Sciencemadness Discussion Board

Diphoronepentaperoxide (DPPP)

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vulture - 22-12-2004 at 11:32

I don't need multiple egos fending for me.

J-scan and Matsewhatever are banned. You crossed the line.

Rosco Bodine - 22-12-2004 at 13:31

Maybe it escaped notice , but in one of the posts by one of the various aliases of what has become a tiresome "clown club" was the declaration " I am a *chemist* " ,
( not a chemist wannabe mind you , but a genuine , goggles and glove equipped , *thermometer literate* , hour and minute and second hand time telling , actual for real chemist ) So.....you have to keep wondering about why there isn't a somewhat conventional writeup giving a step by step in concise language , describing the parameters of the experiment in the usual way .

DPPP synth

Smoer - 22-12-2004 at 14:04

So,I tried to make phoron first ,but the solution didn't turned red,but just orange.Then after I added the H2O2(30%) it just turned clearless with a yellow shine.

No crystals found....
What could be the problem?

cheerz

The_Davster - 22-12-2004 at 14:52

Well, more experimentation :cool:

1. 25mL of 31.45% HCl was mixed with 25mL of acetone in a 150mL beaker. This was heated on a waterbath for 2h at 55->65C the tremp was stable at around 62C most of the time. The beaker was covered with saran wrap to prevent evaporation of the acetone
2. After 2h had elapsed the saran wrap was removed and the temp was increased to a max of 80C over a period of 10min to drive off the excess acetone. I was left with an incredibly deep red solution.
3. This is being cooled to -20C

More to come soon.....

When the red solution of dichlorophorone was at -10C an eyedropper full of it was removed and placed in a small testtube. To this was added an equell volume of 35% H2O2. Some heating was noticed after around 10s, by 20s the solution was yellow, but there was no ppt, the solution was quite warm, but not too hot to touch. 4mL of commmercial ammonia was added, the solution cleared up but still no ppt :(.

I am letting the rest of the DCP solution cool to at least -20 before coninuing experimentation.

[Edited on 22-12-2004 by rogue chemist]

My experience

Dodoman - 22-12-2004 at 15:18

I've decided to give it a go. And here is what I did, and I'll try to give as much details as I can so please bare with me.

Chemicals:

100 ml acetone
100 ml 30% HCl
200 ml 50% H2O2 (the bottle says 50% but I don't trust that to be correct because it was opened and laying for a couple of month)

I added 10 ml of HCl to the 100 ml acetone and the temp rised 10 c. 40 ml more and 10 c more, the rest was added. The temp was raised a total of 20 c.

I heated the solution in a 900 ml beaker. There wee some nasty fumes of HCl and Acetone. I saw the beaker was refluxing the acetone so I transferred the sol to a 250 ml beaker and used the 900 ml one as a water bath.

The color of the solution started to change around 65 C. And I noticed the sol boils at 70 c (at that time). The color doesn't seem to get darker below 70C because I held it at 65C for 10 mins with almost no change in color. So the temp was held at 75C for 15 mins. The solution started to turn orange and dark orange at the end of the 15 mins. And noticed that the HCl fumes has stoped only acetone is fuming now. The boiling point has changed and I let the temp rise to 80C (the new boiling point). The reaction was held at 80C for 10 more mins. At the end of the 15 mins the solution have a tea color. I decided to stop the heat and left the solution in the hot water bath to cool slowly (for 30 mins) to drive as mush acetone off as possible. At the end of the 30 mins the sol smelled like acetone but the smell was very strong.

