Sciencemadness Discussion Board

Diphoronepentaperoxide (DPPP)

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The_Davster - 10-1-2005 at 19:41

Quote:
Originally posted by Rosco Bodine


Are you going to weigh your yield and do the math to get the percentage ?
( 27.57 grams would be 100% of theoretical ) 24.8 grams would be 90% of theoretical .


11.6 g of pale yellow DPPP + 1.2g pure white DPPP recovered from filtrate=12.8g
46.4% yield:mad::mad::mad:
Very little DPPP was lost during the procedure. At max a gram of DPPP. But even taking that into account a terrible yield for a procedure that is reporting 90%. Is it possible that some DPPP sublimated during drying. Damn, and just when we think that a appropriate procedure has been worked out.

Anyone else have yields using a procedure like Rosco's on p19?

Pyroz - 10-1-2005 at 20:47

i always get a good solid yield... you might want to let the reaction take place over a little longer period of time. keep you reaction temperature stable around 2C-3C or less.

oh yeah--- you might want to see some damage for yourself. Remember these are .223 rifle shell cases filled with 1 gram of explosive. DPPP vs AP test.

100_2619.jpg - 193kB

Rosco Bodine - 10-1-2005 at 20:50

An experiment is in progress now regarding the reverse order of addition for the peroxidation step , that is to add the precursor very slowly by drops to the well stirred H2O2 at -10 to 0 C . Presently about two thirds of the precursor have been added and the mixture is orange with almost zero crystals , maybe an isolated few crystals but no massive precipitation as when using the other order of addition . No real noticeable fumes either , the entire dynamic of the reaction is quite different .
I plan on leaving the reaction mixture in the salted ice bath overnight when the addition is finished . Will update on the results when I have anything further to report .

Suprise you are not getting a runaway ?

Matsumoto_Hideki - 10-1-2005 at 21:40

Well, I am officially letting the chem department in on this DPPP project of ours.
A collegue of mine thinks that the punjent smell is most defentlyMESITYLENE an aromatic hydrocarbon C9H12 and colour possibly by some crude Mestityl oxide.

Now about adding your reactants in backwards, I tried this once never to repeat it again.. as the result was massive overheating ..think a yellowstone national park geyser... This of course was partly to do with the reaction being done at room temp.

Rosco Bodine - 10-1-2005 at 22:08

Mesitylene and mesityl oxide are both colorless . They are irritants however , so that could be relevant .

Adding the precursor at about one drop every 2 to 3 seconds to the H2O2 in a beaker sitting in a salted ice bath on a magnetic stirrer and having a thermometer in the mixture the entire time , the peak temperature I got was
- 2 C minus two degrees , and the average was about - 4 C , so you are simply not controlling the reaction closely if you got that sort of runaway . There are crystals forming in the reaction now that the addition is finished , and the mixture is stable so far at - 4 C .

[Edited on 11-1-2005 by Rosco Bodine]

Pyroz - 10-1-2005 at 22:37

Very interesting...I wonder what those crystal might end up actually being? humm, curious to know.
I hope more people begin testing the power of supposed DPPP product so we can get an accurate depiction of what is going on here.

Rosco Bodine - 11-1-2005 at 00:31

Two hours after the end of the slow dropwise addition of the precursor , the reaction mixture is now a thick slurry of fine crystals , and the color of the mixture
is bright yellow . A few globules of insoluble black goo are present , a small quantity perhaps a quarter gram total unreacted material from the 100 ml of precursor which was used for the reaction . One test which may shed light on the difference between samples is a side by side identical weight sample , test for weight loss on heating for a fixed time .
I have some very accurate scales for the before and after weighing .

UPDATE :

Eight hours past the end of the addition , after standing overnight , the mixture in the beaker has set up to a semi-solid consistency of nearly white cystals having a very pale yellowish green color . The ice bath is almost completely melted and the temperature of the mixture has risen to 5 C . The pasty mixture is loosened by manually stirring it with the thermometer and is just barely fluid enough consistency to be stirred by the magnetic stirrer set to maximum if given an assist with a little help to get the mixture moving with the thermometer . Some larger globules of insoluble black goo have separated and accumulated on the bottom . Stirring was immediately stopped to avoid breaking up the separated insoluble material and contaminating the crystals . The reaction mixture will be allowed to stand awhile longer in the melted bath and then dumped into a larger container of icewater
to separate the crystals , and rinse them away from the insoluble black goo which separated during the crystallization . There appears to be a couple of grams of the insoluble black material . I wish to dilute some of the separated goo with acetone and see if has a color , but simply appears black as would some concentrated
portion of an intensely colored dyestuff . I am curious as to whether this separated material is the substance responsible for the red tinting of the precursor mixture originally .

UPDATE : After another hour the color of the crystals is faded more and now the color of the crystals is pure white , the temperature is 10 C .

Update : The reaction mixture has been diluted to twice its volume with water and
the crystals have been decanted and rinsed away from the insoluble residue ,
nearly all of which is adhering to the stirbar . I overestimated the amount before and the quantity appears to be no more than a quarter gram to a half gram of insoluble material , which is no longer globular but has solidified to a light brown solid , not really intensely colored as would be a dyestuff but more caramel color of low intensity . The white crystals are very nearly the density of water , sink only slowly and some crystals float or suspend at neutral buoyancy from adherent bubbles of oxygen from the peroxide . There is no noticeable smell except ( I hate to say it ) there is a faint clear clean odor typical of AP , having none of the irritant effects of the product
from the other order of addition . It is too soon to be conclusive , but this stuff looks like AP and smells like AP . I'll know for sure after filtering and drying and doing a weight loss on heating comparison with a sample of known AP made by the usual method .

[Edited on 11-1-2005 by Rosco Bodine]

Nice!

Joeychemist - 11-1-2005 at 08:36

Good work Rosco!

So it would appear that reversing the process will also work, but may produce AP:o:(.Hmmm......:(

Also as i have mentioned before, that brown insoluble junk burns producing a thick black smoke, it is highly flamable but does not deflagrate. I would suggest you try burning a sample.Just to be sure we are on the same page.;):):D

[Edited on 11-1-2005 by Joeychemist]

Is "DPPP" for real or only "tinted" AP ?

Rosco Bodine - 11-1-2005 at 09:15

That is the page we are on about right now . And I intend to get to the bottom of this with some no bullshit analysis and sample comparisons that will nail this down by instrumental measurements and
scientific method which won't leave any wiggle room for opinions or high hopes .

I have rectangular crystals right now from the sublimation overnight of the side by side samples of AP and "DPPP" and the crystals from sublimation of the "DPPP" look just like AP .

The most interesting thing to me at this point is the extreme exotherm that occurs upon the very initial part of the peroxidation when the peroxide is added to the precursor in the usual order of addition , and the irritant byproduct . Both of these things tend to strongly suggest that a quite different reaction mechanism is at work when the reaction order of addition is done that way . I am not yet ready to give up on the idea that DPPP is indeed for real , but there are some good reasons for the skepticisms expressed by Axt and others , even though these would seem to be disproven by the witness plate tests .
I have also wondered if DPPP may actually be AP but occurring as an unusal and unidentified polymer , not the trimer nor the tetramer , but perhaps a "hexamer" form . Sometimes a specific polymer form and crystal form can demonstrate quite different properties from other forms . There are a lot of angles to look at in studying "DPPP" to discover the real story on exactly just what it is , and that could turn out to be different from what Mackowiak says . Let's reserve our conclusions until we do and interpret the results of various experiments which may shed some light on what are valid questions about the curiosity which we are calling DPPP , and which may well not even be DPPP but may not be garden variety AP either .

[Edited on 11-1-2005 by Rosco Bodine]

Cursed!

Joeychemist - 11-1-2005 at 10:37

A different version of AP is a possability. (Maybe we'll get the patent on it) :D As of now I don't know. As I have said Under a microscope I can clearly see 3 different crystal forms, they appear to me to be DCAP,TCAP and what I thought were "DPPP" crystals. maybe I was wrong in asuming it was "DPPP",maybe you're right, maybe their is somthing else happeing. Does it smell like "funky AP" or plain old runofthemill AP?

Maybe we should let Hideki bring it to his school lab, better his ass than ours right?:D

Rosco Bodine - 11-1-2005 at 10:55

About the smell now it is on the filter I can't tell because I neutralized it by flooding it on the filter with 2% ammonium hydroxide , let it drain through and then flooded it again with distilled water , drained and rinsed again with distilled water , leaving a slight odor of ammonia on the still damp crystals which is the only smell I can detect . But before the rinsing and neutralization it smelled like plain AP and looks like AP in every respect but one , it doesn't glitter like AP even though it is snow white in color .

The possibility of a different isomer of AP seems likely . The tetrameric AP is something which looks and smells very close to trimeric AP but has slightly greater power and way less volatility . I haven't quantified the volatility but the terameric sits happily in storage in a loosely covered container for *years* without dissipating greatly , while a like sample of the trimer sitting right beside it and stored exactly the same way is 90% evaporated away . So it is entirely possible to have different forms of AP which generally look and smell the same but most definitely do not behave identically otherwise .

UPDATE : The crystals are very nearly dry and strangely enough the crystals seem to have almost no detectable odor at all ,
not the distinct AP odor that they had when wet . I'll know more when the crystals are completely dry , but as I recall AP has a very slight odor all the time , wet or dry , and these white crystals are at this point of drying nearly odorless which may or may not change when they are dried completely . To my nose regular AP has a slight aromatic odor which is similar to the immediate smell of the discharge of a firearm using ammunition loaded with double base smokeless powder , which could itself be an odor related to traces of acetone used in the manufacture of the cordite .
AP ( in the unburned condition ) smells very similar to that transient smell of fresh gunsmoke which is slightly fragrant and dissipates in a second or two to a heavier smoky odor . Does anyone else detect this , any shooters out there ?

The material is basically dry now and it does have a very faint AP like odor barely discernable to smell by getting the nose right down to a half inch away from a paper plate covered with crystals in a layer 3 mm thick . The smell still seems fainter to me than regular AP , but it has been awhile since I made a batch of AP and what I have on hand is a saved sample . I will let the crystals continue to air out overnight and see if there is any further decrease of the odor before I weigh the product and transfer it to a container for keeping . There is plenty for further testing against the existing sample of "DPPP" which I have already .
I may take the remaining half of the refrigerated precursor and subject it to the conventional order of addition at the same temperature and slow rates as were used for producing this sample to
observe what differences occur using the same batch of precursor both ways .

[Edited on 12-1-2005 by Rosco Bodine]

So if colour isn't coming from Mesityl oxide ?

Matsumoto_Hideki - 11-1-2005 at 17:36

Well, why would one say mesityl oxide perhaps this person ment mesityl oxide interating with chlorine
forming a benzene chloride ???
Again i am having the university figure this stuff out for us/// we will soon get some resuts.

PainKilla - 11-1-2005 at 19:32

Mesytil Oxide itself is a ketone and can (I would assume) form peroxides....having discussed this with mumbles eariler, I think it's been concluded (others have doubts as well) that this is NOT DPPP, but possibly even TCAP... which would not surprise me, since every thing seems about the same. Benzene can form peroxides too, so it could be that we are getting some wierd benzene peroxide. I can't pretend to know though as I am still a super novice in chem. What does puzzle me however is where exactly this colour is actaully coming from, as mesitylene and methyl isobutynel ketone (mesytyl oxide) are both basically clear or pale yellow. I can't imagine any Cl compound making a deep deep red, but where else could the answer lie..... I am expecting some intersting results soon from a certain someone ;).


Also, I am sure SOME phorone is formed, but I think it plays little or even no role in foming this compound. They have disticnt melting and decompostion point, so if anyone would like to test this out.... Also, is there crystals (I dont remeber...thread is a WEE bit too long) when the "DCP" is frozen.....because there SHOULD be assuming phorone IS actually formed..... from what I recall there is not and this further leads me to believe that no actual phorone is made. With "DCP" I think its melting point would be lower, but nontheless still achievable with freezer temperatures, again, I am not the most advanced person in the field (translates to I suck) but it should be tested as much mroe conclusive results may be obtained whenwe actually know what we are working with....

