolamine dinitrate is known, so does diethanolamine trinitrate and triethanolamine tetranitrate.





In your case with tris you will get a much better compound

As I said maybe a perchlorate anion might be exchanged to increase density, sensitivity and OB on the positive side.
To my feeling (as Kaboom wrote) tris upon reaction with HONO will yield a tetraalcohol that can be tertranitrated and that must be more powerfull than PETN but as sensitive as NG.
(HOCH2-)3C-OH --> (O2NOCH2-)3C-ONO2

Chemical Peach - 2-7-2004 at 09:30

I may be incorrect here, please tell me if anyone disagrees (my knowlege of thses type of reactions is very limited).

On direct nitration of the molecule using a method like that for the synthesis of PETN, the three nitrate groups should attatch in a similar way. However, the amine group (in acidic conditions afterall) would tend to protonate, (--> C-NH3+) which of course would then like to split off and a double C=C bond form to stablise the delta positive carbon, except due to there being no H on the central carbon atom (and no lone pairs of electrons) this removal of the protonated amine group may not occur. Instead, there may remain C-NH3+ on the atom, which may then form an ionic substance with ions present in solution once precipitated out. If this were to happen, i would not be sure how it may affect stability of the compound but would slightly concerned if attmpting to synthesize the nitrated product.

(somebody try it! (small))

[Edited on 2-7-2004 by Chemical Peach]

PHILOU Zrealone - 4-7-2004 at 06:28

As I stated
Exist and are wel documented.

The process of elimination and formation of an alcene only comes at relatively high T° 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 ;).


chemoleo - 8-5-2005 at 14:54

3 g Tris base was dissolved carefully in 25 ml icecold 90% HNO3, if added too fast it would produce red fumes and bubbles. After 30 min the yellow colour of the acid disappeared, the solution went clear. Then, under ice cooling, twice the amount of 96% H2SO4 was added, and the solution was allowed to warm up to RT, and kept there for 2 hours.
Pouring this into 400 ml ice water produced a milkyish solution, not clear, but letting it settle overnight did not yield a precipitate. However, the side of the beaker was covered with an oily sheen, even though the solution was still milky.

So it looks like a reaction did indeed happen, although not yielding a precipitate as with pentaerythritol.
Maybe next time try a greater % of HNO3, and longer reaction times at higher temps.

Axt - 5-11-2006 at 02:16

Reviving the topic, Attached is the synthesis of Tris(nitroxymethyl)methylamine via FNO2, OK thats not so interesting, but it does reference to its nitrate salt as being formed by the reaction with nitric acid.

<i>"Here we synthesise tris(nitroxymethyl)methylamine <b>1</b> and tris(nitroxymethyl)nitrosomethane <b>2</b>. Syntheses of the nitrate of 1 that involve either nitric acid[4] or its solutions in dichloromethane[5] have been reported. Attempts to isolate compound <b>1</b> as the free amine by neutralising the nitrate were unsuccessful. This was due to the fact that neutralisation of this salt with alkali metal carbonates or hydroxides or with ammonia occurs ambiguously and is accompanied by the formation of side products thus yielding a complex mixture of nitrogen-containing compounds."</i>

Its DCM solution may be the most convenient way since it would provide easy extraction of the salt which is likely water soluble, also provides an easy way of concentrated HNO3 without distillation. Its an acidic nitrate ester so stability may be questionable. Anyway to give some closure to this, the answer should be found in the following references:

4] Michael A. Hiskey, Melvin J. Hatch, Jimmie C. Oxley
Nitrato Amine Nitrates: Nitrate ester explosives with reduced impact sensitivity
Propellants, Explosives, Pyrotechnics
Volume 16, Issue 1, Date: February 1991, Pages: 40-42

5] L. B. Romanova, M. E. Ivanovo, D. A. Nesterenko and L. T. Eremenko
Synthesis of nitroxyalkylammonium nitrates
Russ. Chem. Bull., 1994, 43, 1207

The attached article is also of interest for the conversion of the nitrate salt into ONC(CH2ONO2)3, a solid MP 72.5-74°C. Possibly unstable in storage though.

[Edited on 5-11-2006 by Axt]

Attachment: tris(nitroxymethyl)methylamine.pdf (170kB)
This file has been downloaded 1106 times

solo - 5-11-2006 at 10:11

Reference Information

Nitrato Amine Nitrates: Nitrate ester explosives with reduced impact sensitivity
Michael A. Hiskey, Melvin J. Hatch, Jimmie C. Oxley
Propellants, Explosives, Pyrotechnics Volume 16, Issue 1, Date: February 1991, Pages: 40-42

The preparation and properties of several nitrato amine nitrates
are given along with calculated detonation velocities and measured
impact sensitivities. Comparison of these compounds with the high
performance explosive PETN is also given.