The mixture was then cooled in a freezer to 2C and H2O2 to the same temp. The liquid now have a volume of 145 ml ( 55 ml acetone seem to have evaporated). I started adding the H2O2 dropwise and kept the temp under 30C. As I added the solution started to become lighter in color. After adding about 30 ml of H2O2 I thought that was enough (the H2O2 seems to be still potent). After a few seconds the solution started to turn white without any rise in temp. The smell was not like AP a decided to add ammonia to neutralize the solution (didn't test the pH but it should be acidic with all that HCl in it). So I spilt a few mls of ammonia. White fumes of NH3 smothered me for a few minutes the temp didn't rise though. I'm pretty sure that what I ended up with is plain old AP. The damp crystals weighted 43 gm. But the strange thing is that when I scarped the crystals with a spoon they turned yellow and the spoon was covered by a white layer that doesn't come off.:o The spoon isn't made of stainless steel it looks like tin. Sorry for the length of the post.

DPPP synthesis ?

leopard - 22-12-2004 at 17:02

About 3 months before reading Matsumoto Hideki's posts I was dabblling with DPPP also and as my results were so similar to his I found his posts interesting. Please bear with me as this is not very scientific and I worked with very small quantities for safety reasons.
My first try involved 10 ml each of acetone and 31.5% HCL heated to 90 degree C for about 30 minutes. The result was a very dark red/brown almost opaque liquid. After cooling to room temperature I added 10 ml of 25% h2o2 fairly quickly. The solution went clear/transparent within about 10 seconds and after about 1 minute began to boil. I left it alone for about 1 hour and found it had stopped boiling and had cooled. I left it sitting for 2 days and I got about 1 small spoonfull ofwhat appeared to be a very fine powdery AP. It behaved the same and smelled the same so probably was the same!
I decided to try someting different and mixed 10 ml each of acetone and 31.5% HCL together and let this sit for 3 days at room temperature. There was a very gradual change of colour to light yellow, orange, light red, dark red, and finally very dark red/brown almost opaque like the heated sample previously. I seperated this into 2 equal quanties and added the first sample drop by drop to an equal volume of h2o2. The colour faded quickly as I added the red liquid and I was left with a clear liquid that did not heat up. I covered it and set it aside.
I took the 2nd sample of red liquid and added h2o2 to it drop by drop (reverse of previous). Almost immediately the dark red liquid began to lighten and after adding about 1/3rd of the total h2o2 the liquid had taken on a pale yellow colour and appeared to be filled with suspended particulate matter. I added the rest of the h2o2 which caused the liquid to lose all colour and it had a small amount of crystal in it.
I left both samples for 3 days and gradually they both developed precipate (a small spoonfull each). The first samples precipitate floated on top and bubbled. The 2nd samples precipited sat on the bottom with no bubbling. I placed both precipites on a filter paper and let them air dry for a week. Upon inspection the 1st sample was a very white sugar crystal powder that looked just like AP. Upon flame it woomphed with flash of flame (very short lived and clean burning). The hammer test set it off easilly with the characteristic smell of AP.
The second sample had a very light yellowish tint to it and was a very fine talcum like powder. Upon flame it woomphed but noticeably slower and with a dark sooty orange fireball. The hammer test set it off but not easilly and there was no detectable AP odour or much of anything else for that matter!
I have not had time for further testing but I recognized some similarities between what I experienced and Mr. Hideki experienced. I feel this warrants further exploration. One note; When I added the h2o2 to the red liquid I noticed the crystal precipate occured allmost immediately and at very low h2o2 amounts. I should mention that I tried another sample of h2o2 added to the red liquid but accidently added double the recommended amount and I was left with a water clear liquid that never produced any precipitate. I conclude that there is allmost no minimum point where precipate begins to form but there is a critical point which if exceeded prevents precipitate from forming.
One last note: I found the treatment of Hideki exccesive, vulgar, unkind and immature. It destroyed the enthusiasm of the thread and left me with a poor opinion of some members. This board has been a terrific forum for the exchange of mature subject matter. A little more maturity and patience please, lets get long a little better and get excited about discovering.
Leopard

The_Davster - 22-12-2004 at 19:28

All righty then.... I think I got some DPPP:cool:.

