Sciencemadness Discussion Board

Diphoronepentaperoxide (DPPP)

 Pages:  1  ..  7    9  

Chris The Great - 6-2-2005 at 18:09

Damn, somehow got it to submit accidentally...anyway editing in my post now....

[Edited on 7-2-2005 by Chris The Great]

So, I filtered out my "DPPP" last week, and it was dry enough to do some tests on this weekend.

Filtering was somewhat problematic for me, I lost alot of the product from the A batch.
The A mixture was poured into the filter, and distilled water was used to get the rest of the crystals out of the jar. A small amount of sodium bicarbonate solution was poured onto it, however there was no acidity, so I stopped pouring it and rinsed it again with distilled water. Then, it was rinsed with methanol, which caused about a third of the product to go through the filter! I was somewhat upset, so rinsed again with distilled water and then with isopropyl alcohol (99%). The isopropyl went through the filter very slowly however it did not take a bunch of crystals with it as the methanol did. I squeezed the rest of the isopropyl alcohol out of the filter by hand and put it in a small dessicator.
The B mix was dumped into the filter and distilled water was used to get the rest of the crystals out of the jar. A large amount of sodium bicarbonate solution was required to nuetralize, and it foamed a large amount during nuetralization. After the product stopped foaming when sodium bicarbonate solution was added, I rinsed it with distilled water and then 99% isopropyl alcohol. After most of the alcohol had gone through the filter I squeezed out the rest by hand and put it into another dessicator.

This weekend I had time again, so I went out to check on the "DPPP". It has dried completely in the dessicator, and both the A and B mix seemed to be exactly the same thing. A few deflagration tests also gave that impression.

About 1 gram of "DPPP" in the form of many small chunks was ignited on a spoon, with a very nice think black smoke ring being formed. I then deflagrated ~1 gram of each the A and B mixtures on a piece of wood. Both burned very quickly, seemingly more quickly then AP, with think black smoke being formed each time.
A then took a pill sized piece, also approximatly 1 gram, perhaps a very small amount more, and had it DDT with a very large amount of force. I had put in hearing protection for these tests, as I didn't know exactly how easily it was to detonate, so my ears only had a very slight ringing that quickly faded away. Although it was very loud, and I felt a substantial shockwave hit my hand which was in a leather glove about 4 inches away, there was only a small 1cm dent on the soft particle board. No smoke was produced, and the distinctive smell of detonating AP was not smelt.
I detonated a small <0.5 gram AP initiator I made to test, and the smell was very strong, indicating that what I have was definatly not AP.

I then tried dissolving it in toluene to check the moisture content, as Rosco had found his full of water. About 3 grams where dissolved in 25mL toluene, and absolutly no water was seen. So, whatever it is, it's pretty pure.

I am hopefully going to try peroxidizing my precursor prepared with sulfuric acid instead of hydrochloric acid tommorrow.

[Edited on 7-2-2005 by Chris The Great]

Atom - 7-2-2005 at 09:12

Yeah I just tried to make some but it failed. I read you can make Phorone when using sulfiric acid 96 %. So I tried to make some but it had a runaway of some sort. Theres this distinct smell in the whole house now. Does anyonen know what happenend. By the way I used 5 ml SA and 5 ml acetone. With no cooling.

Hehe uhm I just made it with cooling and everything works just fine.:D

[Edited on 7-2-2005 by Atom]

Mumbles - 7-2-2005 at 14:47

No one is 100% sure on the phorone synthesis as of yet. What you made mostly is probably mesitylene. If the liquid turned orange/red/black it is mesitylene at least party. The proceedure that you took is the exact one I take for mesitylene when I need it in a hurry.

Chris The Great - 7-2-2005 at 20:34

Wow, didn't you read my post about using 96%+ H2SO4 sulfuric? I had mine explode using less acid to acetone ratio than you.

I found 14mL H2SO4 for 55mL acetone worked well, the reaction sustains itself to completion in about ten minutes, when the jar is sealed and mostly empty. This allows the acetone vapour to reflux by condensing on the sides of the jar. In this case it was a 250mL jar, I wouldn't try putting any more liquid in or the pressure may rise too quickly and too high.

I am going to try peroxydizing my mixture soon, I haven't had a chance today, but hopefully tommorrow, to confirm that the method using sulfuric acid works.

Also, I recently aquired approximatly 25 to 30 pounds of lead. While a trauzl block typically is 165 pounds or so, I can probably make a smaller one and test some explosives with well known block test ratings, and see what I get with this. While the results will definatly not be conclusive, it might establish a ballpark figure.
I can see problems however, with such a "small" block I would need to use small amounts of explosives, so incomplete detonation may occur.

Hot Toluene is excellent recrystallization solvent

Rosco Bodine - 7-2-2005 at 21:22

When toluene is heated in a sealed jar and then the crude AP / DPPP is is added ,
it literally will form a syrup which is two thirds or more by weight the dissolved organic peroxide . Any water trapped in the fluffy crude crystals separates and rises to the top of the hot solution where it can be decanted or ladled off . If the hot saturated toluene solution is allowed to cool slowly while being stirred slowly on a magnetic stirrer , gritty anhydrous crystals of much improved density gradually precipitate . I tried adding denatured alcohol to the toluene solution hoping that this would speed the precipitation , but this was unsuccessful because the alcohol / toluene mixture exhibited a cosolvent effect and no organic peroxide precipitated . The alcohol did form an upper layer containing the water in solution , along with a fair amount of the organic peroxide also in solution . Upon evaporation , this separated moist alcoholic solution also deposited gritty crystals of much improved density .

Atom - 7-2-2005 at 23:51

What do you use mesitylene for then?
'Cause I just tried to peroxidise this but it didnt work. There were just these two seperate layers and they wouldn't mix properly. One turned green and the other one just stayed oily sticking to everything it could.

And I thought mesitylene is colourless but this has a deepred colour.

[Edited on 8-2-2005 by Atom]

Quince - 11-2-2005 at 23:45

So, is this thread dead or what? And what happened to Rosco, he hasn't been on the board for like three days? Maybe some accident in the lab? :o

Rosco Bodine - 12-2-2005 at 05:41

Still around , just not much time for experiments lately . Been too busy otherwise . The hot toluene recrystallization of a mixed product produced what appears to be a single material . From 100 ml of toluene heated
and then saturated while hot with the organic peroxide , 75 grams of the anhydrous crystals were obtained when the solution cooled . The solution was stirred slowly using a magnetic stirrer during the several hours it was cooling ,
and gritty cystals of improved density were obtained , which dried much more quickly than crystals from aqueous solution .

BASF - 12-2-2005 at 06:53

Hello!

A few hints: color changes are a bad indicator for purity or a specific product in org. chem....for example: you can have a 99% pure product which is colourless in the pure state and it can eventually be anything from red - yellow- orange or black -coloured in your finished batch.

I´d propose adding 1/2 g of fine activated charcoal to decolourize the solution and stirring/warming for 1-2 hours.

Another thing: somebody mentioned using hot toluene as recrystallizing solvent.....isnt that hazardous? - toluene boils at ~110°C....acetone peroxides (which are most likely major products when following the mackowiak-patent) explode at 130-140°C, no?

Imagine using boiling xylene(dimethylbenzene, SP ~140°C) instead.....more than likely....kawumm.....

[Edited on 12-2-2005 by BASF]

[Edited on 12-2-2005 by BASF]

thedestroyer5150 - 12-2-2005 at 15:10

Has anyone tried a synth with 100% HCL? That water content could be inhibiting DPPP production.

Joeychemist - 12-2-2005 at 15:39

There is no such thing as 100% HCl, the highest I have seen is about 40%.:P;)

$0meb0dy - 12-2-2005 at 15:54

Maiby he means bubbeling HCl trough the aceton.

thedestroyer5150 - 12-2-2005 at 16:47

I mean concentrating it.

The_Davster - 12-2-2005 at 17:05

You cannot have 100% liquid HCl, at least not at room temperature. Pure HCl is a gas, the common forms of HCl are aqueous solutions of it.

And if you want to concentrate it how would you do that? Boiling? Just remember if you attempt to concentrate HCl by boiling that gasses are less soluble in water at higher temperatures. So boiling it would not work.

The only way possible that you could use HCl without water is to bubble the anhydrous gas into the acetone.

thedestroyer5150 - 12-2-2005 at 22:45

Cool gaseous compression like liquid oxygen. Or dry ice. But you're right, 100% can't really be done (for this purpose), but a higher concenteation of about 60-80% can.

Atom - 13-2-2005 at 07:32

Can't one concentrate HCl by freezing the water and pour the remaining liquid ( a higher percentage HCl ) in a flask?
Just like you can with H2O2

Freezing HCl

sparkgap - 13-2-2005 at 09:18

The attached graph may be of interest.

Meaning, concentrating HCl might be difficult this way.

edit: picture from http://www.resistoflex.com/hci_graphs.htm

sparky (^_^)

[Edited on 13-2-2005 by sparkgap]

hcl_freezing.jpg - 26kB

Atom - 13-2-2005 at 09:30

I cant see why it is difficult, 'cause water just freezes at 0C and you can get as much water out of your solution as wanted. Cant you?

