| Pages:
1
2 |
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
Diphoronpentaperoxyd & Chloroacetone
Dipheronpentaperoxyd.
After the german patent in the library.
Anybody actually tried this synth?
With success?
My 2 cents:
Acetone + HCl doesnt polymerize so easily to phorone.
I propose that a catalyst is needed twice in the synthesis as it is hinted in the formula drawing at end of the patent but stays unnamed in the
written part. For safety reasons I guess - this high-power explosive is much to OTC and easy to produce nevertheless. A metalchloride could do the
trick for the polymerization, FeCl3 for example, ZnCl2 etc. Maybee also ironoxide works....
...what catalyst for the dehydration? - any suggestions?
Ok. I tried it as written.
Result:
Seems to be a good way to chloroacetone. Stupid me added the H2O2 to fast and it boiled like mad and nearly everything was spilled.
This time I cried my eyes out.
Chloroacetone boiling hot spilled all over - cry baby cry.
Nothing precipitated from the rest left.
[Edited on 10-2-2004 by Organikum]
|
|
|
Blind Angel
National Hazard
Posts: 845
Registered: 24-11-2002
Location: Québec
Member Is Offline
Mood: Meh!
|
|
Look on this thread and this one too.
It has been discussed to death, but strangely you bring new by saying about chloroacetone and the use of catalyst
/}/_//|//) /-\\/|//¬/=/_
My PGP Key Fingerprint: D4EA A609 55E4 7ADD 8529 359D D6E2 33F6 4C76 78ED |
|
|
froot
Hazard to Others
Posts: 347
Registered: 23-10-2003
Location: South Africa
Member Is Offline
Mood: refluxed
|
|
I think that catalysts in this synthesis needs more research and could produce interesting results. Go for it. Obviously a few ways of doing it exist.
Send me a possible synth and I'll give it a try. Could we continue this discussion in the relevant thread and I'll stay tuned.
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 |
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
I go for chloroacetone
and that was the reason I opened the new thread.
As I discovered under tears of joy something what wasnt told up to now - that chloroacetone in big amounts can be formed by this way.
But I will edit the headline for making this clear. Sorry I see now that it is misunderstandable.
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
and
the first thread is endless and inconsistant.
Blast X says he made it, Philou says it is against basic chemistry rules.
BASF made it from bought phorone with success as it seems.
I fucked around a little bit and made heaps of chloroacetone - what nobody seems to have produced before whilst trying this synth what puzzles me.
Why did I try it?
Because I read (again) the patent in the library here and thought something must be wrong here.
I have seen two references for making chloroacetone by electrolytical methods which both work by mixing acetone and HCl and electrolysing the mixture
at RTm or above. Hey, if acetone would form phorone so fast and easy, how could those guys get (electrochemical) yields of chloroacetone up to 97% ?
Also the MERCK knows nothing from this quick and easy phorone production method - what is a hint - not more of course.
It is btw. no patent but only a pre-patent what says the method has not been approved by the patent office. I guess that the paper was published this
way to protect the pathway, there was no real patent filed for not being forced to publish the detailed working synthesis as would be necessary for
the official approvement.
I propose:
- There is a trick - or more tricks.
- Blast X made something but not (mainly) the wanted compound.
- It could be probably tweaked for chloroacetone production - quick and easy, I will be verifying this as soon I can work in my lab again.
- "Japan Drier" would be a catalyic mixture which might be woth a try.
Blind Angel: I read both threads and found nothing resembling my post.
Froot: Why dont research by your own if interested?
I brought up something VERY new here and I will not add this to a thread which resembles a tibetian prayermill (BASFs and a few other posts excluded)
Last not least: Anybody had a close look at the formulas drawing in the pre-patent?
There is two times "Katalysator" written, but the sign to the formula is different. And thats not by accidentl - thats a hint. And more: The
bastard uses "Teile" aka "parts" - this actually got out of fashion after the year 1900.
Somebody with good library access here interested in tracking this REALLY down?
|
|
|
Blind Angel
National Hazard
Posts: 845
Registered: 24-11-2002
Location: Québec
Member Is Offline
Mood: Meh!
|
|
I might have produced chloroacetone during my synthesis tryout, bu i didn't knew what is was and i still can verify the presence, though i still
have my solution which I then filtered and electrolysed for the fun (Its now green at room temp and yellow in freezing temp du to iron and copper
oxide)
/}/_//|//) /-\\/|//¬/=/_
My PGP Key Fingerprint: D4EA A609 55E4 7ADD 8529 359D D6E2 33F6 4C76 78ED |
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
Ok. I have left a clear liquid (from whats not got spilled) with a nice blob of an dark oil on the bottom which I suspect to be chloroacetone either
in its monochlorinated or dichlorinated state or monochloroacetone which is partially polymerized.