The solution that I mentioned in my last post was cooled all the way down to near -30( an estimate because my thermometer ends at -25). An eyedropper of this was transfered to a small testtube and an eyedropper of room temp 35% hydrogen peroxide was slowly added. I recieved a precipitate:D. I let it react for around 30s more and halted the reaction with an ammonia solution. The yield did not seem as good as was mentioned earlier. Despite the very small volume I filtered it. I was rewarded with a small ammount of powder, about the size of 1/4 a .177 BB. It was a cream color. It had a unusual smell that I cannot describe, the english language is severly lacking in words to describe smells, the smell was nothing like that of AP. When it deflagrates a new smell is formed, very different from the smell of AP when it deflagrates, the smell seemed 'related' ( If that makes any sense when describing smells) to that of the solid DPPP powder.

I repeated the testtube sized test with similar results.

The problems occured when scaling it up... I used the rest of the DCP and poured it into the 1.5L beaker that was in a salt ice bath. I then slowly added the -30C peroxide, after around 30s I recieved a precipitate. Nowhere near the high yields reported earlier. 300mL of a cold solution of 10g NaOH in 300mL commercial ammonia was added an the residual orange yellow color disappaared. I filtered out the ppt of (hopefully) DPPP. Unfortunatly around 1/2 of the ppt was lost as a result of inadvertantly overfilling the funnel ( thanks to a lungfull of ammonia fumes). I am estimating the mass of powder formed to be at most 0.2g:(

[Edited on 23-12-2004 by rogue chemist]

Dodoman - 23-12-2004 at 02:51

I think i failed to explain what happened in my experiment. At the end of the addetion of the 30 ml H2O2 the ppt (which started to form from the first drop) had a pale yellow color (off white) that didn't look or smell like AP. It smelled like a mixture of acetone and HCl but much stronger and made my eyes tear. Did you get the same resultes rogue......?

Then it started to turn white (without any rise in temp). That's when i decided to add the ammonia. And after the addition the ppt conteniued to turn white. I lost alot of the ppt also thatnks to the ammonia fumes. But the remaining whighed 43 gms.

43g,good show!

Joeychemist - 23-12-2004 at 03:18

You have 43gms??? Great, would you mind purifying half of the batch?
:)
Weigh out say 20gms and place in a coffee filter or two, then fold the coffee filter over and dip it in a bowl of hot water (like a tea bag) and let it sit for several minutes at about 100°C.Then wash remaining crystals with distilled water and dry the crystals and measure out how much is left from the original 20gms, The product left should be almost pure DPPP and mostly AP free. (As I’ve said in previous posts, this will work since AP readily decomposes at 90°C and DPPP will stand up to higher temperatures than AP will). Doing this would give crucial info about yields and purity, plus it’s nice to have credible people to compare findings with.

Dodoman - 23-12-2004 at 05:18

I'm pretty sure it's pure AP with no DPPP in it.

The yellow crystals (probably DPPP) decomposed and I think the components left in the beaker gave AP. Althou i didn't see the crystals dissapear and new ones form.

I don't have any time to do further testing my term exapms are next week. Besides the smell of AP hurt my eyes and chest (inspite of being left outside) so I threw them away.

I'll probably give it another go but not before I finish my exams (in a month:o).

KemiRockarFett - 23-12-2004 at 05:35

Quote:
Originally posted by Joeychemist
You have 43gms??? Great, would you mind purifying half of the batch?
:)
Weigh out say 20gms and place in a coffee filter or two, then fold the coffee filter over and dip it in a bowl of hot water (like a tea bag) and let it sit for several minutes at about 100°C.Then wash remaining crystals with distilled water and dry the crystals and measure out how much is left from the original 20gms, The product left should be almost pure DPPP and mostly AP free. (As I’ve said in previous posts, this will work since AP readily decomposes at 90°C and DPPP will stand up to higher temperatures than AP will). Doing this would give crucial info about yields and purity, plus it’s nice to have credible people to compare findings with.


According to Federof TATP, acetoneperoxide, is stable in boiling water for 6 hours !!!