Rosco Bodine - 13-2-2005 at 15:46

Quote:
Originally posted by BASF Another thing: somebody mentioned using hot toluene as recrystallizing solvent.....isnt that hazardous? - toluene boils at ~110°C....acetone peroxides (which are most likely major products when following the mackowiak-patent) explode at 130-140°C, no?
The toluene was heated in a sealed jar which was sitting in a hot water bath at 90 C .
I used a teflon rare earth stirbar and a solid teflon stirring rod for manual stirring sometimes when the sludge of crystals would solidify so much on standing for a few minutes as to stall the stirbar in the mixture which was almost as stiff as wet sand . How safe it is to do this I don't really know . It is not a mixture which I would subject to rough handling with glass on glass , but I supposed it would probably be okay with teflon to glass .
And the temperature wasn't kept high for very long , just sufficiently to get everything in solution .

BASF - 13-2-2005 at 18:19

This was found by typing in "mackowiak" (inventor of patent) in scifinder.....

Note that this is the ONLY hit using the name of the inventor.
(acronym and also Beilstein Crossfire`s drawing function: no hits)

Bibliographic Information

Explosive diphoron pentaperoxide. Mackowiak, Wolfgang. Ger. Offen. (1971), 4 pp. CODEN: GWXXBX DE 1951660 19710422 Patent written in German. Application: DE 69-1951660 19691014. CAN 74:143985 AN 1971:143985 CAPLUS

Patent Family Information

Patent No. Kind Date Application No. Date
DE 1951660 A 19710422 DE 1969-1951660 19691014

Priority Application
DE 1969-1951660 A 19691014


Abstract

The H2O-insol. title compd. (I) of 9000 m/sec detonation velocity and 200 explosion temp., useful for blastings in mines and quarries or for military purposes, was prepd. with 90% yield from 1:1:2 Me2CO, HCl, and H2O2. I has the formula C18H26O2(O2)5.

Patent Classifications

IPC: C07D; C06B.

Indexing -- Section 50 (Propellants and Explosives)

Explosives
(diphorone pentaperoxide)

32619-19-5
Role: USES (Uses)
(explosives)




Registry Number: 32619-19-5

Formula: C18 H26 O12

CA Index Name: 1,2-Dioxolo[4,3-c][1,2]dioxepin-8(3H)-one, 6,6'-[dioxybis(methylene)]bis[tetrahydro-3a,6-dimethyl- (9CI)

Other Names: Diphorone pentaperoxide

-- Properties --

Calculated
Property Value Condition Note
Bioconc. Factor 17.1 pH 1 (1) ACD
Bioconc. Factor 17.1 pH 4 (1) ACD
Bioconc. Factor 17.1 pH 7 (1) ACD
Bioconc. Factor 17.1 pH 8 (1) ACD
Bioconc. Factor 17.1 pH 10 (1) ACD
Boiling Point 457.0±45.0 °C Press: 760.0 (1) ACD
Torr
Enthalpy of Vap. 71.71±3.0 kJ/mol (1) ACD
Flash Point 197.4±51.8 °C (1) ACD
Freely Rotatable Bonds 5 (1) ACD
H acceptors 12 (1) ACD
H donors 0 (1) ACD
Koc 265 pH 1 (1) ACD
Koc 265 pH 4 (1) ACD
Koc 265 pH 7 (1) ACD
Koc 265 pH 8 (1) ACD
Koc 265 pH 10 (1) ACD
logD 1.92 pH 1 (1) ACD
logD 1.92 pH 4 (1) ACD
logD 1.92 pH 7 (1) ACD
logD 1.92 pH 8 (1) ACD
logD 1.92 pH 10 (1) ACD
logP 1.924±0.967 (1) ACD
Molar Solubility Sparingly Soluble pH 1 (1) ACD
Molar Solubility Sparingly Soluble pH 4 (1) ACD
Molar Solubility Sparingly Soluble pH 7 (1) ACD
Molar Solubility Sparingly Soluble pH 8 (1) ACD
Molar Solubility Sparingly Soluble pH 10 (1) ACD
Molecular Weight 434.39 (1) ACD
Vapor Pressure 1.54E-8 Torr Temp: 25.0 °C (1) ACD

Notes:
(1) Calculated using Advanced Chemistry Development (ACD/Labs) Software Solaris V4.76 ( 1994-2005 ACD/Labs)

-- Resources --

References: ~1

STN Files: CAPLUS, CA

Deleted Registry Number(s): 11067-76-8

Database: REGISTRY


Additional info calculated with ACD-labs demo-version: density=1,3g/ccm (=> thus high Vdet very unlikely!!)

Note the low vapour-pressure. (=> thus rapid sublimation very unlikely!!)

My conclusion is that Wolfgang Mackowiak did eventually only file a patent without ever publishing additional scientific work on the subject ...... this is at least very strange...

[Edited on 14-2-2005 by BASF]

Geomancer - 14-2-2005 at 17:05

Personally, I think the patent is bunk. Just for fun though, let's advocate this devil.

First there is the illustration Mega found. If not traceable back to the original patent, it might mean the compound can be made, even if not by the process in the patent.

Second, we know the first step (aldol to phorone) happens, under the right conditions. This is well documented. So, the (hydro)chlorination is the sticking point.

But this is a free radical reaction right? That's why the H2O2 is labeled as a catalyst. It provides the source of the radicals that cascade to chlorinate the thing. Note that one of the locations substituted is allylic, and so particularly susceptable to this kind of thing. And that leads us to the third point: no one has taken steps to insure the generation of these radicals. I think that a catalyst for the decomposition of the peroxide has been ommited from the patent. My knowledge of this type of chemistry is now expended. Perhaps Iron or Manganese will work?

The peroxidation mechanism is highly unlikely

Rosco Bodine - 14-2-2005 at 18:41

to occur in a manner decribed by the patent even if you get past the fact that the chlorinated precursor doesn't form as proposed by the patent reactions . Usually when hydrogen peroxide reacts , it gives up only one oxygen , forming water as a byproduct , something of a "condensation reaction" which adds the
"active oxygen" from the hydrogen peroxide to an already present oxygen residing on the organic compound , thereby forming an "organic peroxide" .

However in the patents proposed reactions , the complete pair of oxygens is
split off from the two hydrogens of the hydrogen peroxide , and the pair of oxygens with peroxidic bond intact is then added to the chlorinated organic compound , occupying the sites of chlorination preferentially to the chlorine which is split off and further reacts with the hydrogen pair from the cleaved hydrogen peroxide to form two HCL's .

This entire scenario would be far fetched even for singlet ions to participate in such a reaction , and for such a reaction to proceed by involvement of * PAIRS * of
hydrogens , oxygens , and chlorines is just preposterous on its face .

Joeychemist - 14-2-2005 at 19:21

Maybe this compound could be more easily attained through use of a commercial ozone generator? If the patent was correct in preparing the right precursor (probably not) than ozone could be a plausible route to venture, no? It could provide the intact -O-O- to take the place of the Cl moles, but then again the patent would have to be totally right about the chlorinated precursor for that to work.

Chris The Great - 14-2-2005 at 22:17

Quote:
Originally posted by vulture
Painkilla made a good suggestion of summarizing this topic to get rid of all bloated speculation, but unfortunately I don't have much time on my hands right now, so therefore I'm asking if there are a few members who'd like to condense this into a new thread.


Just though that yes, I'm working on it :P I started last weekend, and have gone through 16 pages of this thread, finding the important pieces to be transferred to a summarized version, although all experimental observations etc will remain intact, I'll just edit them to make them contain info from later posts and fix alot of punctuation and spelling mistakes.

There is a very large amount of very useful experimental data that will be VERY useful once it is transferred to a organized form without a large amount of bickering, argueing and useless information (in this case) such as speculation on practical applications that fills a very large amount of this thread's content.

Should I assemble this into a thread by posting several replies to a new topic summing up this thread or make a pdf out of it? It would be handy to have a summarized thread on the forum in my opinion.

Geomancer - 15-2-2005 at 12:03

The peroxidation is plausible. I looked about in the library and it seems this kind of thing happens all the time. A large book entitled "Organic Peroxides: Volume 1" specificly says that ROOR can be made from 2 RX with 1 H<sub>2</sub>O<sub>2</sub>. Conditions aren't mentioned. March seems to say it happens in basic solution. Reagents for Organic Synthesis shows an intramolecular peroxide formation knocking out Bromine, using H<sub>2</sub>O<sub>2</sub> and Silver Triflouroacetate. Many of these reactions proceed by ionic means, though. If the peroxidation is ionic, I don't yet see why it doesn't add to the ketone as well. CuCl might be advantagious at some point.

No, I will not give primary references. I don't have much time and my library isn't all that great for chemistry anyway.

Dodoman - 15-2-2005 at 15:09

I asked a Phd at my university the other day to help point me in the right direction. He told me that the information in most chemical patents are not written in details (may even contain missleading information) so that noone would replicate it without direct contact with the inventor.