The oil is clearly a lachrymator thats sure.
I will filter the compound now over calciumcarbonate for to neutralize any left HCl, separate the oil, wash it with dH2O and dry it over CaCl2 as told
in patent
US2263010 (attached)
Attachment: chloroacetone_stabilisation.djvu (63kB)
This file has been downloaded 914 times
|
|
|
Polverone
Now celebrating 21 years of madness
Posts: 3186
Registered: 19-5-2002
Location: The Sunny Pacific Northwest
Member Is Offline
Mood: Waiting for spring
|
|
acid-catalyzed acetone condensation
| Quote: | My 2 cents:
Acetone + HCl doesnt polymerize so easily to phorone. |
But it does easily polymerize to something, or a mixture of somethings, yes? I haven't done this recently but I recall that strong acids (HCl)
and strong bases (NaOH, Ca(OH)2) made the acetone begin visibly discoloring in a few minutes at room temperature, and the color progressively became
darker over time, yellow to orange to dark red.
But the acetone and HCl were both paintstore-grade. Perhaps there's some impurities in these materials that cause the self-condensation to happen
faster than with pure materials.
PGP Key and corresponding e-mail address
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
tada!
I disclose you a secret Polverone:
It is mainly the light inducing polymerisation after my experience. Light and heat. So its cold and dark polymerisation takes almost not place, this
is valid for acetone as for chloroacetone.
And light doesnt say UV is needed.
If the HCl has an yellow tint it contains Cl2 and/or iron(chloride) as impurities.
At least the iron is a well known catalyst for inducing polymerisations.
btw. anybody an idea how to depolymerize the stuff again?
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
funny stuff...
To 250ml icecold 20% HCl was added 100ml of chilled acetone by an dropping funnel. This took about one hour. The mixture was cloudy but nit discolored
in any way. 50ml chilled H2O2 was added dropwise over half an hour.
A white fluffy precipitate fell out of the solution - it is in the lower part of the bottle - not as Blast X wrote on top.
I didnt proceed by now as I want to make clear how to handle this precipitate in the right way. Blast X wrote washing with warm EtOH - but as his
stuff swam on top and mine does not I want to ask - how to go on. I wont mutilate myself just because being to stupid to ask.
|
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
whoa I bet you must be shitting your pants... not knowing what to do with it! This is tension! Scared that it might blow up any second!
If I was you I would, first of all, LEAVE it in solution. But, as left-over HCl and other reactants/products might catalyse adverse reactions, I would
clean/wash it soon!
Easiest might be just to let the preciptiate settle, syphon off the above liquid, mix the preciptitate with distilled icecold water, and repeat - for
a few times.
Then do it with ethanol.
Take a small amount of precipiitate and allow it to dry on a piece of paper.
Set fire to it, and see what happens with the precipitate!
Anyway, i guess the bigger problem is to discern it from AP - how do you know this isn't what you got?
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
Huh?
My pants are still clean.
I left it in solution.
I added a reasonable amount of dH2O.
Decanted, added, decanted....
Yes and thats my question: How to separate AP and Diphoronepentaperoxide?
I thought the EtOH wash would take care of this?
Wrong - right - dont know?
Dry it, press it, send it to vulture? 
|
|
|
Blind Angel
National Hazard
Posts: 845
Registered: 24-11-2002
Location: Québec
Member Is Offline
Mood: Meh!
|
|
DPPP float, AP sink, i think that it's the best way
/}/_//|//) /-\\/|//¬/=/_
My PGP Key Fingerprint: D4EA A609 55E4 7ADD 8529 359D D6E2 33F6 4C76 78ED |
|
|
vulture
Forum Gatekeeper
Posts: 3330
Registered: 25-5-2002
Location: France
Member Is Offline
Mood: No Mood
|
|
DPPP should sink because it's density is higher than the density of water.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
|
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
Well I don't think you can use this property (whether it floats up or down) as a means of discerning AP from DPPP.
Ever tried making HMTD? At a density of 1.57 g/cm^3, it still floats up to the top of the solution. This is because bubbles (O2?) adhere to HMTD
crystals, thus decreasing their density. You may have noticed that once HMTD was washed, it nicely sinks to the bottom in H2O.
Organikum, when you did your reaction, did gas bubbles evolve at all? I.e. when you stirred the mix? That is, if you dared stirring
it 
Else, do you have a Mass Spec? That way you could easily tell if you got the right stuff
Could you list the concentrations of the reactants, please, too?
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
Sorry forgot the H2O2 concentration: It was 30%.