Joeychemist - 23-12-2004 at 05:46

Quote:
Originally posted by KemiRockarFettAccording to Federof TATP, acetoneperoxide, is stable in boiling water for 6 hours !!!


It may be stable, but It will still decompose in hot water, (try it) the dimmer version decomposes at lower temperature than the trimer form dose. (I don't know exactly how much lower) But I can assure you it dose. As I said, try it for yourself.It's AP, it's not that hard to make some and find out if i'm right or if i'm wrong.

KemiRockarFett - 23-12-2004 at 06:06

Quote:
Originally posted by Joeychemist
Quote:
Originally posted by KemiRockarFettAccording to Federof TATP, acetoneperoxide, is stable in boiling water for 6 hours !!!


It may be stable, but It will still decompose in hot water, (try it) the dimmer version decomposes at lower temperature than the trimer form dose. (I don't know exactly how much lower) But I can assure you it dose. As I said, try it for yourself.It's AP, it's not that hard to make some and find out if i'm right or if i'm wrong.


Okey but I think that the info about DPPP sucks, so where to read about the properties of that compound if its even exist. I think you will end up with pure tremericacetoneperoxide and that is what you have left after boiling, say I am wrong and Federof telling lies why should the DPPP be stable to boiling?

Rosco Bodine - 23-12-2004 at 08:45

Federoff is generally accurate but it does contain erroneous information in isolated places . One of those places which comes to mind relates to an imaginative synthetic method for nitroguanidine from ammonium nitrate which states a reaction that can be found nowhere else but in Federoff and likely has no validity .

In the early portion of this thread someone stated that they had found a telephone listing for the inventor , and that someone should give him a call . That sounds like a great idea , if for nothing else but to get a good e-mail or FAX number to exchange some business correspondence pertaining to the patent .
Has anyone made an effort to communicate directly with the inventor ?

If anyone knows the details of the process , it is certain to be the inventor . Any developer interested in the technology of the invention would of course need to be able to confirm that the process is technically feasible and reproducible results are necessary to be demonstrated before any negotiations may be considered with regards to royalties or other compensations . An inventor may have a prepared package of detailed information ready to send out in response to any inquiries from potential developers , and the information contained may be more extensive and detailed than the information supplied by the patent . A developer must be assured that a process described by a patent can be reduced to practice .

[Edited on 23-12-2004 by Rosco Bodine]

Lets find him

Joeychemist - 24-12-2004 at 09:12

I never said federof was lying, in fact I have never read the book, but that is irrelevant. I don’t think this info about DPPP is “crap” I just think that we had made due with what was given to us. I don’t know why DPPP is more stable or why it has a higher VoD or why it dose not decompose as fast as other peroxides. I ADDMIT IT, I don’t know. I spent all last night trying to find this out and I came up with little more than what was already stated in this thread.

I think that Rosco has brought fourth the solution too this problem. We must find the creator/inventor which first synthesized this explosive. I cannot track this guy down unless he’s in or around one of the northern states. But we have members from everywhere in the world so I’m sure If we could just get a name we could go from there.

We could surly track this man down after the holidays. But we need a name first, I looked in the beginning of the thread and could not find any links or copies of the patent.(not to mention I can’t speak German so I wouldn’t know what I was even looking at) So I ask who has a copy??? Or who at least knows this guys name???

Rosco Bodine - 24-12-2004 at 13:50

Quote:
Originally posted by magnum page 5 of this thread on 12-26-2002
hi

i did a search on the phonebook and there lives a wolfgang mackowiak in bielefeld (the inventer of the procedure) the phone number is
+49 5 21 33 41 44 . possible he know how it's done. let's call him.

bye


Now why didn't I think of that ?

The address is in Germany .