He also told me that phorone is most unliky to form due to the reaction of acetone with HCl but would rather produce mesytyl oxide. I looked this info in Vogel and it sais that the oppesit is correct. Any way the Phd told me that phorone is most likly to be produced from a hydroxide with acetone rather than HCl with acetone.

So I got this strange idea. Why not make phorone by the reaction of NaOH with acetone then neutralize the solution with HCl and add the equvelent amount to form the phorone chloride stated by the patent and then peroxidise that.

I'd very much like to know your thoughts on that Rosco. Personelly I like that idea and would probably try the synthesis by this week end.

PainKilla - 15-2-2005 at 15:12

They both lead to the same product. I had a batch of NaOH/acetone and they both formed the red liquid, with same properties, and same smell. It got me pissed off so I dumped it. DPPP is not possible via the current method.

Dodoman - 15-2-2005 at 15:22

Quote:
Originally posted by PainKilla
They both lead to the same product. I had a batch of NaOH/acetone and they both formed the red liquid, with same properties, and same smell. It got me pissed off so I dumped it. DPPP is not possible via the current method.


Thats very strange :o I thought you would end up with a ppt.

This means that the red liquid (I thought was phorone chloride) is not phorone chloride since no chlorine is involved in the reaction.

Thats disappointing :(

PainKilla - 15-2-2005 at 15:33

..... Are people missing posts or moreover pages? It was obvious that no Ph-Cl was made when I made "DPPP" using H2SO4....

Rosco Bodine - 15-2-2005 at 20:10

Quote:
Originally posted by Dodoman
I asked a Phd at my university the other day to help point me in the right direction. He told me that the information in most chemical patents are not written in details (may even contain missleading information) so that noone would replicate it without direct contact with the inventor.
Quote:
That is total bullshit . If anything , patents for compositions of matter and chemical processes are about the most detailed disclosures you will find in the patent literature . They have to be detailed and full disclosures in order to have any legal claim to the things being covered by the patent . So like other legal documents the patents tend to be filled with fine print that covers every conceivable variation so the patent can hold up to legal scrutiny or challenges from copycats who would try to steal the technology and claim it is their own invention .
Quote:

He also told me that phorone is most unliky to form due to the reaction of acetone with HCl but would rather produce mesytyl oxide. I looked this info in Vogel and it sais that the oppesit is correct. Any way the Phd told me that phorone is most likly to be produced from a hydroxide with acetone rather than HCl with acetone.
Phorone is not the object of the synthesis , neither is mesitylene . I would be more interested
in the triacetone dialcohol as a precursor .
Quote:

So I got this strange idea. Why not make phorone by the reaction of NaOH with acetone then neutralize the solution with HCl and add the equvelent amount to form the phorone chloride stated by the patent and then peroxidise that.
Phorone is not what you want to produce . What you want to make is triacetone dialcohol , and then phorone dihydrochloride from reaction of the triacetone dialcohol with HCl . All of this presuming of course that you still believe that somehow the patent describes reactions which take place but under more complex conditions than are disclosed by the patent . You are presuming that maybe a trade secret process is involved , and the patents description is an oversimplification .
Quote:

I'd very much like to know your thoughts on that Rosco. Personelly I like that idea and would probably try the synthesis by this week end.
Okay try this theory . Acetone is converted in the cold and in the presence of NaOH to triacetone dialcohol in 10% yield according to a patent process , and isolated by distillation , the unreacted acetone recycled . The triacetone dialcohol is then converted to phorone dihydrochloride by reaction with HCl gas , or by reaction with aqueous HCl , whichever method works . The phorone dihydrochloride is then chlorinated with gaseous chlorine , and then peroxidized .
When you have gone through all of this elaborate work you probably will not have the desired compound , and will be saying to yourself that the trouble and expense would have been effort more rewarded in synthesis of something more straightforward . You see the appeal of the alleged " DPPP " was ease of synthesis . When you remove that appeal by having to resort to extraordinary methods to accomplish the synthesis , well how much appeal actually remains for the
" DPPP " in comparison with more well known and absolutely proven materials which are made straightforwardly by simpler methods ?

Geomancer - 16-2-2005 at 18:02

What intrigues me about this proposal is that it looks so unlikely. Normally when crackpots come up with something, it at least has some intuitive appeal. What in God's name caused M. to ever even think that something like this could happen? Wouldn't he have at least considered the possiblity that the chlorines might not have, you know, read the instructions he gave them? He does have some chemical knowledge after all.

Also, if you're looking for phorone (and I think that's what you want if anything like the descibed process is to happen) you want acid conditions. These are well known to do it. (Many books mention this, none bother to give real references, so it must be common knowledge, right?)

Rosco Bodine - 16-2-2005 at 19:27

Quote:
Originally posted by GeomancerWhat in God's name caused M. to ever even think that something like this could happen? Wouldn't he have at least considered the possiblity that the chlorines might not have, you know, read the instructions he gave them? He does have some chemical knowledge after all.
Some , yeah , but not enough .
In chemistry , stoichiometry is where either the rubber meets the road ,
or the flight of fancy crashes and burns .
Somebody should toss Wolfgang a fire extinguisher so he can put himself out :D

Ok then...now what

Mickhael - 18-2-2005 at 21:58

I've been pretty silent of late, mostly because of my work schedule. However I just wanted to say...that even though this supposed DPPP is not going to result in a high VoD explosive...nor anything super fantastic perhaps, we still have a synth for making a AP similar primary, with very high yeilds....fairly simply, this is worth something is it not? Also if simple recrystalization to rid it out water and make smaller crystal size is simple as well...I'd almost replace making AP by this instead. What say you all?

[Edited on 19-2-2005 by Mickhael]

Chris The Great - 18-2-2005 at 22:15

Crystals are anhydrous if rinsed with isopropyl and put in a really cheap and easy dessicator as well. So there is no need to recrystalize from toluene.

I dissolved some of my "DPPP" in toluene and no water precipitated out. I will leave some sitting in the open for a few days and see if it soaks up any water.

Keep in mind despite the water it still explodes with a fair amount of power anyway.


But yes, this method does produce a cheap, powerful HE primary explosive in large yields.

Out of curiosty has anybody tried to determine the molecular wieght? If you have a super accurate thermometer you dissolve a small amount in a solvent and measure the freezing point change, from which the mw can be calculated. This only works with very small amounts (<1g per 100g of solvent). I would do it but I lack the very accurate thermometer (within 0.01*C is used for this). The accuracy should be within a few percent.

Rosco Bodine - 18-2-2005 at 23:30

GB620498 is a more straightforward method for TCAP
and the product is more pure and obtained more quickly with less time and trouble .

Recrystallizing from toluene does more than just providing the anhydrous product ,
it also improves the density and the purity .

ETN 1 part and TCAP 2 parts makes a nice melt cast , but I have no information yet on the stability or explosive properties of the composite . I have an idea that there is perhaps an ETN / MHN binary eutectic that would be better as a binder for melt
casting TCAP , hopefully to form a fuse sensitive melt cast which would be similar to
" AP putty " , but have higher energy and not involve the shrinkage problems of putty . It is probably possible to get such a melt composition to work like putty , if the correct proportions and combination of materials is discovered .
Such a melt cast might make a decent detonator filler composition .

Dodoman - 19-2-2005 at 18:48

Quote:
Originally posted by PainKilla
They both lead to the same product. I had a batch of NaOH/acetone and they both formed the red liquid, with same properties, and same smell. It got me pissed off so I dumped it. DPPP is not possible via the current method.


I tested it for myself and got a very diffrent result.

After refluxing NaOH with acetone for two hours the solution turned slightly yellow and I got an orange ppt that I'm assuming is phorone.

The yeild was very poor (it seemed to increase by cooling) and smelled like new air mattresses the kind they have in swimming pools.

The yeild was so dissapointing that I threw it away but I'll be trying it again latter this week.

PainKilla - 20-2-2005 at 17:38

I just left mine at room temp for a few days. The precipate is NaOH (I used solid NaOH not in solutiion)

[Edited on 21-2-2005 by PainKilla]

Dodoman - 20-2-2005 at 19:04

I also used solid NaOH but that didn't preciptate, it formed a lower oily (white) layer that solidified on cooling.

The preciptate was suspended above it and was (orange) in color.

PainKilla - 20-2-2005 at 19:06

I didnt heat and the NaOH was "dyed" an orangish color. I dont think it actually went through a reaction.

hello there

Hdk - 7-3-2005 at 12:27

I am currently doing research for university concerning these organic peroxides. They are quite interesting group of materials. Anyway I have to inform you guys that DPPP is difficult to understand at best. I have tried serveral ways of making it but all have seemed to obtain a derivative of DPPP but not pure DPPP itself. It looks as thought this reaction must take place in a vacuum chamber with no air present as high amounts of mesityl oxide co-form with what what seems to be a ~pentameric form of acetone peroxide with only trace amounts of the target phorone peroxide. Hence the punjent odor that is left behind when this substance deflagrates. That is phorone you smell. :)

Joeychemist - 7-3-2005 at 12:48

I was wondering when Hideki would show back up. Maybe I’m just overly paranoid but you remind me of a certain “brain damaged” individual.:P

What is being formed is not a "derivative" of DPPP and as far as I know there is no such thing as an acetoneperoxide isomer containing five peroxide bonds, where is the proof to back up these claims? You haven’t even drawn a plausible reaction scheme to show how you think this reaction is carried out. Let’s see some proof, or at least a theory we can shoot down or something.