This could be some derative of chloroacetone too, speaking of which if phorone is not a byproduct... then you better watch how you handle this as neither benzene (or benzene/zyl?l chloride) are pleasent things to be working around, and neither is chloroacetone or mesytilene compounds in general... basicallly be careful :)....

What are more proficeint in chemistry peoples' input on this? Also, does chloroacetone form peroxides of any kind?

[Edited on 12-1-2005 by PainKilla]

Rosco Bodine - 11-1-2005 at 19:48

The focus at this point is as I understand it is to rule in or out that what we have been calling DPPP , may be a form of AP , either regular AP contaminated or coordinated with some other substance , or possibly AP in some unknown state of polymerization . The side by side sublimation experiment with parallel samples sitting in the same bath in identical culture tubes were producing
identical results when I checked a few hours ago . In effect I am slowly distilling
the solid samples from the bottom of the culture tubes and condensing and crystallizing the vapor on the colder upper
inside surfaces of the tubes . The accumulation of crystals from sublimation are depositing at the same rate and look identical , both white rectangular crystals .
A melting point on each respective type of the sublimed crystals , followed by a melting point on a mixed sample of the two will be revealing . If all three melting points are the same , the two samples of sublimate are the same substance .

I just happen to have on hand some melting point capillary tubes .

Pyroz - 11-1-2005 at 20:38

--they certainly don't act the same when detonated.. they may appear to be the same crystal- wise but they must have different densities.

[Edited on 12-1-2005 by Pyroz]

PainKilla - 11-1-2005 at 20:41

Yes but this could also result in different cooling techniques....when I left my AP in subzero temps, I got crystals nearly impossible to see, and it was very dense and detonated seemingly stronger....it just turned it it was standard TCAP/DCAP with small crystals.... try making AP exactly the same minus the heating and then test the results. I have a feeling this is just regular AP, at least for some of us.



[Edited on 12-1-2005 by PainKilla]

Rosco Bodine - 11-1-2005 at 20:50

The tests certainly suggest something is different about the two substances explosive power . But why ? Suppose that what is being identified as DPPP is actually a binary compound or composite of AP along with something else which is an unknown volatile explosive substance , or a substance which acts as a detonation catalyst for AP , and possibly for other substances as well . The unknown material being responsible for the apparent power of DPPP might be an effective additive for other explosives .

The_Davster - 11-1-2005 at 20:53

I personally feel that "DPPP" is different from regular CTAP. Whether the structure of diphorone pentaperoxide is correct in the patent or if this is some AP varaint( >trimer), Just from what I have observed this does not seem to be the plain old garden variety of AP.

In any case I am eagerly awaiting the results from Matsumoto_Hideki's university.

Unfortunatly my experimentation is on hold for a few weeks due to exams. I do not experiment too close to exam time after an incident in which I got a bad mark on an essay as a result of ( I believe) exposure to chloroform fumes the night before(Oh, and because I must study ;)).



[Edited on 12-1-2005 by rogue chemist]

strange

Pyroz - 11-1-2005 at 20:56

The "DPPP" product was tested against 1gram of cold formed AP (made at -2C) not warm flakey stuff. I'm all too familar with the difference between cold formed AP and AP formed at 10C+. So this is why I'm thinking something else is going on here. I have done test after test and each time ---"DPPP" looks if it has at least double the power of the 1gram AP charge, if not, more.
I am finding all of this truely bizarre.
------------------------------------------
*news flash* I just finished baking some AP in my oven on 110F. The AP is gone--- completely vapoured off while the DPPP has formed a white crust which smell like the inside of a pingpong ball---reminds me of an acidic camphor. Its still very explosive after heating. Interesting :) you may want to try this out for yourself.

[Edited on 12-1-2005 by Pyroz]

Rosco Bodine - 11-1-2005 at 21:16

Indeed it is a thought provoking line of investigation which we are about here .

The "melting point analysis" which I mentioned above is a very old but reliable tool for analysis , and I hope it will be one of the conventional tests done by others at the decently equipped laboratories where this sort of testing is pursued .

It seems every idea I have involves more work for me . And since I don't have a regular melting point apparatus I have to do each of such tests absolutely manually . Such tasks are so easy with all the right equipment .

I believe I will run the synthesis again on the other half of the precursor , using the more conventional order of addition of adding the peroxide to the precursor , so I can compare the product from the different methods run at identical temperatures . Then I need to take a break because of other business which requires my time . The followup tests can be done later with the samples in hand .

[Edited on 12-1-2005 by Rosco Bodine]

PainKilla - 11-1-2005 at 21:28

Well it seems that tradional AP is not formed but i still thing SOME sort of AP is formed... perhaps some chloroacetone derative, with the Cl acting as an extra catalyst or something, maybe its tetrarameric AP, or maybe even pentameric? It's late but I will do the stiochimetry tommorow and see if it works out relative to the ratios for DPPP....

Rosco Bodine - 11-1-2005 at 21:43

Tetrameric is a more dense and reflective material than the trimer which is as refective as frost itself . Tetramer crystals are heavier and more coarse granulation than the trimer . This material we are calling DPPP is very close to density of water , at least the unrecrystallized material is fairly low density near 1 g / cc for the crude material , and it does not have that reflective crystalline glitter , but has a more matte white appearance . Now the sublimate from the sample of DPPP does glitter like frost in sunlight .
So go figure .

[Edited on 12-1-2005 by Rosco Bodine]

The_Davster - 11-1-2005 at 21:49

Quote:
Originally posted by Pyroz
*news flash* I just finished baking some AP in my oven on 110F. The AP is gone--- completely vapoured off while the DPPP has formed a white crust which smell like the inside of a pingpong ball---reminds me of an acidic camphor. Its still very explosive after heating. Interesting :) you may want to try this out for yourself.

[Edited on 12-1-2005 by Pyroz]

Yay, acidic camphor, also known as chlorobutanol. The smells of camphor and chlorobutanol are very close. :D So now we know that the same variety of "DPPP" can be produced by heating the pale yellow variety of "DPPP" as can be by allowing the reaction mix to stand overnight after peroxidization.
Quote:
Originally posted by Rosco Bodine
and it does not have that reflective crystalline glitter , but has a more matte white appearance .

The "DPPP" I recieved after allowing to stand overnight did have a reflective crystalline glitter and was not as powdery as the pale yellow "DPPP", some very small crystalls were visible.

EDIT: I keep spelling "pale" as "paly" :mad:

[Edited on 12-1-2005 by rogue chemist]

Rosco Bodine - 11-1-2005 at 22:02

Yeah that's one of the reasons I need to repeat the synthesis at the same temperatures and see if the crystals
would look more similar in size and reflectivity . The slower crystals form ,
generally the better their appearance .
I'm really mostly interested in purity ,
not so much focused on appearances
because I know that can vary greatly
even for the same pure substance .
Color however is another matter entirely
and since my existing sample of DPPP is
slightly tinted yellowish , I want to try to
get a sample of the white product from
the next synthesis .

[Edited on 12-1-2005 by Rosco Bodine]

So this verifies the formation of Phorone as well !

Matsumoto_Hideki - 11-1-2005 at 23:11

In order for chlorobutanol C4H7Cl30 to be produced it has to be forming around the cracking of acetone to phorone.

DPPP sublimed crystals are Cubical !

Rosco Bodine - 12-1-2005 at 07:21

There may well be a difference developing in the two samples which I have been subjecting to a slow sublimation in order to visualize any obvious differences between the sublimed crystals from DPPP and sublimed crystals from AP . Now that the sublimation has continued for a couple of days , the crystals have grown much larger and are easier to see the difference . While the sublimed crystals of DPPP and AP are both of rectangular shape and white and shiny reflective appearance , the AP are long rectangular
form crystals which are characteristic of AP , but the sublimed crystals of DPPP are definitely cubical and distinctly different in appearance .

Hot fucking damn !

I am tickled shitless :D

Anybody out there please verify me on this . The results take a couple of days to develop . It's a simple slow sublimation test of parallel samples in test tubes .

I have to try subliming my DPPP

Matsumoto_Hideki - 12-1-2005 at 08:53

I am going to sublime my DPPP and see this for myself!
what temperature did you sublime it at?

couple of days ago I tried to see if there was any AP forming with my DPPP so I sunk it in hot water (80-90c) in a bag for approx 15min. Results were nothing, other than a very acrid smell of what we now know is chlorobutanol.

chemoleo - 12-1-2005 at 09:04

Interesting. Pictures please! I take it this sample is the one obtained from the reverse process, i.e. the acetone/HCl being poured into H2O2? Really, of course this has to be done with putative DPPP prepared the original way.

This also confirms the purity of the putative DPPP, else you wouldn't be getting crystals that grow large. Does it look like there is a small amount of left-over that doesn't sublime?
Anyway, a word of warning- from protein crystallography I know that a tiny change in conditions, or the presence/absence of tiny impurities or weakly binding ligands can completely change the crystal geometry, I know of cases that the very same protein, just crystallised in a different buffer, produces once hexagonal, and once crystal needles. Of course this is less a problem for smaller molecules, but it is an issue that shouldn't be forgotten.
And from rectangular flat it's not far to rectangular cubic.

Now, this may or may not be a problem - but it definitely needs further confirmation, preferably by power or something. Plus, the fact that the putative DPPP volatilises is in contrast with what is stated in the original patent.

[Edited on 12-1-2005 by chemoleo]

Rosco Bodine - 12-1-2005 at 09:13

For the sublimation test I am using Sarstedt brand clear polyproplylene culture tubes equipped with a two position venting / sealing polypropylene snap cap , capacity 13 ml . In the bottom of each culture tube is placed a quarter gram sample and the cap is placed on the tube to the first venting position . The two tubes are placed through holes in a support so that they are supported at their upper portion by the shoulder on the cap which is too large to pass through the hole , The lower portions of the two tubes hang freely in the air down to the surface of a small water bath kept at about 70 C , with the lower 2 cm of the tubes immersed in the hot water . Oil would be a better heating medium because the water keeps evaporating and has to be refilled periodically . Anyway , after the initial heating of an hour or so any residual moisture is driven out of the samples and condenses on the inside of the cap and inside surfaces of the upper portion of the tube . The cap is removed and the trace of moisture evaporates on exposure to the air after a few minutes . Then the cap is put back on the tube and the tubes returned to the heating , and after a few minutes the caps are snapped down to the sealing position . The sublimation then proceeds very slowly over several days as the samples are kept warm in the lower part of the tubes immersed in the heated bath , and the vapors are condensed and crystallize on the inside surfaces of the cooler upper portions of the tube . This proceeds very slowly but is a revealing test about the difference in crystal shape for the sublimed materials .

Chemoleo : The sublimation sample is from the first synthesis of DPPP , the yellow colored material which reeked of the irritant impurity , and was made by the addition of peroxide to the phorone dihydrochloride precursor . The sublimation test was already in progress before I began the reverse order of addition peroxidation experiment .
I don't have a good enough macro lens for my digital camera to show the samples , but the cubical crystals are clear , reflective , and about three times the dimensions of table salt . In comparison , the AP crystals are double the dimension at the square cross section and three to four times that edge dimension in length , a very significant difference , not subtle at all . Also the AP cystals are white and have an opaque lamellar structure like mica , they are not crisp clear icelike transparent as are the DPPP crystals .

There is indeed a brown residue accumulating from which the light yellow DPPP sample is subliming , so the coloration is indeed an impurity , and the color of the pure DPPP is white or clear colorless .

[Edited on 12-1-2005 by Rosco Bodine]

$0meb0dy - 12-1-2005 at 09:57

Tried DPPP again today.
I used dark red aceton/HCl mix from a few weeks old, so I think the chance that it still contains aceton is pretty small, it's very dark at this point witch a green tint in it, you see the green when there is a very thin layer on the glas after moving it.