Attachment: Nitrato Amine Nitrates- Nitrate ester explosives with reduced impact sensitivity.pdf (324kB)
This file has been downloaded 1953 times

solo - 5-11-2006 at 10:18

Reference Information

Synthesis of nitroxyalkylammonium nitrates
L. B. Romanova, M. E. Ivanovo, D. A. Nesterenko and L. T. Eremenko
Russ. Chem. Bull., 1994, 43, 1207

A method for O-nitration of amino alcohols with a non-detonating mixture of nitric acid with dichloromethane has been proposed. The target crystalline products were precipitated from the reaction mixture by acetic anhydride. Key words: nitroxyalkylammonium nitrates; amino alcohols; O-nitration; concentration limits of detonation; explosion-proof process.

Attachment: synthesis of nitroxyalkylammonium nitrates.pdf (153kB)
This file has been downloaded 910 times

Axt - 6-11-2006 at 07:53

Thanks solo.

<i>"...the target nitroxyalkyl nitrates are separated from the reaction mixture as oils that contain water formed during O-nitration, in addition to the major compound. When acetic anhydride in an amount sufficient to bind the water is added to the reaction mixture, the target products precipitate as crystalline solids and can be separated by ordinary filtration."</i>

Simple process, looked good until the requirement for acetic anhydride in the DCM/HNO3 nitration solution. Look for ways around the use of acetic anhydride. Isolating the product may be its as simple as extracting the oil and sitting it in a dessicator.

Or, since the nitrate salt isnt so stable anyway it may be possible to form energetic derivatives of it directly from the oil. For example the nitroso derivative ONC(CH2ONO2)3 by reacting with NaNO2, or the dichloramine Cl2NC(CH2ONO2)3 by reacting with NaOCl.

The chlorinated derivative, could possibly then be nitrated to form the nitramine (check US patent 6,603,018 for nitration of dichloramines to nitramines).

chemoleo - 6-11-2006 at 17:00

Many thanks for clearing up a longstanding question.
So Tris trinitrate can be made, but the nitrate salt of this is unstable, perhaps not surprisingly. Did you see anything about the stability of the oil? It seems to me that getting the free amine from the unstable salt shouldnt be too difficult.
I'm adding the prep for this from the first paper that Solo attached:
To 35 ml of 99% HNO3 cooled to 0 deg C or below by means
of an ice-salt bath was slowly added 7.0 g of tris(hydroxymethyl)
aminomethane. Stirring and cooling were maintained
for 30 minutes after the final addition. The nitrating
liquor was slowly stirred into 200 ml of diethyl ether, at
10°C or below. The partially nitrated product immediately
precipitated and was suction filtered and washed with
CHCl3. Exhaustive nitration of the flaky white product was
accomplished by redissolving the entire amount in 20 ml of
99% HNO3 at - 20°C for 20 minutes. The product was
reprecipitated as before with diethyl ether, filtered, and
washed with ether and chloroform.The flaky white product
was dried under vacuum overnight. Upon weighing, the
product yielded 15.1 g (82%) with a m.p. of 110°C

Sounds tedious. Here's the prep involving DCM (second paper from Solo)
A solution of
monoethanolamine (1.2 g) (substitute with the appropriate amount of Tris) in CH2C12 (5 mL) was added
dropwise over a period of 20 min to a cooled mixture of
HNO3 (3.8 g) and CH2C2 (25 mL). The temperature of the
bath was maintained in the range 0--5 deg C. Then the reaction
mixture was stirred at this temperature for 15 rain, acetic
anhydride (3 mL) was added dropwise, and the mixture was
stirred for an additional 15 min. The precipitate was separated
and dried in a vacuum desiccator over P205 to give 3.1 g
(91.2 %), m.p. 100--102 deg C. After recrystallization
from EtOH, the yield was
69--72 %, m.p. 102--103 deg C

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 :)



bis (2-hydroxypropyl)amine

Bis-tris propane


Axt - 9-11-2006 at 01:59

It seems to me that getting the free amine from the unstable salt shouldnt be too difficult.

See last post on page two of this thread, theres problems with that.

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

I think you'd want an anhydride of a weak acid that soluble in DCM. P2O5 and H2SO4 aint you' end up with a slop under the DCM with a mixture of nitrate/phosphate/sulphate salts. As with the MgSO4, it'd create problems in isolating the wanted product.

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.