Your claims mean shit without evidence to back them.

Quince - 7-3-2005 at 23:02

Someone's pushing the DPPP scam over at the Amateur Pyrotechnics & Chemistry Forum too. I wonder if it's our 'friend' here...

HDK isn't Hideki rather H&raquo;D&raquo;K from RedOrchestra online

Hdk - 17-3-2005 at 12:34

Ya well I am not "hideki" sorry. I am just a passer by.
NONE of you have actually proven anything either on this little DPPP thread either so..... whats your point?
All people on this thread believe the Bullshit patent that was rigged on purpose to keep people away from it. This precusor material needed to be formed under tightly controlled conditions, unlike most people on this thread who beleived otherwise. It seems air cannot be present when Acetone is digested by HCl, but both materials must be in a gasious state in order to react properly!!! 2:1 HCl vapour to Acetone vapour. This condensed material is a ***dark green material** rather than dark red-yellow you were all getting. This is the material you peroxidize. The other was a highly explosive mesitylene-phorone derivative. as well as a whole host of acetone-peroxides. The ending DPPP is chalk white and acts very simularly to AP but is much more dense. I sure hope you skeptics are brave enough to try this, or you could hide behind all the BS theory floating around the web or textbooks... .

PainKilla - 17-3-2005 at 12:41

Before you go critizaing all the hard wrok everyone ahs done, where are YOUR results. I want to see a rxn mechanism not some "o yea i seen it happen!!111." NOONE wants you here so leave.... espeically with dumb accusation that have no validity.

On top of that, who really wants to bother with this if :
Needs to be done with no air, strict conditons, pure chems etc....

Does that not defy the entire point of a powerful and SIMPLE primary. Id rather make an existant explosive that is proven and true.

If this is such a great esplosive why dont you go patent it and stop bitching to us because noone cares.

O yea, and I just looked on red orchestra online and um... your not a member... hideki!

[Edited on 17-3-2005 by PainKilla]

Chris The Great - 17-3-2005 at 18:28

Um, go easy on this guy! 99% of the info is this thread is stated by those who did the experiment, no other info provided. And with that info we've made a new primary explosive, even if it isn't DPPP or is just some larger AP molecule, it's still different. And no one has provided a reaction mechanism, it's all been just speculation so far. You don't need to have a reaction mechanism to prove that a reaction works, you only need it to understand why the reaction works.

I think that this is highly interesting, if I can I will cobble together something to attempt this gas-phase reaction.

What are the conditions and set up for your experiment? It has been stated before in the thread many times to provide a large amount of detail on exactly what you did to get your results. Can someone use an inert atmosphere (ie propane) instead of having a vacuum, which I assume is what you used. Even better can you provide a sketch of the reactor vessel and setup you used, this would be a great help for anyone attempting to reproduce your experiments.

Many people care about explosives that need strict conditions, etc to be made. I certainly do, making a new, very powerful HE is definatly an interest to me, and if it is challenging to do even better. Just throwing something out the window because it's 'hard to do' is not science, it's almost forced ignorance. There is no reason to assume that because the reaction is hard to do it is completely useless and no one should even think about it.

BASF - 18-3-2005 at 09:29

Quote:

Just throwing something out the window because it's 'hard to do' is not science, it's almost forced ignorance.


???

Read the whole thread and the conclusions of so many different contributors.
This dream is over. - Try to accept it.

[Edited on 18-3-2005 by BASF]

Chris The Great - 19-3-2005 at 14:40

I have read the whole thread. He has offered a new route which has not been explored, tossing it out the window is not the way to go about it. Whether it produces DPPP is unkown, however, just going "Oh, he must be Hideki, ignore him, after all he's offering some new route but it's hard so lets just pretend everything he says means nothing."
Nothing has been tried that is even similar to performing a gas phase reaction in vacuum/inert atmosphere, and perhaps the method may work. There is only one way to find out. So, it looks like I'm going to be making HCl(g) and acetone vapour generator and inert atmosphere reaction vessel over the next for days.

I am thinking of a stainless steel pipe, heating up using a heating element or something, filled with a butane atmosphere. HCl will be generated by dehydrating HCl, acetone by heating. The pipe will lead into a gas trap (water). I am thinking of a pipe length of maybe 4 feet, and a 1/2 inch diameter. I have some old stove heating elements I can use to ensure the reaction proceeds rapidly enough so that it can take place in such a short pipe. If I end up with something different, I won't be able to peroxidize it as I have no H2O2, but it will at least determine if this approach may work. If not I get experience in building a reaction vessel for gas phase reactions under inert atmosphere.

EDIT:
Hmm, PVC pipe would probably work better. It should be fine up to about 160*C according to the limited information I could find, though it's ability to resist impact drops off sharply above 40*C. If I keep the internal temperature at about 100*C I should have no problem. This is mainly because I have 5 feet of PVC pipe and no stainless steel. The acetone will not attack the PVC as it is reacting with the HCl and will not be able to enter the liquid phase and start dissolving....I hope.

[Edited on 20-3-2005 by Chris The Great]

PainKilla - 20-3-2005 at 01:56

The thing is he didnt give any results. Theorizing about what COULD happen vs what WILL happen is two totally different things. Sort of like C + H2 --> Benzene. Its not happening.

The same results can be achieved if one leaves there H+/acetone mixture for a while, it turns green. Does anyone care, no. Because it doesn't do anything new. This isnt one product being formed, its a slew. Obviously in presence of H2O2 most react to form this peroxide. It also doesnt seem to matter how complex or simple it is (acetone vs phorone) as they all seem to make the same thing or near same thing.

And I never said anything about it being too hard. I basically said that there is a point unto which something is not worth pursuing. I understand maybe for the adventure of it... but seriously think about what you are talking about, you are going to react Acid vapors with a flammable solvent in an enclosed space.... thats really smart. Of course, assuming we are still alive, we can then try to add H2O2 and make the EXACT SAME THING as before. Oh damn, I forget this was to be done in a oxygen-free enviroment (assumption from the vague post) OK well, you try it and tell us how it goes.

If you really want to get some REAL results stop playing around with acetone condensation products order some damn phorone and see for yourself that it doesnt peroxidise. If it does, kudos to you, but Im almost postive that it doesnt.

On another note, what is the point of making compounds which you do not the properties or anything of anyway. I would like to know the structure mechanism of reaction etc... There is like 15+ different condensation products from acetone, I want to see which react. I bet you its just diacetone alcohol forming a peroxide, via AP mechanism, except with less water and more direct reaction. Regardless, I am disregarding anything past Rosco's results because THAT was *DPPP.* It was proven to be false as per the patent. If you want to experiment with some random new things, I would start a new thread because its not DPPP.

O yea, Nitrous kicks ass :). Any incoherency is blamed on it ;). Errr.... I mean not nitrous.... :D



BTW: I hve came up with resalts! THis was form a LAB!!! Heating acetone with Chlorine at 500C in a inret atmo$phere (NITROGEN) makes phorone, I KNOW because its GREEN and it has no phase, its just material!!!!!! *sarcasm*

[Edited on 20-3-2005 by PainKilla]

Chris The Great - 20-3-2005 at 15:14

Quote:
Originally posted by PainKilla
If you really want to get some REAL results stop playing around with acetone condensation products order some damn phorone and see for yourself that it doesnt peroxidise. If it does, kudos to you, but Im almost postive that it doesnt.


That fact was already well established in the beginning of the thread, and it was determined that any route that lead to DPPP would have nothing to do with phorone at all, but would be through derivatives of phorone, which would not be formed from phorone itself.

Quote:
On another note, what is the point of making compounds which you do not the properties or anything of anyway. I would like to know the structure mechanism of reaction etc...


Once we find a successful route to something that seems to be it, we can then look back and try to figure out what is going on. We can do that by determining the molecular weight of this new product, it's atomic structure, our observations of the reactions which led to it, and then figure out what the reaction is from that information. We obviously can do none of that until we have actually made the product.

Quote:
I bet you its just diacetone alcohol forming a peroxide, via AP mechanism, except with less water and more direct reaction.


You are betting, and I am going to keep experimenting and see if I get any closer to the truth. I don't really care if I don't ever end up with something useful, I will then know that by doing such and such, you will not end up with something useful. *Insert overused quote of Edison and lightbulbs here*
As of right now, nothing about the reaction is known for sure. None of it, other than that the acid and acetone react, and when it is peroxidized, we get an explosive. We don;t know for sure what the reaction is. We don't know for sure what the end product is. Sure, we've made some good educated guesses, but none of them have been confirmed for sure by good hard evidence such as molecular structure and weight, etc.

