Sciencemadness Discussion Board - Diphoronpentaperoxyd & Chloroacetone

Diphoronpentaperoxyd & Chloroacetone

Organikum - 10-2-2004 at 04:02

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 - 10-2-2004 at 04:47

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

froot - 10-2-2004 at 07:23

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.

I go for chloroacetone

Organikum - 10-2-2004 at 10:30

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.

and

Organikum - 10-2-2004 at 11:30

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 - 10-2-2004 at 14:35

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)

Organikum - 11-2-2004 at 11:37

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 919 times

acid-catalyzed acetone condensation

Polverone - 11-2-2004 at 11:58

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.

tada!

Organikum - 11-2-2004 at 12:47

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?

funny stuff...

Organikum - 12-2-2004 at 07:25

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 - 12-2-2004 at 07:47

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?

Organikum - 12-2-2004 at 09:13

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 - 12-2-2004 at 11:18

DPPP float, AP sink, i think that it's the best way

vulture - 12-2-2004 at 13:37

DPPP should sink because it's density is higher than the density of water.

chemoleo - 12-2-2004 at 14:33

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?

Organikum - 12-2-2004 at 15:19

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.

PIC00002.JPG - 41kB

Awesome!

chemoleo - 12-2-2004 at 15:32

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!

Organikum - 12-2-2004 at 16:37

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 - 13-2-2004 at 17:43

This is it whilst filtering:

dppp1.JPG - 23kB

Organikum - 14-2-2004 at 14:21

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 - 14-2-2004 at 23:37

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

vulture - 15-2-2004 at 07:24

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.

Organikum - 15-2-2004 at 08:01

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 - 15-2-2004 at 08:41

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]

Organikum - 15-2-2004 at 09:57

! 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]

BASF - 16-2-2004 at 08:22

What a surprise... - The dead patient DPPP awakes!

I still have about 7 g of commercial phorone, and don´t know what it could be useful for.

However, on the contrary to Organikums statement, i was not able to peroxidize it.
- I tried an AP-like procedure, but it failed.

One problem surely is to find a suitable solvent. If anybody could assist with some advanced organic-chemistry-knowledge, i would still be loving to give it some additional tries on the micro-scale...

Maybe it is worth mentioning that a mixture of acetone/HCl/H2O2 (AP-proportions) behaved quite unreactive(no ppte!) with some dissolved phorone.

I doubt that a peroxide like DPPP could have a density much higher than 1.3 .
Create some peroxide-compounds in chemsketch, for example. While its density predictions seem completely off the range for high-densities(+2.0g/ccm) it seems quite reliable for low density-C,H,O-compounds. Look for other peroxides in the literature...they all have something in common: density below or around 1.3g/ccm.

vulture - 16-2-2004 at 09:07

You can always determine the FeSO4 content by titrating your FeSO4 with KMnO4 first. Commercial grade KMnO4 is mostly of reasonable purity because of it's applications (water treatment).

A slight difference shouldn't matter, because the difference between AP and DPPP should be 2 peroxide bonds per mole, which is a difference of 64g/mole.

my way to go

Organikum - 16-2-2004 at 11:33

The stuff is set for sublimation now and I will not touch it for some time.

After I decide it could be done, say all AP, TATP, etc. has sublimated away, I will wait for some days more and then do like vulture suggested and try to determine the peroxide content of the remaining substance.

So this indicates this being DPPP, I will not explode it but do some extensive tests for the properties of DPPP, like solubility etc. to get some data on this stuff as this is what we lack most I believe.

good idea?

BASF, perhaps you like to do some tests for properties on the phorone you have left, I believe there is almost no data available on this compound also....

BASF - 18-2-2004 at 01:34

Last year I bought 97% phorone at Sigma-Aldrich, which seemed to be the only supplier of small quantities.

The substance could easily be melted in a warm water bath and crystallized upon cooling(room temperature) in the form of long yellow(-green) needles.

Solubility tests:

-Insoluble in 30% HCl(i also tried heating)

-soluble in commercial acetone

-excellent solubility in 98% acetic acid

-Insoluble in commercial denaturated 98% ethanol(i also tried heating; absolute ethanol needed?)

(These are for RT)

Not that i am expert in peroxidation of unknown substances...i tried the following:

phorone(1ml) in 98% acetic acid (5ml=excess to prevent seperation of phases upon addition of the aqueous peroxidation-mix) and then adding a 1:1 mix (by volume) of 30%H2O2 and 30%HCl(total of 2ml) in a test tube.

It heated up strong (+50°C) and i repeated the whole procedure with proper cooling(ice bath), no ppte occured.

For the sake of it, i added some mL of water...no surprise, only the phorone left the solution.

The last experiment i did was to dissolve phorone in acetone and then tried to peroxidize both.
I was surprised that the phorone seemed to prevent the formation of the usual white AP-ppte.

Organikum: falls noch sinnvolle Ideen...es sind noch um die 7g da...