Wolfgang Mackowiak
4800 Bielefeld
Meller Str. 59 a

The German patent is DE1951660
( see attached file )

There is an idea I have been wondering about concerning the initial condensation reaction of three molecules of acetone under acidic conditions . It is known that two molecules of acetone will condense under very slight basic conditions to form diacetone alcohol , ( GB356609 ) , and the first reaction shown on page 1 of GB362204 . I have been thinking that perhaps the first 2 molecules of acetone are condensed under basic conditions to first form diacetone alcohol , and then the diacetone alcohol is futher reacted with a third molecule of acetone under acidic conditions which results in the phoron precursor of the patent .
Well I think I may be on the right track . Indeed the precursor shown by the patent in the first reaction condensing three acetones is a compound called triacetone dialcohol , which is a known precursor for phorone , see GB830813 , page 1 line 58 . GB616740 and GB583863 are phorone from acetone related synthesis . Hmmmm , alkaline conditions not acid , very strange . And the conditions described by such patents for condensation of three acetones to triacetone dialcohol then subsequently dehydrated to phorone , all use autoclave extreme pressure and high temperature alkaline conditions which are low yield per pass , multiple pass processes . It could be that there are autoclave conditions required for the Mackowiak acid catalyzed condensation and dehydration of acetone to phorone or phorone dihydrochloride .

[Edited on 25-12-2004 by Rosco Bodine]

Attachment: DE1951660.pdf (155kB)
This file has been downloaded 1146 times

Rosco Bodine - 25-12-2004 at 08:13

Earlier in the thread PainKilla suggested use of free chlorine as possibly being useful in producing the chlorinated phorone intermediates for DPPP . The suggestion is interesting and it caused me to consider a source for chlorine which may have value in this reaction . There is a high chlorine content compound which is used as a chlorinator for swimming pools , and it is highly soluble in acetone , which dissolves 385 grams per liter of acetone . The chlorinator is called trichloroisocyanurate or trichloro-triazine-trione . The material is very soluble in concentrated H2SO4 , from which it may be recrystallized . But in the presence of moisture the compound slowly hydrolyzes with the evolution of free chlorine . It would seem to be a promising candidate for facilitating the formation of the chlorophorone intermediates of the Mackowiak patent , where trichloroisocyanurate might substitute for much of the HCl / H2O2 used as a source for free chlorine . Some free cyanuric acid added to such a reaction system might also be useful . It would be an interesting experiment to dissolve in acetone some trichloroisocyanurate and see what may occur when this is mixed with hydrogen peroxide , in reaction systems where is also present HCl or H2SO4 , or both . This may provide a new area of experimentation for pursuit of DPPP by a modified approach . Or perhaps other interesting cyclic peroxides may result . On an entirely different subject , an acetone solution of trichloroisocyanurate may have interest as to possible reaction with urea . Just off the top of my head it would seem there may be potential there perhaps as a route to hydrazones or hydrazine . I have not drawn the first reaction diagram to see if this seems plausible so this is pure speculation on my part .

[Edited on 25-12-2004 by Rosco Bodine]

kclo4 - 26-12-2004 at 21:35

There may be a way with sodium percarbonate :)

Rosco Bodine - 27-12-2004 at 09:03

At last it would seem the Mackowiak patent for DPPP is gaining some validity , even though certain details remain to be fully understood . My contemplation of the process has been based entirely upon reading with interest the threads here and at E&W , and deliberately not doing the first experiment of my own , until I have confidence in the theoretical basis for the compound attempted to be synthesized . This is my typical method following years of time and wasted reagents with purely trial and error experiments , to spend much more time with the theory of reactions being worked out on paper , before proceeding with the more fun part of actually attempting the synthesis . It is much easier to perfect a synthesis when observations can be made with the benefit of some understanding derived from a plausible theory concerning the reaction being observed . This is at the heart of the matter when the task at hand is knowing how to get the most of the purest product desired from the precursors , by an efficient method whose details are unknown , but being discovered by way of experiment . From the reading of these threads , an understanding has developed for me , now sufficient to describe what I believe are logical conclusions in summary of the various experiments done by others concerning DPPP .