Quote:
Regardless, I am disregarding anything past Rosco's results because THAT was *DPPP.*


No, we are not completely sure exactly what it is, although it appears to be a derivative of acetone peroxide, or something else. This has not been established in fact.

Quote:
It was proven to be false as per the patent.


I believe this was established perhaps around page 10 of the thread, but we all kept going, to see if we could perhaps figure out what we where doing. I don't see how it's any different right now.

Quote:
If you want to experiment with some random new things, I would start a new thread because its not DPPP.


The general concensus (which you are a part of) is that NOTHING in this thread ever was DPPP anyway.


But I don't see what this argueing has to do at all with science. You have stopped and figure you know all the answers, I have decided to keep experimenting because we DON'T have all the answers. I don't care if all I end up doing is showing for sure that we only have pentameric acetone peroxide, or a slew of different chemicals, or true DPPP or something completely different, the point is we don't know for sure, and I want to discover answers to these questions. Now, if someone has found the answers with great, undisputable evidence, I'd love to see it and be proved wrong, but I'm sure that no one has those answers.

chemoleo - 20-3-2005 at 15:36

Quote:
By the way, in Gattermann I read today that acetone reacts in the presence of HCl-gas to mesityl oxide and phoron.
This may be another thing to try, to bubble HCl gas into acetone!
According to Beyer&Walters Book on Organic chemistry, mesityl oxide is a clear liquid that smells slightly of peppermint (!!).
Phorone is, on the other hand, a yellow substance that has a melting point of 28 deg C !!! In this book it also says that it is obtained by reacitng HCl gas with acetone, while mesityl oxide is a side product.


May I just remind you of that. Two independent sources describe this route to phorone. Not wanting to hype anything, but maybe that's something that shouldnt be forgotten, to try this under anhydrous conditions.

BASF - 21-3-2005 at 08:51

(Originally written by Rosco Bodine)

Quote:

In a very real sense this thread is a " Classic "

It may serve a useful purpose to just leave the thread as it is , because it shows the contrast between scientific method and tests designed to develop pertinent data versus intuition and anecdotal but non-conclusive approaches ,
applied to the task of learning an unknown by experiments intended to reveal what is secret . Reading through the thread , there are portraits of various persons struggle with methods and tools for investigation , verification or dismissal of a set of reactions descrbed by an obscure patent . The result is an "epic" work , which is sort of
the "War and Peace" of organic peroxide threads


Yep. There`s so much truth in that :P

@vulture: it was great at the beginning, this kind of gold-digger-mood, was it? :P

I want to repeat my offer on samples of my 97% phorone (from Sigma-Aldrich) ..... it could be used as reference for chromatographic comparison and the like. - Since i dont have any ambitions in trying the peroxidation again.....U2U me, if interested....

vulture - 21-3-2005 at 14:16

Gold digger mood is always fun in the beginning. But it quickly turns ugly when only pyrite is found and gold fever catches on.

Don't say I didn't warn you.

You've done the experiment , now see it all on DVD !

Rosco Bodine - 21-3-2005 at 18:47

Yes , next it is being made into a feature length movie ,

" DPPP " ( part deux )

or perhaps .....

" Mackowiaks Folly " ( the sequel ) ;):D

coming soon to a theater of madness of the scientific variety near you ,

unless you spare yourself and escape now

while you still can . :D:D:D

Better watch that boy ,
he's become anhydrously reactionary ,

singing

How dry I am ,

How dry I am ,

How wet I'll be ,

If I don't find .......

a place to pee.

[Edited on 22-3-2005 by Rosco Bodine]

Hello!

Sickman - 29-3-2005 at 23:42

Dear Rosco Bodine,

As always thank you for your reply,
I didn't figure that patent was worth
much anyway. As I said in my latest
post to you I have enjoyed discussing
that blasting cap setup with you. I
didn't figure the scaling up of the idea
to a 2,000 pound bomb would have worked, or the military would have
discovered it along time ago. Well
here's our new place to talk if your not mad at me about what I said to "you know who" (name starts with an N) and how things are now with "you know what" (name starts with R)!

As always, thanks for your reply!

P.S. By the way this is a very awesome
thread!:D

dppp

EBAYID_cheap_stuph - 6-4-2005 at 23:36

I found the key. to get rid of the mesityl compounds you add very little h2o2 to the cold black liquid. and let it sit for a day in the freezer. the black stuff will precipitate to the bottom. next add h2o2 to the yellow liquid and don't let the temp get over 5c. You will get dppp.

Quince - 7-4-2005 at 02:16

It's not even funny any more. Give it up, Hideki.

Chris The Great - 7-4-2005 at 21:20

Ok, here's the real secret. DPPP isn't going to be made by any reactions proposed in this thread.

However, we can make phorone peroxides. You may notice phorone is an alkene, it will react with chlorine to form phorone tetrachloride.

That can be peroxidized to phorone diperoxide. Since phorone is a ketone it will most likely also react at that point of the molecule to make diphorone hexaperoxide.

All the reactions I just proposed are known reactions. Doing that will give you phorone diperoxide or diphorone hexaperoxide, I'm not sure if the ketone part would react on such a large molecule.

Now, since everyone wants to make phorone, I found a preperation by searching.
http://67.15.145.24/~sciencem/talk/viewthread.php?tid=1203

So, there's the secret. I'm surprised nobody has mentioned it before (especially the alkene thing). Look over my proposed scheme, try and find any flaws, but there are none. Alot for those of you were asking for reactions, they are here.
I will try this when I get some calcium chloride and a cheaper source of ammonia.

EBAYID_cheap_stuph - 7-4-2005 at 22:33

If it is not dppp we are getting then why is it more powerful than AP? Do you think the process in the patent is BS but the product is real. If you think about it there are explosives that are top secret. and maybe this is one of them.

-------------------------------

Yah, yah, yah. There are more daft patents than you think. Read the thread.


[Edited on 8-4-2005 by vulture]

Chris The Great - 22-4-2005 at 11:45

I did some paper chromatography of my H<sub>2</sub>SO<sub>4</sub> + Acetone mix, and found that it appears to be made up of at least 3 or 4 different compounds.

I'll scan in the paper strips, I did the chromatography with isopropyl alcohol, toluene, acetone, methanol and water, to see both what the thick black goo was made of, as well as what the different compounds were soluble in.
Only acetone could dissolve all the components, so it was fairly easy to seperate out one of the compounds by solubility alone.

Anyway, methanol seems to dissolve only the black coloured compound, leaving behind a pale yellow material.
I added some of the black goo to methanol, and filtered out a huge amount of dark green solid. Another wash with methanol got all the remaining black chemical out, but I also had a large amount go through the filter and so I lost a large amount.
I then rinsed in water/methanol, and filtered again, losing even more of the green solid.
I dissolved what remained in acetone, and poured into 5 times the volume of water to precipitate it out. I filtered again, and as it was going through the filter it slowly changed from the deep green colour to a sulfur yellow.

I ended up with maybe 5% of the original solid, so obviously I need to do something different, perhaps not use pure methanol as that seems to bring things through my coffee filters.

Now, this stuff looks to me like the same colour of the first "DPPP" made in this thread. The mixture I seperated it out was far beyond the oily stage, it's "oily layer" was actually a nearly solid mass. This could explain why I got so much of the stuff.
It also has a strong, unpleasant smell, but not strong enough to cause watery eyes like my "DPPP" could do.

It would appear I have found the yellow impurity.

It has a very high melting point, so it isn't phorone. After melting it solidifies to become a solid plastic mass.

I'll put up the chromatography strips later as well as some pictures so you can see the colour. I'll try to do better seperation of all the components on the weekend.
If I get more hydrogen peroxide then I'll try to peroxidize the different chemicals, but that's no quarantee.


EDIT:
The paper strips:
http://img223.echo.cx/my.php?image=pc0016nz.jpg

Green Stuff (right after the first filtration):
http://img89.echo.cx/my.php?image=precipitate8qq.jpg

After it turned yellow:
http://img89.echo.cx/my.php?image=yellow5ug.jpg

Also, got another liter of 35% H<sub>2</sub>O<sub>2</sub>.

[Edited on 23-4-2005 by Chris The Great]

Pyro_boy - 26-4-2005 at 11:34

Quote:
Originally posted by responsible blaster
I have been in contact with a fellow by the name of The R_Sert on Rogue science and he gave me a link to this sites DPPP synth page.
I have produced some of the material in question, and the yeild is very good. It is also far more powerful than AP or APAN or MEKP. I think this materials full power can be realized when it is highly compressed and blasting cap placed at dead center of the device.


Interesting enough, I too made a batch of the material in question. I had to make it at very low temperatures and it is very similar to AP, but is ever so slightly mint green/yellow. Crystals are cubic...

[Edited on 26-4-2005 by Pyro_boy]

Theoretic - 27-4-2005 at 10:38

Holy Jesus Christ. If I attempted to read the whole thread, MEDGO. Yet somehow, you have managed to talk for 35 pages about a preparation of a somewhat obscure organic peroxide and things related thereof. Shows how far humans are prepared to go in their quest to attain and perfect knowledge. :o:);)

frogfot - 3-5-2005 at 03:06

Excuse me, but I was just wondering how the formula of DPPP was obtained. I'm referring to the one that you all are referring to:
http://www.sciencemadness.org/talk/viewthread.php?action=att...