I cooled it to around 0C, then I added H2O2(30%) till the reaction stopped and keeping the temp. under 7C.
The mix was bright yellow and there were pretty much fine crystals.
I filtered it and the crystals were white and the filtrate was bright yellow.
It's drying now, I will do some test compared to AP.

Rosco Bodine - 12-1-2005 at 10:20

One thing I can tell you is you don't want to keep the phorone dihydrochloride precursor "for a few weeks" even in the refrigerator the polymerization continues slowly . It should be used for the peroxidation within a couple of days after preparation , and probably stored in the freezer or refrigerated at least .
Otherwise filtering it before peroxidation would be a good idea , because if not , you will have insoluble material in the mixture which won't peroxidize and will precipitate as a globular impurity with the crystals . The proportions and time of reaction for the precursor are tenatively worked out at 93 ml of 31.45% HCl to 100 ml acetone , in a sealed bottle self reacted for 1 1/2 hours and then supplementally heated at about
65 C for 2 1/2 hours to development of a deep red but transparent liquid which appears bright yellow in thin layers swirled against the inside of the sealed bottle . The details have been described in preceeding pages where we are trying to standardize the method . For anyone reporting results , please give all relevant details so that we can all make reasonable conclusions of what the data means .

[Edited on 12-1-2005 by Rosco Bodine]

Rosco Bodine - 12-1-2005 at 11:17

Quote:
Originally posted by rogue chemist
Quote:
Originally posted by Rosco Bodine
Are you going to weigh your yield and do the math to get the percentage ?
( 27.57 grams would be 100% of theoretical ) 24.8 grams would be 90% of theoretical .


11.6 g of pale yellow DPPP + 1.2g pure white DPPP recovered from filtrate=12.8g
46.4% yield:mad::mad::mad:
Very little DPPP was lost during the procedure. At max a gram of DPPP. But even taking that into account a terrible yield for a procedure that is reporting 90%. Is it possible that some DPPP sublimated during drying. Damn, and just when we think that a appropriate procedure has been worked out.

Anyone else have yields using a procedure like Rosco's on p19?


The dried *unknown* product from my reverse order of addition peroxidation experiment has been weighed and the yield calculated at 79% of theoretical based upon acetone if the product is DPPP.

The dried *unknown* product smells distinctly different now from the AP like odor it had when still damp . After a couple of days of airing out the odor seems to have stabilized on the dry white material , and the odor is very faint , an inseciticidal odor which smells like the natural pyrethrin based sprays such as are used to spray sleeping bags and tents to clear mosquitoes . That is exactly the smell of the dry crystals , like pyrethrin based bug spray not irritating and a very faint odor .

79% is more closely aligned with the figure of 90% stated by the patent so I am hopeful I may be onto something here but it is too soon to have any solid conclusions because no tests have been done yet on the product .

The precursor had been made from 112 ml acetone and 105 ml HCL 31.45% as described earlier , in a sealed bottle self reacted for 1 1/2 hours , then heated gently for 2 hours at 65 C to obtain the ruby red solution , allowed to stand overnight , and then refrigerated for keeping until the experiment a day later .

A 100 ml portion of the above precursor was added dropwise over the course of 2 hours to 130 ml of H2O2 26.6% , well stirred in a beaker sitting in a salted ice mixture , at a temperature range of -5 to a peak of -2 C . The detailed real time description of the experiment was posted earlier absent these details . I won't retype the entire experiment description that was posted earlier , but you can refer to the earlier posts for all the other details . The weight of the dried material is 41 grams .

UPDATE : A quarter gram sample of the material from this experiment has been placed in a culture tube and added to the other tubes partcipating in the sublimation test . A fair amount of moisture was driven out of what I supposed was a dry sample after it was warmed so it is evident that some gentle heating for a day or so should be used to complete the drying of these samples before they are considered completely dry . The moisture content has skewed my yield calculation also , so the 79% yield I first reported is likely closer to 74 or 75% .

[Edited on 12-1-2005 by Rosco Bodine]

Mickhael - 12-1-2005 at 12:55

Wow...long thread, and execelent work being done! I'm very glad you are doing these tests Rosco, since I know myself at least would not have the inclination for taking the time to make apperatus for these fairly conclusive results. I think my max yield so far has been around 60%, but I think my precursur has sat to long, and was heated to long for much better results then that. Its also very nice to read clear and concise results and methods...since there far to many dummies making statements without backup or method. My crystals I have left (about 25g) have lightened alot but still have a yellow tinge, in the camera flash they look white, however in normal light the yellow is still there.

I have tried about 0.6g in duct tape and that made a decent bang alright, left a hole in the snow bank about 8" across...I'll be trying a mix of MEKP/DPPP tomorrow...I'll post the results. I'm also very much looking forward to hearing what the lab analysis will be, if it can't b gotten for some reason, I may be able to get some myself through a couple contacts...what was the 100% liquid it was said it should be desolved in for lab tests? deuterated methanol. Where might it be possible to find that? thankyou

[Edited on 13-1-2005 by Mickhael]

alright I have one result to share, THIS IS MAJOR

Matsumoto_Hideki - 13-1-2005 at 00:16

The colour red-black is NOT being caused by Phorone itself but by a precusor to phorone called mesityl oxide as it stands at room temp or higher colour degrades from clear to yellow to red then to black at
this then becomes Phorone HCl when the peroxide is added. The mesityl oxide starts to digest into Phorone & related HCl's then into Pentachlorophorone and then finally crystallizes into DPPP with the release of Cl2 with some chlorobutanol as byproducts . The yellow colour is due to a chlorinated byproduct? not sure yet..
http://www.cdc.gov/niosh/ipcsneng/neng0814.html
This result was forwarded to me from a chemist at my university!!
:o

BTW this proves that the extreamly powerful explosive peroxide is indeed a PEROXIDE OF PHORONE and not a simple trimeric actone peroxide!


[Edited on 13-1-2005 by Matsumoto_Hideki]

[Edited on 13-1-2005 by Matsumoto_Hideki]

[Edited on 13-1-2005 by Matsumoto_Hideki]

yeehaw...

Pyroz - 13-1-2005 at 00:27

*information from labratory test so far*
I gave a chem grad a challange to make the infamous D.P.P.P explosive to synthasize and here is what he found out:

"Adding Acetone to equal parts of HCL(aq) gives the product MESITYL OXIDE after the material is left to digest. When further HCL is added as a cataylist and conc. Hydrogen peroxide is added to the MESITYL OXIDE. MESITYL OXIDE turns into a PeroxyPhorone when conc. Hydrogen peroxide is added. During the addition--- crystallization occurs instantainously with a bright yellow chloride by-product which settles in with the very pale green crystalline mass.
Further filtering of the crystals is needed to purify the product in a solvent. The yield is very high --- upwards of 70%, and in larger batches could be in the high 80% range. The theoretical explosive properties (while unmeasured) would put peroxyPhorone in a very powerful class of explosives well beyond that of a regular trimeric-Peroxyacetone due the complexity and strength of its molecular bonds and mass. Further testing needs to be conducted here to determine true VoD."

[Edited on 13-1-2005 by Pyroz]

Hmmm...

Joeychemist - 13-1-2005 at 02:22

Could you guys maybe show some proof to back these theories or at least tell us what leads you to believe this is mesityl oxide?

What exactly have you told the "people" from you're school about this? Have you given them the work that we have so far or are you makeing them start from scratch? Do they know that it might be another explosive?, they might want to test samples of AP next to "DPPP" side by side.Do they have a copy of the patent, both original and translated versions?

And hideki, when you gets those results from school please scan all the work onto you computer, so you can attach it as a file for all to read.
;)




[Edited on 13-1-2005 by Joeychemist]

Mesityl Oxide

chemoleo - 13-1-2005 at 03:08

Interestingly, in the MSDS of mesityloxide ( (CH3)2C=CHCOCH3), it says it is a colourless viscous liquid of bp 130 deg C, and a liquid that darkens on standing that has a characteristic odor.
The fact that the solution is indeed dark, or gets increasingly darker seems to support this. In addition, it mentions it is only barely soluble in water ( g/100 ml at 20°C: 3.3 (moderate)), and specifically that its density is LESS than water, i.e. 0.86 g/cm^3.

So- this seems something that MUST be tried and tested!

1) incubate the HCl with the acetone, until the colour is black/dark red.
2) Add water, mix thoroughly and for some time, and see if you can separate an upper insoluble layer, which should be mesityl oxide. This should be fairly viscous!
Also, bring a small amount of this upper insoluble layer to the BOIL, and measure the temperature - it should be at 130 deg C or thereabouts (once water & unreacted acetone has boiled off- so boil for a good while!)!
3) If 2) works, add more HCl to get the dichloro version, and add H2O2 to see if this is what is needed to get a precipitate!

Furthermore, I checked Orgsyn.

It gives a method straight from diacetone alcohol, but more importantly, it lists several references on the production of mesityl oxide from acetone! It says 'the yields are poor and considerable quantities of phorone and similar substances are invariably produced'. It might be good to look up some of those references and see which ones produce most mesityl oxide and phorone. See for instance: Fitting, Ann. 110, 32 (1859); Heintz, Ann. 178, 343 (1875); Claisen, Ann. 180, 4 (1875); Freer and Lachmann, Am. Chem. J. 19, 887 (1897); Currie, J. Am. Chem. Soc. 35, 1061 (1913); Couturier and Meunier, Compt. rend. 140, 721 (1905); Mannich and Hâncu, Ber. 41, 574 (1908); Bodroux and Taboury, Bull. soc. chim. (4) 3, 829 (1908); Yllner, Svensk. Kem. Tids. 37, 227 (1925) [C. A. 20, 739 (1926)]; Gasopoulos, Ber. 59, 2188 (1926); Brederick, Lehmann, Schönfeld, and Fritsche, Ber. 72, 1417 (1939).
I am sure one or two of these should be accessible for you. Please be sure to post a scan!

However, there is also a proper preparation of diacetone alcohol in OrgSyn, which employs Ba(OH)2 and acetone, and which is used directly for the production of mesityl oxide , which in turn can be peroxidised to hopefully give DPPP or some peroxidised derivative thereof!
There's plenty do do and to test!!

[Edited on 13-1-2005 by chemoleo]

Rosco Bodine - 13-1-2005 at 06:45

Before I put forth my own theory about the polymerization of 3 acetones to a trimer called triacetone dialcohol and its subsequent condensation with 2 HCl's to form phorone dihydrochloride while freeing
2 H2O's , the route through mesityl oxide was considered . For reasons I don't recall now it did not seem to add up . It has been a month ago now and I didn't make notes , but did read that organic synthesis article along with several patents which are related . What I do recall is that I became certain that phorone itself is not a reactant in the synthesis as Mackowiak has it written ,
but that the triacetone dialcohol which Mackwiak does show , reacts as it forms directly with the HCl in a condensation reaction to form phorone dihydrochloride , as the product of that condensation , without any intermediate formation of free phorone itself . I still hold to this theory . And it will take more than a contradictory opinion from a PHD with no citations or proofs to convince me otherwise , since it is already stated in the literature generally that polymers of acetone are known to be reactive to chlorination , and other reactions , as well as to continue formation of higher acetone polymers ultimately resulting in materials which are solid plastics at room temperature .

And one thing I do recall is that the process of acetone polymerization is definitely affected by the severity of the conditions , aqueous versus anhydrous , low temperature versus high , and pH and catalyst sensitive . It is not a process where a simple reaction mechanism stated for one set of conditions applies to what happens with the same reactants under different conditions . The conditions for the formation of the precursor for DPPP are at the mild end of the spectrum for reaction conditions which would lead to mesitylene
at higher temperatures and anhydrous conditions , for example 150 C with concentrated sulfuric acid and distillation of the product would produce substantial amounts of mesitylene , but not likely for an aqueous reaction mixture af acetone and HCl ~ 30% at 65 C for 2 to 3 hours .