[Edited on 18-2-2004 by BASF]

[Edited on 18-2-2004 by BASF]

Rosco Bodine - 25-12-2004 at 18:23

Quote:

Originally posted by Organikum
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

Acetone Peroxide indeed does sublimate away gradually if it is exposed to free air circulation . However it behaves in this way similarly as does naphthalene crystals , the vapor pressure of the solid is so very low that if the escaping vapors are retained as a captive blanket over the crystals , the sublimation will almost cease . For example , if the crystals rest in a layer about 3 cm deep in the bottom of a tall container 20 cm tall , and the top of the container is firmly covered by a sheet of paper or closely woven cloth secured with a rubber band , the sublimation of AP will nearly cease from the weight of the column height of trapped vapor . A similar storage strategy
can be to use a tall poly jar or bottle with the closure deliberately left slightly loose or having a piece of string draped across the sealing surface to allow a very slight venting of vapor . AP can be stored for several years before evaporative loss of 50% occurs , by using this method of lightly covered but not sealed storage .

When AP is stored in a completely sealed container whose dimensions are more nearly equal in diameter and much lower in height , an interesting phenomena of sublimation and recrystallization occurs . The fine mesh crystals stored in a sealed container will gradually grow in size after a period of months storage in a sealed container , kept outdoors and exposed to the natural temperature changes which occur daily , until all of the crystals are on average like aquarium gravel or rock salt , with some crystals 6mm by 3 mm in size or larger . A soft poly food storage container with a sure sealing , non threaded cover should be used for any experiment to observe this phenomena of sublimation driven recrystallization . Easily characterized crystal samples can be obtained by this method for comparison of bona fide AP samples with
other unknown samples of similar materials , such as "suspected DPPP" .

So what was the eventual *finding* concerning your sample of suspected DPPP ?

[Edited on 26-12-2004 by Rosco Bodine]

Pyroz - 27-12-2004 at 21:24

Quote:

Originally posted by Organikum

My 2 cents:
Acetone + HCl doesnt polymerize so easily to phorone.

[Edited on 10-2-2004 by Organikum]

Really? It doesn't occur easily? The temperature around Acetone + HCL has to up around 110C for at least 40-50minutes. I leave the solution for an extra 2hrs without the heat on...the solution matures quickly.
You will see the colour change in that time from yellow to orange then to red and then it will finally go black. The reaction will continue until the solution thickens to motor oil consistancy and become Phorone diHydrogen Chloride. Its as pure as you can get.

Joeychemist - 28-12-2004 at 00:33

It has already been proven fact that HCl will cause acetone to polymerize to phorone very easily even without heat, it just takes longer, (about two weeks longer). This has been tried several times and proven successful every time. The reason we use the heat is to speed up the reaction. Another way to speed up the reaction is to bubble Cl through acetone.

[Edited on 28-12-2004 by Joeychemist]

Pyroz - 28-12-2004 at 00:42

..err, I'd be REALLY careful with adding straight Chlorine to Acetone. That make just makes chloroAcetone which from my understanding can't polymerize into a phorone -it is a base for nerve gas though--->

maybe i'm just out to lunch here--- I've never had success using this method.

Joeychemist - 28-12-2004 at 01:32

Chloroacetone is a form of tear gas IICR, and I was joking.

Tear gas ... nope, how about blister agent?

Matsumoto_Hideki - 28-12-2004 at 09:37

Chloroacetone is listed under chemicals used in WWI and a blister gas agent. It is also considered to be a carcinogen :mad:

Tweenk - 30-12-2004 at 09:27

How do you heat acetone to 110*C when it boils at 56*C? Is it a gas phase reaction?

Still wondering why the condensation of acetone happens in very acidic soln while all other aldol condensation reactions happen in basic ones...

[Edited on 30-12-2004 by Tweenk]

Pyroz - 30-12-2004 at 09:54

I'll explain:

--- when the temperature is raised up slowly over a long period of time--- acetone and HCL boiling point will raise once the reaction starts taking place. Past 65C ---and the mixture will begin to boil. At my last step to take off any water or left over HCL, I boil the solution at 110C using a salted water bath for 2 minutes---I reallise the the inside of the conatiner may only reach 85C or so.

Then I cool the mixture down for several hours

[Edited on 30-12-2004 by Pyroz]

[Edited on 30-12-2004 by Pyroz]

Rosco Bodine - 30-12-2004 at 10:25

Pyroz is correct . In the other thread you can read my observations about the reaction of 3 moles acetone with 2 moles HCl in a sealed bottle . A condensation of the acetone occurs spontaneously after mixing and the reaction is exothermic enough to boil away a lot of the acetone *if* it is permitted to escape . However , if it is in a sealed bottle it continues to react until after 45 minutes to an hour from the time of mixing , nearly all the acetone has been converted to a higher boiling point material so there is little to no unconverted acetone remaining . Then a second reaction takes place upon continued heating and a highly colored yellow material is produced . I have been deliberately performing this reaction slowly in an effort to observe definite "markers" for the progress of the reaction , to identify the point in the process where is the highest yield for the desired precursor for peroxidation to DPPP . Presently 3 distinct reaction development stages have been observed , even though the analysis of what is occurring is just getting started .

Please resize attached file

Polverone - 30-12-2004 at 22:49

Not only is it large and unwieldy to view, it takes up almost a megabyte of board space and will consume considerable time for people on dialup to download.