I tried to write some mechanisms.. and this is what showed to be the most obvious prods (hope I havn't posted same thing earlier in this thread :o), see attachement.

I'm too lazy to draw the whole mech.. but it doesn't include many steps..
It seems that prod 1 should dominate since reaction should start with H2O2 (hard nucleophile) attacking the carbonyl group (hard electrophile), rather than attacking the conjugated C=C bond (soft electrophile).
Conversely, prods 2 and 3 starts with H2O2 attacking the conjugated C=C bond (prod 3 is formed from 2, although it could probably form from 1 too if one of the double bonds was hydrolysed).

On the other hand, product 2 may also be dominating if we take into account that the carbonyl group is conjugated and therefore makes not that good electrophile. While plus charge on the tertiary carbon is nicely stabilized (should be therefore in big concentration)..

Another good point to mention, prod 1 has an energy benefit due to the formed diene.. though it could be reactive..

Come on do anybody has a free access to a lab with a HPLC-MS instrument, where one could analyse the contents of that overly discussed reaction mix? Some really soft ionization technique would probably reveal it all...
Without such data, going after smell/color of product seems to be quite useless..

phorperox.gif - 2kB

PainKilla - 3-5-2005 at 18:02

Peroxide formation scheme attached.

peroxide schenme.gif - 7kB

The_Davster - 3-5-2005 at 18:13

Frogfot, I thought the DPPP everyone was refering to was:

Attachment: DPPP molecule.pdf (18kB)
This file has been downloaded 1082 times


frogfot - 4-5-2005 at 12:04

Oh, than I probably missed it in all those pages of this thread..
Though still, it seems that this dimer is quite improbable to form. You sure that this compound really is produced from phorone in one batch reaction? I mean is there any other references than that german patent..

PainKilla, that mech wouldn't be true since phorone has some double bonds too..

PainKilla - 10-5-2005 at 02:27

No, that is the scheme for AP formation in my organic chem. textbook.... Im not saying its DPPP, but for general reference... We really have no idea what the "real" molecule looks like anyway, so it could be like tetraAP or something.

Summary?

Tweenk - 30-5-2005 at 09:55

Could someone make conclusions of what has been done yet? ie some proven methods for preparation?

Summary

DirtyDan - 23-6-2005 at 10:38

In short, many claims have been made with many different syntheses and many different magnitudes of the compounds. Results have been black, green, yellow, etc. Nobody is sure why and it could all be contaminents.

In other words, everyone is at the drawing board still (as far as I can tell)

Anyone have anything to add?

Rosco Bodine - 23-6-2005 at 15:13

It's black and white .

DPPP doesn't withstand scrutiny .

Rusk - 24-7-2005 at 19:05

Hey, im a Yr 12 chem student, but i am quite advanced in contrast to most of my class, especially in the pyrotechnics field. I have been a member of totse backyard ballistics forums for quite a while now, and i have taken a real interest in this "dppp" discussion. i have read through most of your pages, and is far as i see it, i think this illusive "dppp" does not exist. Instead people have managed to create an alternative form of AP, that is more stable, slightly more powerfull and is faster to create, without having to worry too much about trimer ap causing accidents. I wander if what i have meantioned has summed it up, and if it has can someone post a full "walkthrough" to succesfully making this new improved form of ap.

The_Davster - 14-8-2005 at 13:09

If you dump the chilled solution made from heating the acetone and HCl together into cold peroxide fast, then add household ammonia it makes an awesome cleaning solution...I had spilled some of this a long time ago in a failed DPPP attempt and it cleaned the horribly stained bench very well. I am posting this as I make more of this to clean some very badly chemically stained wood.

neutrino - 14-8-2005 at 15:27

So, the end product of this wild goose chase is... a cleaning solution. Perhaps the title should be changed appropriately? :D

humm...going to wing this one.

((Blasta)) - 16-8-2005 at 09:27

When I was in high school I remember a demonstration using HCL gas in Acetone. The production Mesityl Oxide, Acetone DiAlcohol and Phorone all existed in the same container. However, after about 2 months this liquid became resinous and globs of Phorone stuck to the pyrex flask.
On an interesting note Mesityl Oxide can certainly become a part of an unstable Organic peroxide...this much I know. Pure Mesityl Oxide is a dark liquid which can easily react with Hydrogen Peroxide. However the temperature must be quite low or the heat generated by the two chemicals can cause a SERIOUS and sometimes EXPLOSIVE run-away reaction. I think this is where people are having issues. The Patent "DPPP" is a fraud. I have attemped this reaction several times in lab settings...each time I have created the same product. I produced my own Mesityl Oxide and I also used lab grade Mesityl Oxide. In both sistuations I recieved the same product...this was a fine crystalline power which had similar properties to TCAP, but appeared slightly yellow/green in color. This material was formed only at low temperatures, 0 Celcius to be exact.

Dream of the iris - 28-9-2005 at 10:44

Quote:
Originally posted by Polverone

One thing that just came to mind: when I was young and foolish, I experimented with acetone peroxide, not really knowing what it was, and so did many of my friends. One of these friends once claimed that he had made a batch of acetone peroxide using a huge amount of HCl. He claimed that the mixture grew hot enough to boil, and that when it had calmed down he was left with crystals large enough to be easily visible to the naked eye, and that they had a slight yellowish cast. He also claimed that, unlike other batches of acetone peroxide, this one would explode, unconfined, even in the smallest amounts.



That happened to me, all though my AP didn't have a yellowish tint. The crystals were huge, but the solution didn't boil. All the AP fused together to form a "chunk". One time my solution did boil; however, but I discarded the solution before any soild could form. I should have pics of the crystals, unless I deleted them...

[Edited on 28-9-2005 by Dream of the iris]

lets test it

coldzero - 29-9-2005 at 18:06

I have read this thread with alot of interest. And many people consider this to be another form of TCAP.
Nobody has tried to measure the density of the dpp product only to make comparisons againts color and texture. which mean nothing. Are we that bad in chemistry that we cannot dry out a couple of grams of this and put it into a known volume of water and measure how much water it displaces?

ordenblitz - 7-10-2005 at 19:38

I have begun the process of trying to solve some mysteries in this long and contentious saga.

The plan is:
1) Make the acetone + HCl precursor, divide the result in two parts.
2) Half will be fractionally distilled and the fractions tested in the FTIR as they come off. 3) The remainder will be used in the synthesis of the DPPP for further testing both against my current libraries and also compared to a sample of trimeric acetone peroxide that will be prepared for same.
4) Both the suspected DPPP and AP will be recrystalized in toluene and compared again.

My intentions were to do most of the work then post the results, however I have found some interesting things so far and decided to post them now.

I mixed the acetone and HCl according to the proportions suggested by Roscoe. I intended to get at the distillation the next day but was distracted by some pesky work so I had to let it sit for 2 more days. Due to the age, I decided to discard this batch and begin again. Upon opening the closed bottle the contents consisted of a viscous goo on the top and a slightly thinner fluid below. I separated the two portions and let the upper residue dry out to a thin plastic looking film in a few hours. This film was run on the FTIR using the MIR accessory and compared to the library.

It came up as an excellent match.....poly epichlorohydrin!
Ok this is interesting. I can see the first two steps of the possible reaction mechanism below, being very probable but the last seems to require a base to complete.

acetone + Cl ---> dichloroacetone
dichloroacetone + H2 ---> dichloropropanol
dichloropropanol + xOH ---> epichlorohydrin + xCl + H2O

Regardless, it was a very good IR spectra and I agree with Nicolet's conclusions.

This leads me to believe that dichloroacetone and not phorone is being produced in the initial reaction. I will continue further testing and post the results as they come in.

For those who were sick of this thread, I apologize for re-awaking the sleeping giant.

Excellent!

vulture - 8-10-2005 at 08:05

This is great! Reliable analytical data is what we need.

So, please continue, because these are some unsuspected, yet interesting results.

Quince - 8-10-2005 at 18:24

Quote:
Originally posted by ordenblitz
This film was run on the FTIR using the MIR accessory and compared to the library.

Pardon me, but could you explain FTIR and MIR for those of us not in the know?


BTW, vulture, you used the wrong conjunction there. The results are interesting because they are unexpected, not despite that; thus, you need an 'and' rather than a 'yet'.

Just because English may not be one's first language, it's no excuse to molest its structure like that. You know, I go downtown Vancouver, and all these asians, half of them barely know a word of English; it's sickening. Immigration is run terribly wrong: they shouldn't let anyone in that doesn't know English. Rather than assimilating immigrants, Canada has a nation-destroying policy of supporting the creation of growing pieces of foreign nations on Canadian soil. Chinatown here really is a part of China. I've heard the Canadian government actually advertises in asian countries that Canada is one of the only Western nations that one can come to without having to learn English! As an immigrant myself, who has become a proud Canadian and loves the good language, I feel very justified in commenting on this.