Mesityl oxide is something I will look at again and try to recall why I also considered it unlikely , but I believe that it was for the same reasons that the reaction conditions were unfavorable for its formation .

chemoleo - 13-1-2005 at 07:04

Well, whoever prepares the next batch, could you please check whether the dark solution is soluble in water, and, if possible, the boiling point? If it is soluble, at least that will rule out mesityl oxide, and peroxidation products thereof. Case closed. Experiment proves theory, not vice versa. Damn, I will try this myself later this week.

As to whether the formation of mesityl oxide is likely or not - I'd be delighted to have a look at these references to see what conditions these authors employ to obtain mesityl oxide (and what conditions specifically exlude the formation of mesityl oxide). As I said above, it seems difficult to get clean mesityl oxide by acetone condensation and consecutive dehydration (see orgsyn reference), as multiple byproducts, including phorone are produced.
It's only a question of how much phorone, acetone alcohols, mesityloxide, chlorinated derivatives and mesitylene are produced in a given set of reaction conditions, as these things are all in equilibrium.

Anyway. Let's just test it shall we. If the black viscous oil is completly and easily soluble, we KNOW that mesityl oxide itself does NOT produce the precipitate lateron. If it forms a separate layer, we KNOW it COULD be mesityl oxide. It could be other things too, of course.
But please, do quote those conditions of those papers that you looked up that are required to PREVENT the formation of mesityl oxide. If those conditions are identical/similar to ours, then I guess it's unlikely that mesityl oxide is a major player. But the experiment could ultimatley confirm this too (solubility test).


[Edited on 13-1-2005 by chemoleo]

Solubility test;

Joeychemist - 13-1-2005 at 08:18

I took the Phorone Dihydrochloride precursor I would normally use in the synthesis to be peroxidized to form the “DPPP”, not the over heated week old decomposed precursor like with Rosco’s first bottle test, so there was only a few ml of the upper oily layer in the solution.

I poured 50ml of Phorone Dihydrochloride down the side of the beaker into 100ml water at room temp.
I received 3 layers in my beaker,

The bottom layer was a cloudy orange color, I could tell that some of the precursor had dissolved in the water which increased the bottom layers volume slightly.

The second layer was water, slightly tinted orange but was over all clear water,

The top layer (the clear “oily” layer, that floats atop the Phorone Dihydrochloride) is *NOT* soluble in water, It also slowly “sheets” across the glass as opposed to water which runs down the side very fast so it is viscous.

It took a little stirring to get the two lower layers homogonous, but it has 1 hour since and the two still seem to be an homogonous mixture. The upper oily layer remains un-fazed by all of this.:o

I don’t have enough of the top layer to test the boiling point but I have started another batch and we’ll see then.
:D

chemoleo - 13-1-2005 at 08:46

Interesting. Is it possible you can take a picture and attach it, i.e. the original sample and what it looked like after mixing with water and settling?
Also, what's the smell of the upper layer like? Acc. to the MSDS it is fairly strong and characteristic. If it barely smells presumably this won't be mesityl oxide.
Anyway - it would be interesting to see if each of these layers could be peroxidised, after adding a bit of HCl.

[Edited on 13-1-2005 by chemoleo]

Joeychemist - 13-1-2005 at 09:00

Nope, no pictures, No camera and no scanner, someday perhaps.:(

The upper layer is pungent “sweetly acidic” if that makes sense, but I can’t really tell a big difference between the lower layer and the upper insoluble layer when it comes to smell. As I said I have another batch brewing and will try to separate the two layers, then I will try the boil test and I will try to peroxidise both layers as well.

Full report about DPPP synth will be posted ASAP

Matsumoto_Hideki - 13-1-2005 at 11:53

I will post the report form my universities team of organic chemists on DPPP synthesis, so far as I said the darkening colour (clear to thick black-red) is mesityl oxide that is a known fact, Phorone is also produced along side this reaction as well at much much higher amounts.

what is known at present
1) DPPP is being formed as the peroxide
2) Mesityl oxide is responsible for the initial colouration (black red) before peroxidation
3) Smell of crude DPPP is caused by Chlorobutanol (camphor like).

Unknown
1) how is DPPP forming exactly
2) yellow colouration of DPPP is ?
3) Exact DVol we do know that it detonates extreamly fast and is 6x more powerful than TCAP.
4) best temperature for sythesis?

Theoretical

Rosco Bodine - 13-1-2005 at 15:01

In the first and only synthesis of DPPP which I have done so far using the conventional order of addition of the peroxide to the precursor , I was applying a certain rationale which is suggested by the Mackowiak patent where he shows that H2O2 is "catalytic" in the formation of the phorone dihydrochloride from phorone . I disagree that the reaction proceeds exactly as Mackowiak has written , but I agree that H2O2 may be catalytic in the formation of the phorone dihydrochloride , only not from phorone .
What I guess is occurring is that triacetone dialcohol is being produced and then condensing with HCl to produce phorone dihydrochloride from the initial self reaction which then slows because water being produced dilutes the acidity which has been catalyzing the polymerization of the acetone , and the amount of HCl present is actually being reduced at the same time as it ties itself to the triacetone dialcohol to form phorone dihydrochloride . The self reaction starts intensely and then quickly tapers off because of the unfavorable equilibrium increasing with the reaction which quenches the self reaction in its own product mixture . Then we have to add supplemental heating to make the reaction continue at a reasonable rate .
Heat increases the rate of polymerization of the unreacted acetone to triacetone dialcohol in the mixture in spite of the lower acidity and more phorone dihydrochloride forms until we have that deeply colored ruby red but still transparent mixture . However some free acetone and free HCl still remains in the unreacted state even in the "matured" phorone dihydrochloride mixture . Now this is where the first drops of hydrogen peroxide added to the precursor mixture have their catalytic effect , in much the same way as peroxide catalysts are used as a polymerization catalyst for styrene and polyester resin , the addition of a small amount of peroxide further kicks the polymerization of any unreacted acetone to form the trimer , triacetone dialcohol and subsequent condensation with the available HCl remaining , completing the
conversion of the precursor mixture to phorone dihydrochloride during the initial addition of what many are calling the "peroxidation" step . The so called peroxidation step is actually 3 sequential and partially overlapping reactions , with any actual "peroxidation" occurring only in the third stage of the reactions which occur over the course of the peroxide addition . Initially , the first addition of a small amount of H2O2 has the effect of completing the formation of the phorone dihydrochloride , which prior self reaction and supplemental heating has not fully driven to completion . That is precisely the theory which made me believe that it is perhaps best to run the initial part of the "peroxidation" warm , not cold , in order to complete the polymerization of any unpolymerized acetone in the presence of H2O2 in catalytic amount , along with gentle heating of its own exotherm , much the same way as one would employ a heat lamp to speed the curing of polymerizing fiberglass resin , knowing that gentle heating and the catalyst both help to complete the polymerization . As the addition of peroxide continues , the phorone dihydrochloride is converted to pentachlorophorone , and I am uncertain
as to whether this "second stage" may also be a reaction
aided by warm temperature , or if it is a simultaneous reaction involving the formation of DPPP by immediate decomposition of the transient unstable species which pentachlorophorone may be , never existing as a stable and distinct intermediate precursor , to which the entire batch of phorone dihydrochloride is fully first converted before any DPPP begins to precipitate , so I am uncertain about what is the most favorable reaction temperature . I strongly suspect that these reactions all three overlap to an extent and the optimum thermal curve is something which begins warm at the beginning of the addition of peroxide and then supplemental cooling is optimally coordinated with the peroxide addition to ramp the temperature *downward* lower and lower as the addition of peroxide proceeds , and that this is the *only* way that any 90% yields would ever be possible , by driving the reaction along an optimized thermal curve , where the reaction temperature corresponds with the amount of peroxide having been added at any point in time , the whole time the temperature is dropping . Now that's what my theory on this reaction is and why it would take some fancy equipment to ever get any 90% yields .
It would be my guess that using any standard lab method , non-industrial process , will likely be doing good to get
60-70% yield .

In my next experiment I plan to test this theory by starting the peroxidation slowly and allowing a gentle exotherm at first , and then regulating the addition so the temperature of the reaction is actually falling over the course of the remaining addition , as the beaker sits in a salted ice bath . Then I'm going to let the reaction mixture sit there in the cold until loss of color , and hopefully loss of the disgusting irritant impurity which complicated my first experiment with an impure product from a reaction not allowed to proceed to completion .
I think I'll also make a fresh batch of precursor for the next experiment to
remove that variable . I have suspicions that our unidentified nose and eye stinging irritant may be unperoxidized pentachlorophorone .

chemoleo :

The upper layer of acetone HCl advanced reaction polymerization condensate is not mesityl oxide . It is a yellowish brown transparent oil which has a smell like scorched vegetable oil or linseed oil , only milder . It is alcohol and water insoluble , soluble in acetone . It solidifies to a hard residue upon exposure to air for a day or so . If mixed with concentrated HCl and heated , it reforms the ruby red solution from which it precipitated .

Matsumoto : Please share my post here about the "Theoretical" with your scholarly friends . Also have them look at various HCl to acetone ratios for the preparation of the precursor , including the ratio I like at 93 ml HCl 31.45% to 100 ml acetone in a sealed bottle self reacted for 1 1/2 hours and then heated at 65 C for 2 hours .

[Edited on 14-1-2005 by Rosco Bodine]

Range test of filtered DPPP coming this saturday

Matsumoto_Hideki - 14-1-2005 at 09:35

I will be conducting BIG tests of DPPP this weekend at a range. I will be testing the DPPP detcord as well as a shaped Al charge. It should be interesting. I am borrowing a pro digital movie camera to capture the video to 30fps DV.
I am going to try and edit/compress the movies into MPG4 to get them to fit them on this forum. we will see !

MEKP/DPPP Tests

Mickhael - 14-1-2005 at 10:25

Now I don't know all the proper methods, but I'm attempting to test a MEKP/DPPP 4/1 = 1.25g mixture, sealed in tubing, detonated by fuse...in just a min.

Results: I think I should have had the mixture more contained and sealed in, because an air bubble formed around the fuse, which caused a small explosion - delay - second larger explosion, this is all pretty tiny, but with a decent pop. Container is nowhere to be found, all I could find was a small piece of fuse that had been burnt on the outside before the detonation. Obviously a plate test of some sort would be helpful and I'll work on that. Do I have to use a shell casing for that?

The DPPP seems to mix with the MEKP ok, making the liquid cloudy and thick with crystals, although they stayed clumped up a little. I'll try some more, but let the mixture sit and see if there are further reactions and if it remains stable.

[Edited on 14-1-2005 by Mickhael]

Rosco Bodine - 14-1-2005 at 10:58

The sublimation experiment has reached endpoint on the first DPPP sample which had the light yellow color , and a brown nonvolatile residue remains in the tip of the culture tube , which appears to have been maybe 2% of the volume of the original sample , while all of the sublimed crystals are colorless . Towards the end of the sublimation , a very few of the rectangular crystals having the white opaque appearance of ordinary AP crystals appeared , estimated at maybe 3 or 4% of the sample , while the bulk of the sublimed crystals are cubical and colorless . A similar result is developing for the reverse order of addition experiment where the precursor was added to the peroxide , cubical crystals are the sublimate , and the crystals are clear colorless , and different in appearance from the crystals subliming from the garden variety AP control sample . From this initial experiment with sublimation I have a few preliminary conclusions . DPPP is colorless when pure . And DPPP sublimes to form cubical crystals upon condensation of the vapors .
The DPPP condensed crystals are clear colorless cubes , while AP condensed crystals are white opaque rectangular having a length 3 to 4 times the square edge dimension . In the DPPP samples is
a small quantity of material which appears
to form a minority of crystals which are consistent in appearance with the crystals
sublimed from the AP control sample , but the large majority ~ 95% of the sublimed crystals from the DPPP samples are of different appearance from the sublimed crystals of the AP control sample .