First of all , phorone itself is *not* a valid precursor for diphoronepentaperoxide ( DPPP ) . This is one of those cases where the structure of the DPPP "derivative" is related in name only to the "parent" compound as a compliance with naming convention only , to designate structural similarity for the derivative , but *not* to suggest that the route of synthesis must involve the "parent" phorone itself , but rather another derivative of phorone . This sort of occurrence is not uncommon in chemistry . The actual "phorone related" precursor for DPPP is "phorone dihydrochloride" not phorone itself . Since phorone was reported to be insoluble in HCl , then it would seem likely that "phorone dihydrochloride" is also a derivative of phorone in name only , not to sugggest it is synthetically derived directly from phorone , but from a phorone related structure , the hydrated form of phorone , which is triacetone dialcohol . The triacetone dialcohol is initially formed from the condensation of 3 acetone molecules in the presence of HCl , and then further combines with 2 HCl's while at the same time losing 2 H2O's to form phorone dihydrochloride .
So we see that "phorone dihydrochloride" does *not* form from phorone and hydrochloric acid , but does derive instead from triacetone dialcohol and 2 HCl's with the loss of 2 H2O's .

The phorone dihydrochloride is then chlorinated further by the action of free chlorine to form pentachlorophorone , according to a chlorination scheme described by the patent , which involves a side reaction between HCl and H2O2 .
This chlorination mechanism appears to be speculative , and the actual reaction may involve hypochlorous acid as an intermediate , or the reaction with "free chlorine" stated by the patent may be a gross oversimplification for a complex reaction involving HCl and H2O2 and the
phorone dihydrochloride through the formation of an undefined and unspecified unstable intermediate for the end product DPPP which precipitates spontaneously from that unknown transition species .
This seems likely to me since the mixing of H2O2 and HCl does not produce clouds of free chlorine , in my experience , but simply produces a mixed solution of HCl and H2O2 in H2O . Generally reaction of such a mixture is observed only after some additional material is added to the system , as would be occurring with the process of peroxidation of some organic material added to the solution , which we have in the process for DPPP . Further experiments would be required for clarification of the actual reaction mechanism involving the formation of pentachlorophorone from phorone dihydrochloride .

Following the controversy in the heated discussion here which has led to some members being blocked or banned from posting , the discussion was carried a bit further with similar controversy at another forum where the same topic has been followed with interest . Since a more lucid writeup of the synthesis has been provided , which has pertinence to the development of the topic originating in this forum , including my own investment of time studying these reported experiments , I hope it is allowable to quote with credit and provide a link to the more detailed information about the latest efforts at a synthesis of DPPP . Some difference will be noted in the identification and naming of intermediates in the description below , but the discrepancies are reconcilable and it is the process being described in detail which is significant . The following updated description of the synthesis of DPPP is credited to j-scan , and quoted from his post at E&W ,
http://www.roguesci.org/theforum/showthread.php?p=68338&...
Quote:

j-scan December 26th, 2004 04:09 PM

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

Here is my write up...

I started with a 1:1 ratio of HCL and Acetone and added heat until the color changed to a dark orange. I continued the boil on a low setting and got the color down to a dark red -black) and then cooled it down over a period of days "freezer would have sufficed just fine".. The solution changed color again and the viscosity also changed to a motor oil consitency(very thick). This oily liquid is relitivly pure Pentacholorphorone (dark yellow orange.. looks black in standard light) say 90-95% and about 10-5% H20.. Ok I am guessing here... It has not much acidity to it anymore. You then have to add a few mls of HCL to get the peroxidation happening. After adding the HCl you then add H2O2 and give the solution a stir.
Cl2 is immediatly ejected from the solution (you can smell this)which turns bright yellow ( heat climbs up rapidly) and a yellowish orange precip is immediatly formed at the bottom of the flask... this then eventually migrates to the top of the flask where you can scoop it out with a plastic spoon. The more pure the liquid the better the yeild.. a small flask say 100ml SHOULD optimally yeild you around 80ml of crystals.
---problem occured the first time I tried this: because the solution was not completely reacted , TC AP formed with the DPPP... ALL of the left over acetone must be evaporated in open air for their to be pure DPPP.