[Edited on 9-10-2005 by Quince]

ordenblitz - 8-10-2005 at 19:19

Acetone + HCl precursor tests.

I prepared the precursor once again according to the method used by Roscoe using known good chemicals.
http://img217.imageshack.us/img217/2672/chems0rj.jpg

You can see that it had the required color. For some reason I expected it to be more viscous, but it met the general descriptions that were given.
http://img217.imageshack.us/img217/6569/redstuff3pq.jpg

Distillation was accomplished using the pictured set up. I opted for a jacketed, packed column to afford the best separation. I should have used a 2 neck flask and put a thermometer in the other neck but alas I didn't think of it in time.
http://img217.imageshack.us/img217/4633/distsetup10pl.jpg
http://img217.imageshack.us/img217/3958/distsetup28ui.jpg

As the fractions came off I collected a small portion in some sample tubes and marked them with the temperature. I should have measured the volume of the total distillate, but I was too busy running back and forth to the FTIR to be bothered.
http://img217.imageshack.us/img217/8158/ftir7fu.jpg

The first drops came over at 51º…. and you guessed it…
http://img361.imageshack.us/img361/8774/spec1556dp.jpg

The temperature held fairly constant at the head for quite some time as the acetone came over. I took many samples but the FTIR kept showing the same result.

The temperature rose to about 62º and held there while white fumes smelling of HCl began to come off. Not much distillate was collected. The temperature rose again to 80º and a small amount of yellow colored liquid collected.
http://img361.imageshack.us/img361/2057/spec2802rb.jpg

I would disregard this last spectra as it wasn't a good match and I'm sure the distillate was quite the mix of things, which tends to confuse the spectrometer.

The temperature rose again to 103º where upon the water began to come over in quantity along with trace amounts of a thin oil. I was unable to collect enough of it to test unfortunately. After the water substantially stopped coming the temperature rose to 108º and I turned off the heat. This is what was left.
http://img217.imageshack.us/img217/6222/remainder6aj.jpg

I tested the reddish remainder and what I got was interesting.
http://img217.imageshack.us/img217/7947/spec3rem1gg.jpg

It also said that it could possibly be this as well. We all know that isn't possible but you will notice that the spectra is very similar, enough to confuse the software.
http://img217.imageshack.us/img217/8306/spec4rem6wk.jpg

Sorry folks… no sign of any phorone. I will continue tomorrow using the precursor to form the peroxide and run those samples.

ordenblitz - 8-10-2005 at 19:39

Quince said:
------------------------------------------------------------
Pardon me, but could you explain FTIR and
MIR for those of us not in the know?
------------------------------------------------------------

MIR stands for multiple internal reflectance attenuated total reflectance accessory. Also known as MIRacle ATR.
http://www.kromatek.co.uk/Attenuated_Total_Reflectance_77.as...
It is an accessory attached to my FTIR. It allows for fast sample setup and testing in powders, liquids and films. It's not so good for hard crystalline material though for that a KBr tablet is best.

I could go on for pages explaining how all this works, so instead I got this from a site that explains the basic theory of FTIR.


Fourier Transform Infra-Red Spectroscopy, FTIR

Theory of Operation
The component atoms of polyatomic molecular groups are in constant dynamic state of motion with respect to each other. They are changing between the molecular ground state and quantum mechanically allowed excited states due to thermal excitation. This movement allows the spectroscopist to observe the twisting, bending, rotating and stretching motions of the atoms within a molecule occur at frequencies that are in the infra-red (IR) portion of the electromagnetic spectrum (0.7500 um). When infra-red light of energy coincident with the difference between the ground state and excited state of a particular molecular vibration is radiated onto a sample, the vibrations are stimulated (it jumps from the ground state to an excited state), and the light of that particular wavelength is absorbed by the molecule (IR absorbance). By monitoring the absorbance of the a range of wavelengths or frequencies of an infra-red light as it is transmitted through or reflected from (IR reflectance) a sample, a characteristic infra-red spectrum can be obtained. In Fourier transform infra-red spectroscopy, the source is modulated with a Michelson interferometer. This results in a signal at the detector which has a distribution of frequencies determined by the speed of the moving mirror of the interferometer. The resulting interferogram in the amplitude time domain is then transformed via the Fourier algorithm into the appropriate amplitude-wavelength domain, resulting in a characteristic infra-red spectrum for a particular compound.

Typical Applications

-Identification of extractable organic components from a device or wafer surface or PWB

-Identification of contamination (oils, polymers, solvents, fluxes, greases, etc.)

-Identification of unknown solid organic compounds (powders or residues and solvent or liquid organic)

FTIR is the leading analytical instrumentation for identification of organic substances

Rosco Bodine - 8-10-2005 at 20:35

Hmmmm .... that is interesting how
the FTIR is reading an indeterminate
compound it suspects is dimethylamine iodate , especially given the impossibility
that either iodine or nitrogen are present
in the sample :D

Whoever paid good money for that POS equipment got robbed :o :D ;)

Or maybe it's the software ? If Microsoft is involved somehow , maybe that explains things :D

[Edited on 9-10-2005 by Rosco Bodine]

ordenblitz - 8-10-2005 at 20:45

That was simply a case of a very similar spectrum. If you look at the two that came up on the search they are pretty close. That however does not mean that the chemistry is similar. You have to know what to believe and what to ignore.

These machines do not like soups of many things mixed together. But they are dead nuts right on if you do a good job with the glassware first.

Roscoe,

Where did you get dimethylamine iodate?
The search turned up two possibilities.. hydriodic acid or dimethylamine.

[Edited on 9-10-2005 by ordenblitz]

Rosco Bodine - 8-10-2005 at 21:01

peaks for dimethylamine and hydroiodic acid would be dimethylamine iodate .....

right ?

ordenblitz - 8-10-2005 at 21:09

No.
Individual peaks are not representative of compounds or elements.
They can however help to identify groups and bonds, etc. It's very different than GC or GCMS etc.

Rosco Bodine - 8-10-2005 at 21:18

Got it , FTIR sees a color signature in infra red , not a map of spectral peaks , but more like a tint value ....a mixed spectrum value .

So FTIR doesn't recognize the acetone polymer . It is probably the epichlorohydrin polymer at a lower level of polymerization , and even in the visible spectrum it does have something of an iodine color , especially for thin films of the solidified higher polymer which looks like spar varnish and is about as tough as polyurethane , sticks to glass tenaciously like an adhesive .

ordenblitz - 8-10-2005 at 21:29

It has nothing to do with colors or tints etc. It has to do with frequencies that are absorbed and those that are reflected.

If you go back a few posts you will see I posted a theory of FTIR.

It took me a long time to get it straight in my head. If your interested, there are a number of online resources that can explain it better than I.

Rosco Bodine - 8-10-2005 at 21:41

When you illuminate a sample with an emission source in visible spectrum , and detect what wavelengths are reflected and absorbed , " color " is exactly what you are detecting , along with albedo , reflectivity ..it is the same in astronomy and instruments used on telescopes for spectral analysis of objects to guess at their composition . The same thing can be done in the UV and X-Ray spectrum .

Comon - he's doing great work!

chemoleo - 11-10-2005 at 18:54

First, to clarify: If a compound has a blue colour, it actually means it absorbs at lower wavelengths, like red, yellow and green. Thus blue light is left, which is what we perceive.
So the light you monitor is not the light you absorb of course.
Conversely, a compound may absorb infrared at a specific frequency, corresponding to the various bonds stimulated. This excitation of course is lost in due course in several ways, possibly even by resonant energy transfer.

Regardless, the method is very good in detecting the different rotational/translational/vibrational levels of each bonds, forming a compound spectrum that of course depends on other bonds in the molecule.


Anyway, I think, Ordenblitz, you are doing fantastic work.
The fact that a reference spectrum cannot be matched (or only to some obscure chemicals such as iodic acid) doesn't mean anything here, as it clearly cannot be iodic acid.
Neither does it invalidate FTIR as a technique. It is only to be expected that some molecules are similar but not identical the spectrum ordenblitz observed here, but it doesnt mean the method is invalid. You cannot expect every molecule in the universe to have a clearly distinct spectrum, particularly when there is always some error associated with acquiring each spectrum. In other words, Ordenblitz simply lacks the reference spectrum to compare the compound against. To my knowledge, this is how the company makes money in the first place, with accurate and enormous reference libraries.

Anyway, Ordenblitz, what I meant to say is that the fact that the spectrum of the distilled substance is very broad, with no baseline, means that you indeed are likely to have various products, with various overlapping energy states, all absorbing similarly (see the last pic http://img217.imageshack.us/img217/7947/spec3rem1gg.jpg ), possibly suggesting a polymer or a large array of very similar compounds.
Getting reliable reference libraries for various polymers (i.e. more than one product) is difficult, to say the least.

Furthermore, and more importantly -

The key experiment of course is to DIRECTLY compare the acetone peroxide to the putative DPPP product. If spectra differ, then we KNOW that the compounds are different. This is not necessarily proof for the identity of DPPP, but it is a PROOF for a different peroxide. And that is a big conclusion on its own.