[Edited on 14-1-2005 by Rosco Bodine]

The_Davster - 14-1-2005 at 13:03

Has there been any difference in the ammount of "non-DPPP" crystalls between the sublimate of pale yellow DPPP and DPPP produced in the reverse order of addition?

Rosco Bodine - 14-1-2005 at 13:17

The sample of DPPP from the reverse order of addition experiment has not yet completed sublimation and it will be probably another three days before I will know what sort of mix there may be from that cleaner sample . I am setting up an experiment today with the conventional order of addition , letting the reaction run warm at first and then letting the temperature fall steadily as the addition of peroxide proceeds . There has been some discussion lately about the upper layer that separates after long reaction of the precursor mixture . It seems people forgot that I did test the response to peroxidation of the upper layer in my original sealed bottle experiment , when I later stirred the two layers into an emulsion and peroxidized the emulsion , finding that the lower layer was selectively peroxidized while the upper layer separated unreacted . That was the result which led to efforts at optimizing the procedure for producing the precursor optimized in yield for the red soluble material which does peroxidize , even without ever really knowing for certain what was the actual composition of the upper layer , we could know it wasn't what we needed for the peroxidation .

Update : 47 ml HCl 31.45% and 50 ml acetone were placed in a sealed bottle and after standing 1 hour was then heated at 65 C for 3 hours . A 500 ml tall form beaker
was placed in a plastic bowl sitting on a magnetic stirrer and a stirbar placed in the beaker . The beaker was surrounded by ice cubes to half its height and the ice was sprinkled with a handfull of mixed sodium and calcium chloride salt .
A thermometer was placed in the beaker , and an addition funnel containing 130 ml of prechilled H2O2 26.6% was set in a support clamp above the beaker . The still warm precursor was poured quickly into the beaker and the stirrer was started . The addition of cold H2O2 was begun immediately when the temperature of the precursor had fallen to 24 C and the addition was regulated at about 1 drop every two seconds to maintain a steady temperature of 20 C until about half the peroxide had been added . The mixture was bright orange soon after the addition first began and quickly lightened to a bright yellow color growing even lighter to a pastel yellow as the addition proceeded . No noxious fumes or vapors were noted . After the first half of the peroxide had been added , the rate of addition is slowed to allow for the temperature to gradually fall so that by the end of the addition the temperature is 5 C . By this time the color has faded to just slightly off white ,
very pale yellow . About an hour has been required for the addition of the peroxide . The temperature continues to slowly fall until it stabilizes at - 7 C . Stirring is continued for an additional hour and then stopped . The beaker is a thick slurry of nearly white crystals which do sparkle in the solution and sink forming a clear layer of supernatant liquid , with more than three quarters of the volume of the mixture being crystals . This reaction proceeded very smoothly with no surges in temperature nor instability noted . The mixture will be allowed to stand for likely several hours to see if complete loss of color will occur , indicating an endpoint for the reaction . But it appears 99% complete at 3 hours from the beginning of the peroxidation .
After 8 hours from the beginning of the peroxidation , the color is just barely off white , slightly yellowish green , so pale that I cannot be sure if the color is simply a shade due to the color of the pyrex glass . The bath is half melted and the temperature is - 5 C . Most of the melted icewater is suctioned off and fresh ice is added and the mixture allowed to stand overnight , for an additional 8 hours . The bath is nearly melted by morning and the temperature is -2 C . The crystals have faded in color slightly and appear to be white , and the crystals have lost their glittering effect and have taken on a matte white appearance , as well as now the crystals have formed a floating raft over a clear lower layer of liquid . The mixture is stirred at a moderate speed for a half hour as 100 ml distilled water is added to thin the slurry for filtering .
The mixture is filtered and rinsed well on the filter with distilled H2O , and the filter is twisted into a ball to squeeze out remaining liquid . The damp crystals are rinsed into a clean beaker with 200 ml distilled H2O and stirred rapidly . 10 ml of NH4OH diluted to 200 ml with H2O is added in portions to the rapidly stirred mixture . After 10 minutes the mixture is filtered , and again rinsed on the filter with
distilled H2O , the filter twisted down to squeeze excess water , and the ball of squeezed cystals is blottered for a few minutes , and then spread out in a thin layer on a fresh blotter for drying . A very faint odor of ammonia confirms the neutralization . Considerable moisture remains in the crystals after drying for 6 hours spread in a thin layer upon a sheet of inkjet paper . The offwhite color is apparent against the ultrawhite color of the 110+ brightness inkjet paper . The crystals are about 95 brightness of white by comparison . The same faint insecticidal odor of pyrethrin is barely detectable on these crystals , as was the same result for the reverse order of addition experiment . The odor is different from AP , more faint and a lighter aromatic odor . And the crystals do not glitter like AP . The yield appears lower than the yield for the reverse order of addition for the peroxidation , but the crystals have not yet been weighed for calculation of yield . The yield figure will be provided in an update here after the crystals are dried and weighed .

UPDATE:

The crystals are well dried now and the yield is not good , only 23.2 grams of dried crystals which is 47.1% of the theoretical possible yield from 50 ml acetone . This is a far lower yield than the ~75% yield from the reverse order of addition peroxidation experiment run at low temperature from beginning to end . Therefore it would seem the reaction is favored by low temperature . The precursor for the earlier experiment had been refrigerated for a couple of days following preparation and that may also be a factor . Hmmmm. More work to do on the preparation . I see Pyroz has just posted a procedure below .

[Edited on 16-1-2005 by Rosco Bodine]

:::

Pyroz - 15-1-2005 at 17:56

The lab sythesis has shown the validity of the german patent.

Attachment: chemlabsynth.doc (29kB)
This file has been downloaded 1136 times

The_Davster - 15-1-2005 at 18:03

I am unable to open the file...

Rosco Bodine - 15-1-2005 at 18:13

Quote:
Originally posted by Pyroz
The lab sythesis has shown the validity of the german patent.


Pyroz , see if you can get the yield figure expressed in grams , and the method of drying . My experience is that this material has a significant residual moisture content .

:::

Pyroz - 15-1-2005 at 18:25

try this::: richtextfile

Attachment: chemlabsynth.rtf (20kB)
This file has been downloaded 988 times

Rosco Bodine - 15-1-2005 at 18:52

Pyroz , Nice to see a detailed synthesis report , but I have to say it leaves many unanswered questions . In the start of the synthesis report it says ,
Quote:

"The validity of the German patent DE951660 will be illustrated through a series of tests that will prove or disprove the existence of C18H26O2(O2)5 or diphorone pentaperoxide. "

I don't see enough data in the synthesis report to fulfill that "proof or disproof" for DPPP , but it does confirm and add to some of what we already know .

The_Davster - 15-1-2005 at 18:56

Strange, I still cannot download it correctly. This is what I get when I click the attachment.

bad download.JPG - 28kB

Rosco Bodine - 15-1-2005 at 19:52

rogue chemist :

I like my files like my women ,

acrobatic :D Try this

Attachment: Synthesis produced by R.pdf (81kB)
This file has been downloaded 1595 times

Mickhael - 15-1-2005 at 19:52

Rogue I couldn't download it when I just clicked open, but I could when I hit save instead...maybe try that? otherwise i'm sure someone who got it ok is willing to email it to you...myself included.

The_Davster - 15-1-2005 at 20:28

Thanks everyone, it just must be my computer acting up. I asked a friend of mine to try all of the attachments on his computer and they all worked for him, wheras none of them are working for me. Oh well I have a copy of the lab results now so its all good :D.

Well, back on topic, I agree with Rosco here, this patent and now lab results do not prove the existance of "DPPP", only the production of an explosive organic peroxide, with the exact formula still to be determined.

[Edited on 16-1-2005 by rogue chemist]

Rosco Bodine - 15-1-2005 at 21:18

rogue chemist :

You were asking me earlier about the sublimation test result on the reverse order of addition experiemnt where I got the best yields , and it looks about halfway finished and has produced the good cubical clear crystals which I am pretty convinced are the DPPP sublimate . A sample from my last batch of DPPP by the conventional peroxidation route has just been added to the sublimation test group . The yield was not good on my last DPPP synthesis experiment , only about 47% of theory , but the product appears to be of high purity and it burns extremely fast compared with the other samples . It may be that it is simply finer granulation and more completely dry , but it really burns very quickly in even a small amount actually seeming more like fulminate than AP in the quantity where it gives that mild "pop" where you know doubling the quantity it would likely detonate unconfined , and probably at less than the amount where AP would be demonstrating the same transition . I am simply speculating here based on experience , and have not stepped up the charge weights incrementally to see where DDT actually occurs for unconfined amounts . The flash is quicker for the DPPP ignited in small amounts .
Putty tests may also be revealing. Control samples related to AP , along with a variation upon the method for AP adapted to the peroxidation conditions we are using for attempts to make DPPP are going to be part of my experiments , to provide data going to some of the doubts which Axt related , and frankly I share the same reservations , absent some of the skepticism . I am going to do an experiment where I mix prechilled acetone and prechilled HCl at a low enough temperature to hopefully inhibit any significant polymerization and then peroxidize at low temperature using the same conditions ,
to see what form of regular AP crystals are produced , and if they form any different crystals upon sublimation from the sublimate obtained from AP made in the usual way . This should address any question as to whether the sublimed crystals of regular AP may simply develop differently depending upon the conditions under which the AP was made . Hey Axt , I saw that one coming :D

[Edited on 16-1-2005 by Rosco Bodine]

Chris The Great - 15-1-2005 at 23:14

Can those at the universities determine the IR spectrum and do other tests such as X-ray scattering (Not the correct term, but you know what I mean) to try and determine the structure? That would definatly be some useful information we couldn't get through our home experimentation.

When I get some more H2O2 I'll try the synthesis as well as some other tests, as well as take some microscope pictures of the crystals, such as I did with AP. That would definatly help with determining crystal structure.

More results coming soon

Matsumoto_Hideki - 15-1-2005 at 23:43

My test results from the University are still yet to be
recieved. Hopefully this week.?
As ar as the test footage, nothing yet as I was still unable to get to the range BTW.. it was totaled from the snow storm we had here. This is something I seldom see here on the west coast. SNOW SUCKS

possible variable about precursor identified

Rosco Bodine - 16-1-2005 at 09:44

My last experiment with the conventional order of addition of the peroxide to the precursor seemed to produce the desired product in good purity , however the yield was low at 47% , and I have been thinking about this and trying to identify what variable is responsible for the lowered yield . The precursor which I used had been freshly prepared a few hours earlier from 47ml HCl and 50 ml acetone in a sealed bottle heated for about 3 hours at 65 C to the point of development of that deep ruby red color which has been tenatively identified as the probable endpoint for the reaction producing the precursor . Now I question that assumption because of an unused sample of the precursor which was made the same way but has been refrigerated for a week at about 4 C since it was made . The refrigerated sample has continued to deepen in color to a very dark burgundy or "oxblood" color without
an precipitation of any oily upper layer , so it appears the formation of the soluble precursor continues significantly in the cold , without producing an upper layer as would occcur if the reaction was being driven by heating to the same level of color darkening . The precursor which has been refrigerated for a week is extremely dark in color , almost to a black
appearance , and yet it is actually still transparent to intense light and not yet cloudy or opaque as would indicate a precipitation or formation of an emulsion with some suspended insoluble material .
It seems likely that to a point , initial warming of the acetone and HCl mixture increases the formation of the phorone dihydrochloride precursor , and then begins to also produce the xylitone or xylite oil upper layer precipitate if heating is continued , which represents a loss of precursor . Further heating is counterproductive past that point , but if the reaction mixture is then cooled and kept cold for an extended time , it appears that the reaction proceeds more slowly continuing to increase the concentration of the phorone dihydrochloride , but without producing the greater amounts of xylitone which would be observed accumulating at higher temperatures . If this is indeed true , then patience will be a virtue in preparation of the precursor for highest yield prior to the peroxidation . Because it appears that at low temperatures and slow reaction rate , the formation of the phorone dihydrochloride in increasing concentration is preferential to the formation of the byproduct xylitone as occurs at higher temperatures . If this is the case , then it may increase the DPPP yield by 50% to simply store the "ruby red" precursor cold for a week before it is used , as compared with using that precursor freshly prepared . Does this square with anyone elses observations or thoughts ?