-------------------------------------
more info and improved method as of 11pm Dec 25th:
--------------------------------------
Please follow carefully:

For the best results--->

200mL Acetone
300mL Muriatic Acid (30% HCL)

Mix together into a glass container and place into a hot water bath to 100C
Boil for 45 minutes until solution changes to a dark orange-red. Remove heat.
Allow the solution to cool off to 2 C or so for at least 10 hours without a lid. I left my solution for 24hours at room temperature. The solution should at this time be almost black as the HCL will have converted the majority of the acetone onto thick viscous Chloro-Phorone. Left over HCL content should be minimal.

The next step is to reintroduce 30ml of HCL catalyst into the Chloro-Phorone solution and add 500mL of chilled 35% H202. Chlorine gas will be expelled. A mass of yellowish -orange crystals should appear almost instantously, The temperature should increase slightly but should not boil over.
Dry the crystals using distilled water and ammonia/ or bicarbonate solution. rinse and dry.
-----the end product is quite stable when dry---not as shock sensitive as AP but highly explosive in the presence open flame or any surface temperature above 190C.


Hopefully these additional details and ideas of my own are helpful in further experiments seeking to confirm the Mackowiak patent for DPPP , and resolve some of the valid questions which have ben raised by earlier experiments in that effort .

Pyroz - 27-12-2004 at 21:13

The mistake that most people make while creating Phorone diHydrogen Chloride is in leaving the material to cool off. You have to leave the "chloro-Phorone" to sit in open air to evapourate any unreacted acetone. The result will be a highly vicous oily liquid which has a fruity smell to it..it doesn't smell like HCL or acetone in anyway. Once the liquid has been cooled to 5C add in HCL to prime the reaction and them add 30% H202--- precip will form immediately.

pics related to J-SCAN's developments

Matsumoto_Hideki - 27-12-2004 at 21:20

Alright, I know I am posting from the Same IP adress
but again I am on a router so don't kill me. Ok?

look at the pics at my webshot account.
http://community.webshots.com/user/matsumoto_hideki
see the 2nd to last pic... I assume this is pretty pure DPPP as the characteristics were way different.

[Edited on 28-12-2004 by Matsumoto_Hideki]

Rosco Bodine - 27-12-2004 at 22:08

There is almost certain to be an optimum ratio of acetone to HCl , combined and then heated to a specific temperature and held there for a specific time to produce the optimum yield of phorone dihydrochloride with least amount of higher polymerization products or other undesired byproducts . My guess is that
it requires a bit less HCl for the initial stage of the reaction producing phorone dihydrochloride , than is being used presently . Of course on a molar basis ,
the minimum requirement of HCl is 2 moles of HCl for every 3 moles of acetone . And probably a little excess of that theoretical amount of HCl , on the order of perhaps 5 % excess of theory should be plenty to drive the reaction .
For use of pool grade muriatic which is 31.45% HCl , that would amount to 210 ml of the HCl mixed with 220 ml acetone , which is very close to the patents equivalent volumes . The actual theoretical proportion without any excess for HCl would be 200 ml of HCl 31.45% for each 220 ml acetone . What we don't want is any large excess of HCl since it is catalytic in an already vigorous reaction . And the volatility of acetone insures that some of the acetone is going to be lost to evaporation , which will result in an excess of unreacted HCl as a given . The volatility of the acetone would make this a reaction better suited to being done in a closed system , with some provison for
reflux , that is for condensing and returning any acetone vapors back to the heated reaction mixture . Something as simple as a smaller jar or bowl filled with ice cubes and set into the opening of the container in which the acetone and HCl mixture is being heated would be helpful in keeping the acetone from escaping and
not only reducing the yield by its loss but causing an overly acidic residue to be what remains when the heating is finished .