As the HCl was added to the acetone (98,9% min) this mixed by itself - the H2O2 was droppped into the chilled mixture as told over a longer time - as
no layers formed, mixing seemed unnecessary to me. The high-tech reaction vessel (2-liter PET bottle) was chilled all time - no feelable warming up
occured.
After the crystals precipitated the bottle was swirled sometimes - I dont think the stuff in covered with water will easily explode - it is kept cold
all time also.
Attached a picture.
|
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
Awesome!
I do think you are on to something here!
A question first: Once you started adding H2O2 to your HCl/acetone, did any Cl2 evolve? For that matter, did any gases evolve at any point during the
reaction?
If not, that means all your HCl must have reacted! that means, the precursor for making AP is absent (which is standard acetone) - and hence the
product you have will NOT be AP - so probably DPPP!
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
No gas evolved at no time during the reaction. Absolutely no bubbles and no smell.
I blame this on the low temperature, the slow addition of the H2O2 and time. There was no hurry, never.
If this works out to be DPPP it would say that the polymerisation of acetone to phorone by HCl takes favorably place at low temperatures.
This would also be interesting news for my chloroacetone by electrolysis experiments of course.
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
This is it whilst filtering:
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
The precipitated white substance is now spread out for drying.
I will recrystallize it from IPA as soon it has dried out completely.
Question:
Is the information correct that AP sublimates away and breaks down by time as Blast X wrote?
Does light fasten the breakdown?
thanks
ORG
|
|
|
froot
Hazard to Others
Posts: 347
Registered: 23-10-2003
Location: South Africa
Member Is Offline
Mood: refluxed
|
|
The first and last time I made AP I left a little in the sun to dry (safe distance ofcourse  ) through the course of the day it never detonated but disappeared, evapourated-vanished! This was a while ago and I did not have much info
on it's properties so I had to find out myself. ORG, if your product does not have this unwanted characteristic, you may have a winner.
Put a tiny amount in a very warm place and see what happens.
Well done so far
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 |
|
|
vulture
Forum Gatekeeper
Posts: 3330
Registered: 25-5-2002
Location: France
Member Is Offline
Mood: No Mood
|
|
How about weighing the precipitate, reacting it with excess FeSO4 and titrate the remaining solution with acidified KMnO4?
Assuming that every mol of peroxide would oxidize one mole of Fe2+ to Fe3+, it should be possible to determine the peroxide content.
Not quite safe, but in a solution of sufficient volume this shouldn't be a problem.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
Recrystallization from hot IPA - crashed with cold water.
Dear vulturius: For a correct determination of the weight of a part of the precipitate I would have to get it dry. How to get it dry without the AP
sublimating away?
[Edited on 15-2-2004 by Organikum]
|
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
Maybe we should start to collect the known properties of DPPP, and AP.
What is known about there solubilities (water, toluene, ether, pyridine, IPA, etc etc?)
Sublimating behaviour?
Content O-O per molecule?
Density?
Chemical stability?
and so on....
If we can find a differnce in solubilities, then it should be easy to determine whether it's AP or DPPP. Or, as vulture pointed out, titrate the
OO bonds for a known amount of AP/DPPP. I suspect this won't be trivial though.
PS Org, AP doesnt sublimate THAT fast!!! Just dry a small amount, weigh it and put it into solution right away. The problem there is though... do you
have a scale that can measure milligrams? Cus if you work with larger amounts (where it might be easier to determine the weight), the handling danger
increases proportionally
[Edited on 15-2-2004 by chemoleo]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
! ATTENTION !
Usual filterpaper gets rapidly eaten by this stuff what makes filtration difficult!
The water is neutral to litmus btw. so it is not on remaining acid - which was thorougly neutralized before)
Damn, I have to get me some glassfibre-filters soon.....
Because of the cellulose particles I suggest to be in the AP/DPPP now I redissolve it in warm IPA and try rapidfiltering it at the pump through a
glasswoolplug7filter unit to get the shit out.
Addon:
I didnt want to take vultures suggestion down, but for me I see some drawbacks:
1. There will be some losses by sublimation causing wrong results.
2. I dont have reagent grade FeSO4 and KMnO4 - so this can be a source of failure.
3. It may be dangerous.
4. I am in no hurry.
After I redissolved and refiltered the stuff it is now set for evaporation and I believe it may be the best way just to wait.
What will be left in some days should be DPPP - if nothing is left I got rid of the AP this way - no chance for me to do unhealthy experiments with
it.
ok?
[Edited on 15-2-2004 by Organikum]
|
|
|
| Pages:
1
2 |
![[*]](images/xpblue/default_icon.gif){kind=icon}