A related idea which I have concerns the formation of triacetone dialcohol which is involved in the reaction , as well as it may also be involved in the formation of ordinary trimeric acetone peroxide via the reaction in the cold where HCl is used only in catalytic amounts . It is known that under alkaline conditions that very low temperatures triple the concentration of triacetone dialcohol ultimately reached at equilibrium for the reaction , as would occur at higher temperatures , and this could also be true for acid catalyzed polymerization , which may account for the formation of reguar trimeric AP being favored by low temperatures , if the triacetone dialcohol were actually an intermediate in the reaction sequence which forms the ordinary trimeric AP .
It seems possible that it may even serve to concentrate the yield of phorone dihydrochloride by a series of a few periods of mild warming for a short period followed by longer periods of extreme cooling . This would be the case if the triacetone dialcohol formation is favored by low temperatures , while its condensation with HCl is favored by warmer temperatures . If there is a conflicting thermal parameter for the formation of each , where the optimum condition for the one is opposite for the other , then cycling the reaction through a few cooling and mild warming cycles could drive the reaction further towards completion . This could be as simple as removing the sealed bottle from the refrigerator each day and setting the bottle in a pan of warm water for thirty minutes , and then returning it to the refrigerator . It is possible that some special manipulation of this sort may be required to increase the end yield of DPPP . Whether this particular idea has any validity or not remains to be tested .
There are many variables to be examined about this reaction , thanks to the lack of description of details in the patent .

Matsumoto_Hideki - 16-1-2005 at 10:18

I just got off the phone with the chemistry student doing the DPPP research. He believes that the reaction has to continue until the colour reaches its full dark stage. Triacetone dialcohol does form but it quickly changes into a nearly black Phorone-isomer hydrochloride when free HCl reacts with it. This really seems to make sense to me. The Xylite oil forms as a skim on the surface indicating "Phoronisation" - if thats a word. :) More information will be gathered this week.
I stand behind this claim to...it has been my experience as well.

chemoleo - 16-1-2005 at 10:41

Hmm, what's this suddenly about xylitone and triacetone alcohol?
From what I could find about xylitone on the internet, it is ' A yellow oil having a geraniumlike odor, produced as a side product in making phorone'.
But thats ALL the info. No patents on it, nothing. What's the evidence that this is produced here?
Same goes for triacetone alcohol. From what I read it is formed under basic, that is, alkaline conditions. Numerous patents employ various acetone condensations with Ba(OH)2, KOH, NaOH, whatever. Hardly the conditions we use here, with a large amount of HCl. I am getting confused as to where all these theories come from, and what the evidence for allthose theories is.

Then all these precursors- dichloro/pentachloro phorone - we don't even know the identity of the final product. How can we even dare to speculate on what product is formed at this point or that point during the reaction? Do we even KNOW, at this point, that some phorone derivative is reacting with H2O2, and not something else? Think not.

I guess, before we discuss page upon page the potential reaction products- wouldn't it first make sense to confirm, beyond doubt, that the putative DPPP produced this way, with different crystal structure and all that, is indeed more powerful? From what I have seen this far, there is tentative confirmation, that was disputed lateron again. Including the putative DPPP smelling like AP, sublimating as fast as AP, and with slightly different crystal structures? The fact that it sublimates is also in direct contradiction to what it says in the patent btw.

I don't quite understand what the use of this whole discussion is until we confirmed beyond a shred of doubt that the new substance is indeed a new peroxide, which is NOT AP, and more powerful than AP?

Shouldn't we first properly characterise the end product before we discuss in many pages how it is made the most efficient way, and whatever side products are produced?


Just trying to get this whole thing back onto track, before it turns into an 'acetone condensation' lecture! I realise testing of various conditions is required. But theorising on the reaction itself while we don't even know the identity of the final product...hmmmmm!

[Edited on 16-1-2005 by chemoleo]

Rosco Bodine - 16-1-2005 at 12:00

Quote:
Originally posted by chemoleo
Hmm, what's this suddenly about xylitone and triacetone alcohol?
From what I could find about xylitone on the internet, it is ' A yellow oil having a geraniumlike odor, produced as a side product in making phorone'.
But thats ALL the info. No patents on it, nothing. What's the evidence that this is produced here?
You are right about the "xylitone" and I was using that term , thinking about the "lab report" which Pyroz posted having named this material "xylitone" . I do not know for a fact what it is , and my first thinking is that it is predominately phorone , triacetone dialcohol , and higher acetone polymers in mixture , which smell nothing like geraniums to me :D , but something closer to linseed oil or varnish . The smell is like the stinky odor of oil based paint , especially an old can which has been opened after years of storage and the leftover paint has gelled into an unusable goo .
Quote:

Same goes for triacetone alcohol. From what I read it is formed under basic, that is, alkaline conditions. Numerous patents employ various acetone condensations with Ba(OH)2, KOH, NaOH, whatever. Hardly the conditions we use here, with a large amount of HCl. I am getting confused as to where all these theories come from.
Well it isn't a theory that acetone polymerization also occurs under acidic conditions . The synthesis of mesitylene first involves the formation of acetone polymers at mild temperature under acidic condition , and then those acetone polymers are "cracked" at higher temperature which results in ring closure to form mesitylene . The Mackowiak patent also shows the triacetone dialcohol as the first polymerization product from acetone and HCl .
Quote:

Then all these precursors- dichloro/pentachloro phorone - we don't even know the identity of the final product. How can we even dare to speculate on what product is formed at this point or that point during the reaction? Do we even KNOW, at this point, that some phorone derivative is reacting? Think not.
No not for certain , but we are seeing that certain variables are affecting the yields of the unknown product we are getting , and all the data contributes its small part to helping understand the reactions occurring .
Quote:

I guess, before we discuss page upon page the potential reaction products- wouldn't it first make sense to confirm, beyond doubt, that the putative DPPP produced this way, with different crystal structure and all that, is indeed more powerful?
Chomping at the bit for blast data :D yeah that's where the rubber meets the road , if the tests are done right without any bias towards seeing reasults as you would hope to find , but just being content with the facts , whichever way that goes .
Quote:
From what I have seen this far, there is tentative confirmation, that was disputed lateron again.
Not disputed , just not yet independently confirmed .
Quote:
Including the putative DPPP smelling like AP, sublimating as fast as AP, and with slightly different crystal structures?
Nope , all samples of "speculative" DPPP so far are only producing clear cubical crystals upon sublimation , with very small amount of any other form crystals .
Quote:
The fact that it sublimates is also in direct contradiction to what it says in the patent btw.
Where exactly does the patent say that the DPPP does not sublimate ? Looked carefully and I don't see that declared anywhere .
Quote:

I don't quite understand what the use of this whole discussion is until we confirmed beyond a shred of doubt that the new substance is indeed a new peroxide, which is NOT AP, and more powerful than AP?
That finding could be the result of the experiments being done . It is more than simply shooting in the dark hoping to hit something which I am doing anyway .
Quote:
Shouldn't we first properly characterise the end product before we discuss in many pages how it is made the most efficient way, and whatever side products are produced?
Not when we are all comparing notes and thoughts on what we are seeing to reenforce our identification of the product and its purity , color , smell ect . so that definitive tests for density , melting point will be believed to be data for the pure substance we are calling DPPP , and not some mixture of compounds . It is standard practice to attempt different methods for synthesis and compare different samples properties .
Quote:

Just trying to get this whole thing back onto track, before it turns into an 'acetone condensation' lecture! I realise testing of various conditions is required. But theorising on the reaction itself while we don't even know the identity of the final product...hmmmmm!
Sheeesh , lighten up will you . It takes days for the sublimation tests to develop , and in the time of waiting I am examining other unknowns to see what useful information may be found , testing what ideas I have as I go . Right now I have an experiment underway where I mixed the acetone and HCl very cold and returned them to the freezer for keeping in the cold . Tomorrow when I gently warm that mixture , if I get color development much sooner and more intensely than from the usual method , then I wil know my theory above about the cold favoring the formation of triacetone dialcohol while warm temperature favors its conversion to phorone dihydrochloride is correct . All such experiments are pertinent and germane to supporting what we are speculating are the reactions which lead to the DPPP . Don't worry , I will do the detonation tests myself , including some putty tests comparisons with control samples of known AP , and compressed charge comparisons of DPPP versus AP .
Maybe we should just all retire to the lab and range with our notebooks in hand and then come back when all the work is completed to report our results , as opposed to real time reports of piecemeal
results and ideas . We can tie it all together to make sense later . That's okay by me . I know I had the impression not everybody could follow where I was going with all of this from the beginning with my "sealed bottle experiment" which had its usefulness in my mind anyway . Dittos for the sublimation and other experiments , all working parts of an analytical study of the "DPPP" which is sufficient to satisfy the skeptics with definitive answers and data . I am sure as hell tired of this too , but the experiments are providing useful information and I'll keep going till I have my own "finding" that will withstand scrutiny .

Mickhael - 16-1-2005 at 12:43

Right on Rosco...I for one will continue to look forward to your updates and suggestions on the synth...I have a meager amount of experience and equipment so for the most part I just have to stand back and watch, and then try the occasional method thats brought to light. I think that constant updates by everyone is the best way to keep everyones brains thinking on new possiblities and not drift into single minded opinions...I know my thoughts on the substance have continually grown with the new information discovered by verious people on this thread...I have no doubt that within the new few weeks almost everything we have been wondering about will be solved :) That'll be a day to break out the good stuff and have a toast ;)

Pyroz - 16-1-2005 at 13:40

--we are all coming up with information that will help one another. I am sorry my eagerness is sounding like insanity. Its pretty clear to me that the material created in this synthasis has a much higher VOD than standard TATP-triAcetonetriPeroxide, but like I say it never hurts to have others try it out and see it for themselves.
I will only post lab info from now and keep technobabble to a minimum... sorry, rosco and others.

Guyz, we need more people doing VoD tests! Chemical synthasis information or not it all boils down to detonation tests--- "kaBOOM!" It will become explictly clear once the tests are done.

PainKilla - 16-1-2005 at 13:47

Soon I will be trying this synth with another regeant... hopefully I can disprove the "DPPP" via phorone theory ;).

more details will follow soon.

How interesting.... H2SO4 and Acetone smell EXACTLY like AP. Perhaps DPPP is a mesitylene deritive. If anyone has a good distilliation setup, please try distilling mesitylene and peroxidising it.

It is that sweet smell of AP, when equal portions of h2so4 and acetone are mixed. This produces mesitylene which I think is a direct precursor to the formation of both these substances, perhaps one and the same. Maybe one is tertrameric and the other tri. I don't know, but soon I will make much more exact results. Just something to think about.

[Edited on 16-1-2005 by PainKilla]

Mesitylene and Energetic Deratives

PainKilla - 16-1-2005 at 14:11

Mesitylene is 1,3,5-trimethyl benzene. It's the flammable deritive of H2SO4 and acetone, usually via distillation. It also has a ketone, methyl isobutenyl ketone, which can form peroxides supposedly. I think it is important to research these compounds as they may be more important than the phorone that everyone is so excited about. I know I am not the only one who holds doubts about DPPP.

When I mixed H2SO4 and acetone at room temperature, the temperature of the mixture shot up drastically. The mixture smelled very strongly of AP.... This is something I am quite curious about. DPPP seemingly no one agrees about. It does smell like AP, or it doesn't....

Also to be noted, is that mesitylene often looks JUST LIKE THE "PCP" mixture that everyone regards as a trademark charecteristic. I think we should have some people more experianced add some input on this.

