| Pages:
1
2
3 |
KABOOOM(pyrojustforfun)
Hazard to Others
Posts: 254
Registered: 12-10-2002
Location: Iran (pseudoislamic dictatorship of)
Member Is Offline
Mood: exuviating!
|
|
| Quote: | | 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
| Quote: | | 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.
| Quote: | | 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:
| Quote: | | 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>.
| Quote: | 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
| Quote: | 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
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
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 
|
|
|
KABOOOM(pyrojustforfun)
Hazard to Others
Posts: 254
Registered: 12-10-2002
Location: Iran (pseudoislamic dictatorship of)
Member Is Offline
Mood: exuviating!
|
|
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
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
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]
|
|
|
KABOOOM(pyrojustforfun)
Hazard to Others
Posts: 254
Registered: 12-10-2002
Location: Iran (pseudoislamic dictatorship of)
Member Is Offline
Mood: exuviating!
|
|
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:
(HOCH<sub>2</sub><sub>3</sub>C<font
color=red>-NH<sub>2</sub></font> + Cl<sub>3</sub>CH + 3KOH<s> ></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> ></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> ></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>
conclusion: acetaldehyde isn't really hard to make!
|
|
|
froot
Hazard to Others
Posts: 347
Registered: 23-10-2003
Location: South Africa
Member Is Offline
Mood: refluxed
|
|
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.
(NO2)3C6H2OH(aq)+NH2(CH2OH)3(s)=x(l)
x(l)+HCHO(aq)=?(s)
Any ideas?
We salute the improvement of the human genome by honoring those who remove themselves from it.
Of necessity, this honor is generally bestowed posthumously. - www.darwinawards.com |
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
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??
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
froot
Hazard to Others
Posts: 347
Registered: 23-10-2003
Location: South Africa
Member Is Offline
Mood: refluxed
|
|
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.
We salute the improvement of the human genome by honoring those who remove themselves from it.
Of necessity, this honor is generally bestowed posthumously. - www.darwinawards.com |
|
|
froot
Hazard to Others
Posts: 347
Registered: 23-10-2003
Location: South Africa
Member Is Offline
Mood: refluxed
|
|
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.
We salute the improvement of the human genome by honoring those who remove themselves from it.
Of necessity, this honor is generally bestowed posthumously. - www.darwinawards.com |
|
|
KABOOOM(pyrojustforfun)
Hazard to Others
Posts: 254
Registered: 12-10-2002
Location: Iran (pseudoislamic dictatorship of)
Member Is Offline
Mood: exuviating!
|
|
heptryl!
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="http://groups.google.ca/groups?q=heptryl&hl=en&lr=&ie=UTF-8&selm=dqOY4.12378%24793.772578%40bgtnsc05-news.ops.worldnet.att.
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)
Hazard to Others
Posts: 254
Registered: 12-10-2002
Location: Iran (pseudoislamic dictatorship of)
Member Is Offline
Mood: exuviating!
|
|
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> ></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> </s><u><sup>H2SO4</sup></u><s> ></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> ></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)
|
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
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]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
froot
Hazard to Others
Posts: 347
Registered: 23-10-2003
Location: South Africa
Member Is Offline
Mood: refluxed
|
|
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]
We salute the improvement of the human genome by honoring those who remove themselves from it.
Of necessity, this honor is generally bestowed posthumously. - www.darwinawards.com |
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
Anhydro-Anneaheptite (an off topic sideshoot)
| Quote: |
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
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
froot
Hazard to Others
Posts: 347
Registered: 23-10-2003
Location: South Africa
Member Is Offline
Mood: refluxed
|
|
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?
We salute the improvement of the human genome by honoring those who remove themselves from it.
Of necessity, this honor is generally bestowed posthumously. - www.darwinawards.com |
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
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!
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
KABOOOM(pyrojustforfun)
Hazard to Others
Posts: 254
Registered: 12-10-2002
Location: Iran (pseudoislamic dictatorship of)
Member Is Offline
Mood: exuviating!
|
|
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
International Hazard
Posts: 2893
Registered: 20-5-2002
Location: Brussel
Member Is Offline
Mood: Bis-diazo-dinitro-hydroquinonic
|
|
Chemo,
simply read my U2U and edit it here as proposed.
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)
|
|
|
Nick F
Hazard to Others
Posts: 439
Registered: 7-9-2002
Member Is Offline
Mood: No Mood
|
|
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
Hazard to Others
Posts: 347
Registered: 23-10-2003
Location: South Africa
Member Is Offline
Mood: refluxed
|
|
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.
We salute the improvement of the human genome by honoring those who remove themselves from it.
Of necessity, this honor is generally bestowed posthumously. - www.darwinawards.com |
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
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.
Respectively:
O2NO-CH2-CH2-NH3NO3
(O2NO-CH2-CH2-)2NH2NO3
(O2NO-CH2-CH2-)3NHNO3-
In your case with tris you will get a much better compound
(O2NO-CH2-)3C-NH3NO3
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
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
Chemical Peach
Harmless
Posts: 9
Registered: 15-6-2003
Location: Devon, England
Member Is Offline
Mood: alright, i supp
|
|
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
International Hazard
Posts: 2893
Registered: 20-5-2002
Location: Brussel
Member Is Offline
Mood: Bis-diazo-dinitro-hydroquinonic
|
|
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 .
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)
|
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
Experiment
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.
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
Axt
National Hazard
Posts: 795
Registered: 28-1-2003
Member Is Offline
Mood: No Mood
|
|
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 1487 times
|
|
|
| Pages:
1
2
3 |
![[*]](images/xpblue/default_icon.gif){kind=icon}