I cant see any problems with CH2O, but the condensation product may be quite a mess, maybe not the best choice. By analogy with that of the synthesis of nitraminoethanol nitrate, you could condense tris with ethylchlorocarbonate before nitration followed by ammonolysis to yield the nitramine (US patent 2485855).

Alternatively, a Sandmeyer could be done, turning i.e. the NH2 to OH.

Doesn't that rely on an intermediate diazonium salt, tris in this case forming a stable C-nitroso product.

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.

Yeh that was NIBGTN via CH3NO2/CH2O then nitration.

I doubt chlorination of the NH2 would work, again for the acidic character. It's bound to be unstable.

Acidic character? not sure what you mean there, its a basic amine but also it doesnt necessarily need to be basic to form a chloramine. As long as its a dilute solution the HNO3 shouldnt pose any problems, and actually would be needed to form the HOCl from NaOCl. I too dought its stability in the practical sense of using it for an explosive as is, but that wasn't the point.

What other possibilities are there to play on the amine in simple reactions *before* nitration?

Ethylchlorocarbonate to form the urethane, diethyloxolate to form the oxamide, acetic anhydride to form the acetamide derivatives, all could possibly be converted to the nitramine which I think is the most attractive target.

Mason_Grand_ANNdrews - 13-11-2006 at 10:06

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

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:

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]

Tris.JPG - 219kB

Mason_Grand_ANNdrews - 8-12-2006 at 11:39

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)-
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

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]

Tris.jpg - 29kB

CD-ROM-LAUFWERK - 22-12-2006 at 07:58

the ''U.S. Army Research and Development Command Encyclopedia of Explosives and Related Items CD-ROM.''
CD1, PDF nr. 1 (''VOLUME01''), page A132 left mid, says that both Bis(hydroxymethyl)methylaminomethan-dinitrat and Tris(hydroxymethyl)aminomethan-trinitrat are unstable even at room temp, ref: H. A. Aaronson, P ATR 1412(1942)

Rosco Bodine - 25-4-2007 at 15:09

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

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 " :D

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

chemoleo - 25-4-2007 at 15:28

Certainly sounds like an interesting project!
Question is, will the free NH2 of Tris interfere with the coupling to dinitrochlorobenzene?
If it works of course, then there's a nice NH2 for further derivatisation!

Rosco Bodine - 25-4-2007 at 16:48

I'll be optimistic about this proposed condensation of TRIS
with dinitrochlorobenzene , and say it should work under the same conditions as for ethanolamine .

Why let negative vibes sabotage theory in advance of an experiment .....making it sure to fail ?

Anyway the reaction looks good on paper and in theory
to me .

chemoleo - 25-4-2007 at 16:54

Maybe I missed this, you are saying that the condensation with ethanolamine has been demonstrated? Where? Sorry for overlooking this if that's the case.

Rosco Bodine - 25-4-2007 at 17:18

The condensation of ethanolamine with DNCB has been done .
It produces the precursor for pentryl .

In the pentryl thread we were talking about other
possible condensations of polyhydric alcohols with DNCB ,
and of course the amino-polyhydric alcohols ( like TRIS ) come into consideration there also ,
as being even more likely
condensates , due to the reactivity of the amino towards
the chlorine .....which is like a magnet , and should also
at the same time simplify the solvent requirement for the condensation reaction .

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

chemoleo - 25-4-2007 at 17:45

Yes you are absolutely correct. I only looked at the more recent posts, on the matter of ethyleneglycol, but not on the one of ethanolamine.
Yes, this should work very very nicely!
Axt's indeed got a project there!

So you are thinking of the following compound
DNB-NH(NO2)C(CH2NO3)3 if I am not mistaken?
I viewed the reaction according to Nicodems scheme in the pentryl thread - which is, the OH being coupled to the benzene ring.
I was wondering whether a triply substituted Tris would occur, i.e.
H2N-C(CH2O[DNB])3, similar to the condensation found with ethyleneglycol.

Rosco Bodine - 25-4-2007 at 18:16

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 :D

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]

Explosci - 18-5-2012 at 07:09

Condensing tris with diethyl oxalate followed by nitration gives an explosive that is comparable with PETN

Maniak - 18-5-2012 at 09:20

You probably just forgot to append reference for this statement so I'll do that for who's interested in details:

Thomas M. Klapötke and Norbert T. Mayr: Comparison of explosive performance and sensitivity of N,N'-bis(tris(nitratomethyl)methyl)oxamide with PETN, In proceedings of NTREM 2007, Czech Republic, Pardubice, 2007, p. 773-782

PS: you've got nice blog

Explosci - 19-5-2012 at 00:51

Bingo, that is it.