I think this should stay in the Energetic Materials, as we WILL have an energetic material within the week ;).

WHOA! I am not sure what this picture is, but if it is peroxides then I think we have DPPP....

http://maildbs.c.u-tokyo.ac.jp/~nisikori/mvct.htm


I don't think thats peroxides but still looks interesting as I know ether defiently makes one. I can't read boxes (what my browser shows) so I cant tell what it is.


[Edited on 16-1-2005 by PainKilla]

[Edited on 16-1-2005 by PainKilla]

Pyroz - 16-1-2005 at 14:56

I'll see if Hideki wants to translate--- I too read japanese::: I'll do my best.
well, i can say without a doubt that the sulphur yellow colour I had when I made my 1st successful batch of "DPPP" was obviously there. i didn't add enough hydrogen peroxide and I got a low yield. There was a lot of this yellow material. Very pungent odor! Still I continue to get yellowish crystals and after purification they are almost pale mint green/yellow

PS. my first trip to the lab, I was told that Mestyl Oxide may have been produced --- there was some arguement that amongst some of the chem students and a few people on this forum. ----Mesityl Oxide can form explosive peroxides, this much is known---

Here is a picture:

[Edited on 16-1-2005 by Pyroz]

[Edited on 16-1-2005 by Pyroz]

100_2540.jpg - 188kB

Rosco Bodine - 16-1-2005 at 15:16

Pyroz ,

That pale mint green - yellow , very nearly white is what I got from my last synthesis and the smell to me is like
pyrethrin based bug spray like you use on tents and sleeping bags . It is a very faint odor to me not as strong as regular AP . To me regular AP has very clean light aromatic odor which reminds me of ether ,
but is a definite odor which doesn't require getting your nose down to a half inch away from it to smell it as does the DPPP , which has a barely detectable odor . I have gotten a product having that faint insecticidal odor by either order of addition on the peroxidation , and the exact same barely tinted color , which is sort of like the off white color that lime juice gives a frozen daiquiri . Does that square with your result ?

PainKilla - 16-1-2005 at 15:26

My AP doesn't always have an extremely detecatbale odor etoehr. In fact, most of the time I have to get really close to it... It has an EXTREMELY addicitve smell i think. I can't get enough of it until I realize I'm sniffing a sensitive primary.

PS: Now I know it smells like mesitylene (see my above post)

[Edited on 16-1-2005 by PainKilla]

Pyroz - 16-1-2005 at 15:28

yes, rosco...I have been getting the same material as you have. It is pale green-- like lime juice :0
this is the material i have been getting from all reactions - the last photo which was of a botched batch

here is my yield from last week... its completely dry...here is a photo of it.

100_2637.jpg - 128kB

chemoleo - 16-1-2005 at 15:44

I doubt these pictures from the japanese link are peroxides, as pretty as it may look. The peroxide of diethylether isn't a nicely crystalline solid, as far as I know. It looks a bit more like some crosslinking experiments, with a compound called MV2+, which is some ionised biphenyl derivative.

As there is not much consensus at this point what products of the acetone/HCl reaction react further with H2O2, don't you think it's a little early to create a thread on peroxides of mesityl oxide, or whatever?

Let's just see how this goes, maybe Rosco's experiments sort out which conditions predominantly produce the oily substance, and which don't. From this I hope we can work out which preferentally produces the crystalline substance with H2O2, and from this in turn maybe someone can do some more comparative power tests ... in a perfect world :):P


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.

Could I just point out one thing re. phorone and mesityl oxide - the former is the condensation of three molecules of acetone, and mesityl oxide is the condensation of two molecules. The methyls of the acetone react on either side with the carbonyls of two molecules of acetone to get phorone, while mesityl oxide reacts only with one methyl group.
I.e.

Mesityl oxide

(H3C)2C=CH-CO-CH3

Phorone

(H3C)2C=CH-CO-CH=C(CH3)2


Not surprisingly, the mesityl oxide also forms putative peroxides. If the patent holds any truth, it wouldn't surprise me if the putative DPPP was a mix between mesityl oxide peroxide and DPPP.


Regarding the smell- that's interesting. It looks like this is not a reliable indicator to identify these peroxides.

[Edited on 16-1-2005 by chemoleo]

PainKilla - 16-1-2005 at 15:51

I will be attempting the mesitylene peroxide later this week. I finally stopped being lazy and got acetone. I have like 20ml of H2SO4 though. Anyone with better organic cehm knowdledge mind telling me thier ideas on the stabilty of this compound?

chemoleo - 16-1-2005 at 16:00

Can you provide us with any reliable reference on mesitylen peroxide? I don't see how this would work, it's fairly unreactive and aromatic; the chemistry behind these peroxides (made with acid) is that carbonyls or alcohols are required (except HMTD). Mesitylene has neither.

Now if you meant mesityl oxide peroxide, and if you manage to make it yourself, from diacetone alcohol, and subsequent peroxidation, then create a new thread. I posted references above re. the synthesis of mesityl oxide.

[Edited on 17-1-2005 by chemoleo]

Pyroz - 16-1-2005 at 16:02

---not to confuse the issue but I wonder if Mesityl Oxide can be peroxidized into dicumyl peroxide C18H22O2?
http://www-ilo-mirror.cornell.edu/public/english/protection/...

PainKilla - 16-1-2005 at 16:13

I have no direct information to it's forming of peroxides, but many msds list that it is capable of forming peroxides. Perhaps, methyl isobutenyl ketone is somehow formed as intemediary. I tried adding 1:1:1 ratio, and got crystals? I am not sure, since it began to also smell of ap (this was sepearture from the mesitylene smell) and I poured baking soda on it. So basically it was like this:

h2so4+acetone -->room temp etc-->ap smell plus mesitylene and other goodies---->+h2o2-->crystals and bubbles that smelled stronger of ap

now I know that's like nothing at all but this was out of curiosity and boredom. I will try a much better synth with heatng etc. I will heat h2so4

EDIT: hmm h2so5?

and acetone to exact same temps as DPPP synth. We will see then. I won't peroxidise any large amounts of it though. 1ml at a time until i can verify chemical stability.

-------------------regarding DICUMYL PEROXIDE-----

I would not be surprised.... its structure looks like this:

benzene ring with a tricross at the "2" position...eh screw it ill get a pic....

http://www.inforubber.com/product/peroxide/pic5.jpg

[Edited on 17-1-2005 by PainKilla]

[Edited on 17-1-2005 by PainKilla]

[Edited on 17-1-2005 by PainKilla]

chemoleo - 16-1-2005 at 16:37

No, I think you still mean mesityl oxide, not mesitylene. The latter is stable, and only incompatible with conc HNO3- which is probably true for any aromatic. I checked all MSDS's on mesitylene, no mention of peroxides.

Further, since you keep going on about it - mesitylene isn't rapidly formed. Check OrgSyn's method. It's a water-insoluble oil anyway, and you'd need to separate it away from unreacted acetone. But it won't react with H2O2 anyway...
Also, in case you don't know, H2SO4 and acetone does NOT produce mesitylene as a sole product.


By the way, mesitylene is also produced by HCl and acetone, check the references from the orgsyn method above!

This one really is a killer, so many products from heating acetone and HCl! How are we ever to know what is forming the crystals? :(


PS Rosco, I don't mind updates or anything. But yes, it does get confusing, and I felt it was necessary to point out again what we are after - which is to validate whehter the new product(s) have greater power than AP, or indeed, if they are just something but NOT AP. I am looking forward to the results from the tests you will do tomorrow!

[Edited on 17-1-2005 by chemoleo]

PainKilla - 16-1-2005 at 16:52

Yea I know that it can form various products, but mesitylene is the main one. It's ok. I will post results on my reaction probably Tuesdayish.

Rosco Bodine - 16-1-2005 at 18:01

Quote:
Originally posted by chemoleo
This one really is a killer, so many products from heating acetone and HCl! How are we ever to know what is forming the crystals? :(
Most chemistry is experiments which follow a sort of algebraic logic where you work the unknowns against each other in a bit of detective work to learn exactly what the unknowns most likely are . Each experiment chips away at the unknown "big picture" sort of like the pieces of a jigsaw puzzle being connected until a visualization can materialize .
Quote:

PS Rosco, I don't mind updates or anything. But yes, it does get confusing, and I felt it was necessary to point out again what we are after - which is to validate whehter the new product(s) have greater power than AP, or indeed, if they are just something but NOT AP. I am looking forward to the results from the tests you will do tomorrow!

Actually I got a phone call about some other business which will require my time tomorrow . But I will try to get something done if time permits . I had only a small sample on hand of regular AP leftover from several years ago from other experiments , so I have a new batch in the freezer to produce some fresh material for use as an AP control sample . My storeroom is getting low on materials for experiments so I need to restock some items before continuing much further anyway . When I get to the detonation tests I will probably be comparing several sample materials to get a good indication of what is occurring . One of the definitive tests I like to do on a detonator candidate is to load 2.5 grams of it into a capsule and see if it will fully detonate urea nitrate , which is an excellent challenge . A hot cap with sassy material will surely detonate the urea nitrate every time . AP would never even come close to delivering the impulse required . 2.5 grams of HMTD is about the threshold quantity for a single component charge , moderately pressed in a charge column diameter of 9.5 mm , modest confinement such as provided by a 5 ml 12 mm X 75 mm polypropylene culture tube with a piece of visco inserted through a hole drilled in the culture tube closure and secured in place with tape . This is sort of a test bench reference standard cap which can be used as a control for comparison with other configurations .

[Edited on 17-1-2005 by Rosco Bodine]

japanese website translation says nothing about peroxides

Matsumoto_Hideki - 16-1-2005 at 19:54

This website painkilla found is about the degredation/allteration of diethyl ether's crystal structure to light at +2MV. ie) shortwave UV
Not about peroxidation.. sorry guys..
Fukou ni mo, DPPP no nazo ga tsuzuiteiru........

[Edited on 18-1-2005 by Matsumoto_Hideki]

[Edited on 18-1-2005 by Matsumoto_Hideki]

I did.....but.....

PerFecTioNisT - 18-1-2005 at 10:13

Ok I made DPPP yesterday.
100ml acetone+100ml 30%HCL+175ml 30%H202.And how to look that is sure DPPP?Matsumoto_Hideki could you writte your DPPP proportion, I want to try make by your method.

Ok this is what I did.

Matsumoto_Hideki - 18-1-2005 at 16:54

Step 1#

340ml HCl (muratic acid) 35%Vol
2% below regent grade.

340ml Acetone

Step 2#

cover your mix flask with a balloon or bag
to trap HCl and acetone vapours, this will concentrate your reaction.

Step 3#
Put your flask in a hot water bath
and heat until the colour changes to a dark red. This should take about 30mins. after the dark red/ almost black colouration has been reached let the flask cool down on it's own. empty out the balloon back into the flask.

4#
After the flask has cooled off, remove the balloon
carefully and lt the flask stand at room temperature for at least 48hrs. This allows any unreated acetone to vapour off.

5#check the flask against a light source, there should be no light passing through it. There may be a small reddish transparent layer at the bottom, this is usually leftover HCl and can be removed with a pipet.

6# Peroxidation
****You are advised at this point to put the entire flask into a bucket of cold water and freeze it in a freezer down to around -25c -30c before ANY 35% vol Hydrogen peroxide is added***** You are freeing the flask into a block of ice.
The Phorone HCl is viscous like honey at this point.

7# Adding the peroxide.
680ml H202 is added in total.

Add your first 200ml of H2O2 while you stir you mix with a glass or nitrile rod (acid and solvent intert material)
The colour changes immediatly to a red orange and crystaline rafts start to become instantly visible.
let the temperature cool off after 1-2hrs

8# Add your remaining H2O2 480ml to the crystalizing DPPP, colour now is BRIGHT YELLOW ! give your flask a good stir and leave for at least 9hrs in the freezer. This yellow is mesitlyene and is indicative of phorone production.