More in detail, I'd possibly consider pooling the fractions minus those consisting of acetone (to remove any potential AP 'impurities';), and preparing the peroxide thereof. Then, to make normal trimeric AP.

Recrystallise both from toluene/chloroform/whatever, and compare with FTIR.

I'm looking forward to see the results!!!

Damn I wish someone had NMR, that'd sort it!

Oh, if you find the time, Ordenblitz, could you also please post the respective methods (very briefly) you used for making the respective peroxides, for future reference (in case someone else has analytical ambitions) Sort of to set a comparative standard.



PS Oh, and Quince, did I hear that right? It's an international forum you know? The core issue is that people are understood. To be honest I can't always say that in your case.
If you have an issue with Vulture's or someone else's English (I am sure there's a decent number of native English-speakers you might have an issue with), please, you are welcome to correct it via U2U, be our language ambassador, the conjunction-mod; rather than cluttering the thread with ramblings that are quite inappropriate, particularly in this case. Please just tell me you had a bad day.


[Edited on 12-10-2005 by chemoleo]

ordenblitz - 12-10-2005 at 19:10

I have finally had time to run the samples of TCAP and the suspected
DPPP on the FTIR. Hopefully this will solve the question once and for all.

I have described my method of production of the suspected DPPP
precursor and tests of same in a previous post. I used the method generally described by Roscoe, gleaned from his many posts.
The precursor was chilled and the H2O2 was added small portions, while
maintaining the temperature.
http://img441.imageshack.us/img441/578/synthdppp16xq.jpg
After all the peroxide was added, stirring was continued for a further 10 minutes.
http://img441.imageshack.us/img441/8994/synthdppp21mr.jpg
The material was filtered and washed with successive portions of
DI-H2O.
http://img441.imageshack.us/img441/1960/synthdppp32bf.jpg
The result was pretty much as described by most who have made it and is
evident in the pictures.
http://img441.imageshack.us/img441/5840/wetdppp4vy.jpg


The TCAP was made using Mega's method, with high quality precursors
from Fisher and Anachemia.
I was careful to keep the temperature at ~5º while the H2SO4 was added
dropwise.
http://img441.imageshack.us/img441/1434/synthtcap5yw.jpg
After the additions were complete I continued the stir for 1 hour then
placed the beaker in the freezer for 8 hours. It was then removed and
brought to room temp where it sat for another 2 hours before
filtration.
http://img441.imageshack.us/img441/5937/synthtcap23tb.jpg
The wet crystals were allowed to dry for 6 hours in a dessicator then
were dissolved in acetone, filtered then crashed out with de-ionized water.
http://img441.imageshack.us/img441/3567/wettcap1ce.jpg


Samples of the two materials were prepared for the FTIR using the KBr
pellet method because I was none to keen on pressure clamping samples of
primary explosives to my $1000 germanium MIR-ATR crystal.
http://img441.imageshack.us/img441/7148/kbrpowder9uf.jpg
The KBr method uses powdered potassium bromide mixed with a small
amount of the sample to be tested and compressing it under high pressure to a clear or almost clear "window" which the IR beam passes on it's way to the detector.
KBr is used because it is essentially clear to IR radiation, thus
providing
a substrate that holds the sample in the beam path.
I chose to use NAB dies to compress the sample.
http://img441.imageshack.us/img441/3319/nabdie2np.jpg
These are a simple stainless steel nut and polished bolts that are
tightened to compress the sample. The bolts are then removed and the nut placed in the sample compartment of the FTIR, in the beam path.
http://img441.imageshack.us/img441/4097/samplecomp6wr.jpg
The I did sweat a bit while tightening the KBr samples in the die, but
I don't think it's too dangerous seeing as how the samples are fairly
dilute in the KBr ~5%

And here it is…
The spectra in green is the TCAP. The one in the red is the DPPP.
I made it big so as not to lose any detail in the peaks.
I won't even bother to give my opinions as the spectra speak for
themselves!
Read em and weep boys and girls!
http://img406.imageshack.us/img406/3198/comparescan24el.gif
(It looks best if you the save the gif and open it with paint)

Lastly, I post the individual spectra of the two materials for those
who want the clean individual spectra.
TCAP
http://img442.imageshack.us/img442/3200/tcapscan503ul.gif
Suspect DPPP
http://img442.imageshack.us/img442/2968/sdpppscan508gw.gif


Whew… that was a lot of work!

Regards,
Ordenblitz

[Edited on 13-10-2005 by ordenblitz]

Quince - 12-10-2005 at 19:22

Great work! Finally, this thread can be closed.

Chris The Great - 12-10-2005 at 23:01

Very nice work!
Why couldn't you have been here three years ago! :P

No need to close the thread, we don't yet know how 'strange goo' turns back into AP.

Also, the predicted IR spectrum of AP and DPPP are very similar, with the exception of the C=O peak... but those results are pretty much identical, way to similar for me to doubt.

So it's been AP all along :P Well I can't say I'm not dissapointed, but it's nice to have closure on what it is. Now lets get to work and figure out how the hell we got there from polymeric goo!

Rosco Bodine - 13-10-2005 at 04:34

What I have guessed occurs is a reaction which is analogous to the formation of hexamine from ammonia and formaldehyde in the sense that the reaction proceeds whether the formaldehyde is the monomer formalin or the polymer paraformaldehyde , by the reaction conducted in an aqueous condition . The end product is the same
whether the precursor formaldehyde is polymerized or not . The same or a very similar thing is being observed in the case of acetone where its polymerization products and or reaction products with HCl mixture , is functionally the same in its subsequent reaction with hydrogen peroxide to produce the same end product , irregardless of the order of addition . The principal end product is trimeric acetone peroxide by whatever different reaction paths may lead there .

ordenblitz - 13-10-2005 at 08:33

I have some of the material that was re-crystallized from toluene that I was going to run, but after seeing the spectra from the raw material I didn’t think it was worth the time.

If anyone would like to see the spectra from the re-crystallized material, speak up.

Chris The Great - 13-10-2005 at 18:57

Very nice explanation Roscoe, that does make a great deal of sense.

If it is at all possible, I would be interested in seeing the spectrum of mesityl oxide peroxide, formed by simply reacting mesityl oxide and hydrogen peroxide for a few days. Thats about all the information I have on it, but I would be interested to see how it's spectrum compared to that of AP. If you don't have mesityl oxide then don't bother.
I'm just curious to see how different peroxides compare to each other spectrum-wise, and also because mesityl oxide peroxide should be a contaiminant in the DPPP synthesis, since mesityl oxide is easily formed by dehydrating acetone which we have done.

chemoleo - 13-10-2005 at 20:35

Yes, that was in part the reasoning behind suggesting to make the peroxide of the red distilled oil (aka acetone-free); in order to see whether it would produce a different spectrum upon peroxide formation. Alternatively, compare TCAP to dimeric :o or tetrametric AP.

The point you made (Ctg) is a very valid one indeed.

I am not quite so sure as to the mechanism however. An analogy doesn't mean it holds, other than looking similar. Anyway. It's probably not so important (before we get into a pretty useless debate).

[Edited on 14-10-2005 by chemoleo]

Chris The Great - 14-10-2005 at 21:51

I'm curious what the very large peaks around 1200 represent?

I notice they are the only part that is signifigantly different...
I think it might be worthwhile to get a sample from the recrystalized DPPP to see if that difference is just from an impurity or something (probable in my opinion).

DPPP+UN Mix

PyRoE_Inc - 21-10-2005 at 22:30

Hey there fellow hobby chemists and
of course the higher educated of you...
I dont know if my information have any relevance of this matter, but i do think so.
I noticed, upon mixing DPPP and ureanitrate, there were a sudden change in temperature.. the temperature dropped. the "DPPP" was only about 90% dry, and so was the UN.
The mix was 50/50. i got a complete detonation of 8g mix with 0.8g "DPPP".. it was nothing like the AP/UN mix´ i´ve used
were 20 grams of ap/un didnt detonate properly, that was with a 10g detonating charge of ap. but my question is... Wats with the sudden temperature drop?? by the way, this is my first reply. happy to finally break into the discussion. it was a hard read to end(exept this last page), buuut interesting... hoping to get an answer...:)

Quince - 21-10-2005 at 22:37

Welcome back, Hideki!

Wait, what am I saying... you're not welcome at all.

Hey fucktard, didn't you read the last several posts, which demonstrate beyond any doubt whatsoever that there is no DPPP and it's just some form of AP?

[Edited on 22-10-2005 by Quince]

Joeychemist - 22-10-2005 at 02:42

No need to resort to vulgarities or verbal abuse to make your point, Quince. There may in fact be DPPP, it is just not formed by acting HCl on Acetone and peroxidizing. The structure for DPPP which is given in the patent and by CAS certainly seems like it is a possible one to me.

But anyways, PyRoE_Inc, may I ask how you are determining the temperatures of the "reaction"?



[Edited on 23-10-2005 by Joeychemist]

Quince - 22-10-2005 at 03:45

OK, but why'd you delete the picture post?

[Edited on 23-10-2005 by Quince]

 Pages:  1  ..  7    9