9# After 9hrs you need to filter and neutralize your crystals with baking soda, then again in a wash of distilled H2O. note your yeild will be slightly over 300g with this method when dry.


10# Using pure Isopropyl alcohol you can remove the left over mesitylene form the crystals, this is what stains your end product. I would also keep a bit of Isoproylene to wet your yeild for safetys sake.

[Edited on 19-1-2005 by Matsumoto_Hideki]

[Edited on 19-1-2005 by Matsumoto_Hideki]

Hold on just a minute , Let's do some math

Rosco Bodine - 18-1-2005 at 17:50

The gram molecular weight of DPPP is 434.40 , formation of which requires 6 gram moles of acetone , which is 441.2 ml of acetone . Therefore a 100 % yield of DPPP would be 434.4 / 441.2 = .9845875 grams of DPPP per each 1 ml acetone .

A yield of 100% of theory from 340 ml acetone would be 334.75 grams of DPPP .

Sooooo , if you got 400 grams yield , then it is definitely not dry :D

PainKilla - 18-1-2005 at 17:53

I dont think we can apply stoichimetry yet as we have not determined what this is. Friday I will be trying my project.

Rosco Bodine - 18-1-2005 at 18:39

Agreed that we have not confirmed structure . We need to be accurate about the dry weight however so we can account for anomalies . I thought I had my samples pretty dry , and yet when they were heated in the culture tubes where I am subliming the samples , a pretty good puff of water vapor came off the powder and condensed in the tubes ,
confirming that there is some moisture remaining in the loose powder I thought was fully dried . I have some freshly made AP for a control sample , and may have some preliminary tests on detonations of small amounts in the next few days . I will be stepping up charge amounts , doing some witness plates , and some direct initiation test comparisons with AP at least , and possibly comparisons with some other primaries as well , using carefully weighed quantities . I also plan to make some molded putty comparisons , and some loose powder deflagration comparisons .

Among the initiation tests I plan is to test whether or not the supposed DPPP will initiate pressed crystalline picric acid in an unreinforced compound detonator . Ordinary AP won't do the job in an unreenforced cap , but HMTD will . So if
DPPP has the power and brisance HMTD ,
If I put 2 grams of picric acid in a 5 ml culture tube , pressed in half gram increments with about 10 Kg of pin pressure , and top it with 1 1/2 grams of DPPP , pressed the same way , if the DPPP even matches the performance of HMTD , a full detonation of the 9.5 mm diameter column of picric acid will occur . Garden variety cold formed AP fails this test .

Pyroz - 18-1-2005 at 20:11

...I think the absolute maximum I have achieved in terms of yield is ---- scale---
my scale says: 363.85 grams that is bone dry DPPP and kept warm. It has very little smell and from 510mL acetone --- so it is not the 90% yield talked about in the patent, but close* i am positive the yield would have been much better if the temperature had not been so cold and I have left the phorone-isomer to peroxidize longer say several more hours.
-----------------------------------------------------
I hope to conduct a (((blast))) test on DV on the weekend! This is my chance to show you what I have been seeing in the last few detonation attempts.

[Edited on 19-1-2005 by Pyroz]

Rosco Bodine - 18-1-2005 at 20:30

I haven't done any tests except to simply ignite small amounts of the powder , but just from the subjective impression I had on first glance the DPPP looks faster , makes a briefer and quicker flash and makes a different sound when a small pile is ignited compared to regular AP . I will repeat the tests in the dark with weighed
samples more carefully dried , but to me the visible flash from the DPPP is more white yellow color and quick like a camera flash or flashpowder , while the flash from AP is darker yellow orange burning more like a quick gunpowder .

Pyroz - 18-1-2005 at 20:39

Quote:
Originally posted by Rosco Bodine
visible flash from the DPPP is more white yellow color and quick like a camera flash or flashpowder , while the flash from AP is darker yellow orange burning more like a quick gunpowder .

It has very different burning characteristics--- and won't hesitate to explode in small amounts with heat gradually and liquified--- it then reaches max temperature and then detonates. If lit directly it will burn with an intense white-yellow flame. AP seems to be very orange-yellow by comparison in a flame test.
I agree Rosco, this is what I have seen as well..

[Edited on 19-1-2005 by Pyroz]

Now that you mention stoichiometry .......

Rosco Bodine - 18-1-2005 at 22:46

Quote:
Originally posted by PainKilla
I dont think we can apply stoichimetry yet


Anybody else notice that the stoichiometry is incorrect in the patent itself ? Because the amount of H2O2 30% which is specified by Mackowiak in his own patent is only sufficient for producing a maximum yield of 78.4% if the reactions proceed according to the way Mackowiak has them written . There are 11 moles of H2O2 required for each 6 moles of acetone , and for 30% H2O2 that would require about 2.55 volumes of H2O2 for each 1 volume of acetone .
2.75 volumes of H2O2 30% would be more likely as a minimum , and for 27.5% H2O2 , 2.9 or even 3 volumes of H2O2 per 1 volume of acetone would not be unduly excessive . If the peroxidation reactions do proceed in the way Mackowiak has them written , then there is no way to get 90% yields unless the quantity of H2O2 is increased to or near to these ratios .

[Edited on 19-1-2005 by Rosco Bodine]

Pyroz - 18-1-2005 at 23:09

:)
hey, maybe the patent yield could be increased with a more concentrated peroxide--and a little more of it
35% as apposed to 30% -- I wonder why I'm getting such good yields ~80%. It seems to work for me. As well I'm sure temperature has a lot to do with yield and so does time! I'll try leaving the material for 48 hours @ 0 degrees Celcius and see if I can't get more crystals forming. Mackowaik patent is very interesting indeed but I still think 90% yields are possiable with some tweeking. Maybe the patent should indicate 3:1 or 3X the peroxide to acetone --- so if you had 500mL's acetone/HCL --- you would need 1500 mL's of peroxide? Thats does sound a little excessive---but hey who knows. :)

[Edited on 19-1-2005 by Pyroz]

Rosco Bodine - 18-1-2005 at 23:18

With stoichiometry , it is purely mathematical for solving for minimum molar amounts . And I did the math above . Mackowiak said to use 2 volumes
30% H2O2 for each 1 volume of acetone , but that is not sufficient to balance the reaction equations he wrote , 2.55 volumes of 30% H2O2 would be the minimum for each 1 volume of acetone .
Generally , then there is some excess of theory used for the peroxide , maybe 3 to 10% more than the minmum requirement .
There may be some guesswork there in choosing the optimum excess , but usually the minimum molar amounts are just simple arithmetic , arithmetic which in this case does not square with the ratios Mackowiak stated . The reason it takes more than twice as much peroxide as for making ordinary AP is because more than half of the peroxide 6/11 of it is used in the chlorination reaction which precedes the actual peroxidation . Actually this provides a method of chemical identification of the peroxide formed , knowing how much peroxide would have ben consumed to produce whatever number of grams of DPPP you believe you have , the unreacted peroxide should be found in the filtered reaction mixture , where it may be decomposed and the volume of oxygen produced can be measured . Then a fairly good idea can be gotten of how much of the consumed peroxide is chemically bound in the number of grams of the product obtained ,
and a speculation on its structure can be justified .

These discrepancies concerning the stoichiometry cause me to question if the parts per volume interpretation of the quantities is correct translation . I think I will run the numbers through again on the basis of parts by weight and see if the result better reconciles with the equations as Mackowiak has them written .

UPDATE: The numbers were run on parts by weight basis and the results were not even close to being right so the parts per volume translation is correct , but the volume figure for the peroxide is definitely off by the amount I said .

[Edited on 19-1-2005 by Rosco Bodine]

Wait a sec,

Matsumoto_Hideki - 19-1-2005 at 00:37

Quote:
Originally posted by Rosco Bodine
The gram molecular weight of DPPP is 434.40 , formation of which requires 6 gram moles of acetone , which is 441.2 ml of acetone . Therefore a 100 % yield of DPPP would be 434.4 / 441.2 = .9845875 grams of DPPP per each 1 ml acetone .

A yield of 100% of theory from 340 ml acetone would be 334.75 grams of DPPP .

Sooooo , if you got 400 grams yield , then it is definitely not dry :D



Yes, I understand this 400g would be wet, dry more like closer to 300g or so.

BTW After having a close call with DPPP today when it was dry I do suggest the use of dampening the dPPP with a bit of Isopropylene just to add a bit of safety margin.
Details about my horrific encouter will be posted shortly, that is when I can hear myself again..

Update

Mickhael - 19-1-2005 at 00:52

Just a quick note to everyone, to update my testing to see the stablity of DPPP with MEKP, So far everything is completely fine, the DPPP has settled into the lower part of the test tube, making a smooth silt-like mixture. I imagine I could add quite a bit more...to make a stiff paste, which I will do shortly. No signs of seperation...or decomp has been noticed, its been sitting open to the air, in a 60f garage for a week now.

Detonation results so far have been nothing special, however I am redesigning the electric dets for my BC's, so the results should be more conclusive and powerful when I do the next set of tests.

Nothing special?

Matsumoto_Hideki - 19-1-2005 at 09:09

Well I tell you make the paste 90/95% DPPP and 10/5% MEKP and you wont be saying that for much longer!!

BTW my accident yesterday was in trying to heat DPPP to 160c in a metal spoon and getting it to liquify. Shortly after this DPPP liquified I then let the material recystalize/cool off... this is when it self detonated. The spoon blew itself into a u shape and flew across the room. the amount i was using was maybe 1-3mg.

The_Davster - 19-1-2005 at 10:19

Can we see a pic of the spoon?:D Did the DPPP going off in the spoon cause any deformation in the actuall spoon part of the spoon(the round part), any holes blown through? or was the handle just badly bent.

Mainly I want to compare it to the picture posted by blaster a while back which showed the results of 1 drop of ethyl perchlorate going off in a spoon.

I think the DPPP likely detonated while cooling as a result of posible crystall fracture causd by expansion and contraction of the cooling DPPP.

Rosco Bodine - 19-1-2005 at 10:28

1 to 3 mg wouldn't do that to a spoon .

These exaggerations about effects and yields are serving no constructive purpose and are in fact serving to discredit what useful * F A C T S * you might wish to share with others who are in good faith trying to get at the unvarnished truth about DPPP . So PLEASE knock it off with such "reports" on the "awesome damn nearly thermonuclear POWER of "DPPP" , and stick to the FACTS .

One FACT we do know at this point is that there is an error in the stoichiometry in the patent , and this can be mathematically proven before the first drop of any reagent is measured or the first crystal made . So the accuracy of the other numerical data in the patent is instantly thrown into doubt by that one error in stoichiometry . Actual chemists rarely make errors in stoichiometry in something like a journal or patent publication where peer review is certain to discover and expose the error , which is then usually corrected as an "erratta" declaration page of later publication which then becomes a permanent attachment or insert and an embarrassment to the author for imprecision .

Now Hideki , you don't want to have to go back and do "erratta" corrections on your posts , so let's stick to the facts PLEASE :D

WaveFront - 19-1-2005 at 12:46

My English is not very good, and since I am not a chemist I didn´t want to write for now.
Just to say that it´s extremely dangerous the melted "dppp", can explode without any confinnement if the amount is not tiny. I believe cause I have experienced an accident, but the amount was a little more than a few mg. You can see the spoon:
http://webs.ono.com/rym/cuchara.jpg

You have permission to call me stupid.
My "dppp" was made without the phase separation by freezing (my freezer is not enough powerful). The results for this product (tested by putting small amounts in aluminum foil and perforating metal plates) are better than TCAP, improve much when mixed with KClO3, but from my viewpoint it does not reach the brissance of HMTD. Sorry for the imprecissions.

Joeychemist - 19-1-2005 at 12:57

Shouldn't the spoon be bent the other way?

I only ask because it just doesn't look right to me. Could you please explain in further detail what happened?
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