[Edited on 28-12-2004 by Rosco Bodine]

end product

Pyroz - 27-12-2004 at 22:18

..this was my end product---after peroxidization of the Phorone dihydrogen chloride. I compaired the color to standard AP--- here is what it looks like.

100_2539.jpg - 274kB

Sweet!!

Joeychemist - 27-12-2004 at 22:34

It looks like Rosco is doing most of the work here. I think that you are correct with most of what you said and upon a second glancing of the patent it is actually quite obvious now what reaction is happening. But why the hell don’t they specify and elaborate, I mean why the hell wouldn’t patent specify such important details, I guess they felt it wasn’t necessary. I do however think that the procedure mentioned above is working but it is rather vague and some mistakes need to be fixed but I think we have something to go by now, something to build on. This latest information you have provided is the most crucial piece of the puzzle we needed.

I tried j-scan’s procedure, although I must say I did produce some fine DPPP crystals, I have to report good, bad and strange results.

I used the exact specifications in the procedure mentioned above by j-scan. only I scaled the procedure down to 50ml Acetone and 75ml HCl 30%. I slowly heated the mix for 2 ½ hrs with a plastic sheet over the reaction vessel to minimize the evaporation of the phorone. (I noticed the phorone was condensing on the plastic sheet quite a bit, so I had to put a 1g weight in the middle to cause the condensation to run back into the reaction vessel). After letting the phorone cool and sit for 12hrs without the plastic sheet the phorone smelled very sweet and slightly acidic and was very dark red.

Next I split the solution into two beakers, beaker A and beaker B, I added 7.5ml of 30%HCl to the phorone in beaker A which caused some heat, I did nothing to beaker B. I then chilled both to 2C and added 62.5ml 35%H2O2 to both beakers. The heat increased 10 C in both beakers. Beaker B formed a few yellow crystals almost immediately but then stopped and started a very slow bubbling precip (AP), but not for long. But beaker A with the additional HCl added beforehand formed very nice yellow crystals, but they smelled acidic! I washed in sodium-bicarb 2 times and dried on a paper towel, 2g is what I ended up with. That’s not too good. The dried crystals smelled weird. It was a soft smell not like phorone and not like AP.

I noticed a very peculiar smell before and after burning. This was is not AP, the two were nothing alike. The substance recovered was a very light yellow/green in color and smelled like umm… I can’t really describe it, but I like it, it’s a weird odor and it’s not very strong. The collected crystals will detonate with sharp report when held 3” above a Bunsen burner in quantities less than 0.2g and only produce a miniscule amount of smoke, no real smoke to report thought. A hammer test proved it to be more stable than AP but not much. Density was higher than AP but only slightly.(I can’t really tell with my crapy method and scale). Upon examination of 0.1g under a microscope at 100X I could clearly see DPPP crystals. Not only that but I could see both TCAP and DCAP and I could also see broken DPPP crystals that broke when I put the sample between the glass sample slides.

After I was done with the usual tests I had enough left for a brisance and power test. I packed 1g of the suspected DPPP into a tube with exactly 2½ kg pressure (I have a press) I did the same with 1g AP. I drilled a hole in two red masonry bricks and placed the mini charges in the holes, they fit snug. The AP broke the brick into several large pieces while the DPPP shattered the brick into many smaller pieces. It was quite clear who the winner of this test was.

I don’t like the fact that I only produced 2g with all that H2O2 I dumped into the mix I should have made more. I would have made atlest 10 grams of AP with the same amount.

In conclusion, this procedure works but not well. We now have to solve the other side of this “rubrics cube”, the details of j-scan’s procedure are sketchy, but I think that we are on the right track now, but this is going to take a lot of testing now to set the difinative synthesis for DPPP down on paper. We now need to find temperature and time range, how to increase total product yield and I would really like to know if this explosive could be prepared from other precursors.

Rosco, since you do not wish to waste you’re reagents and you have obviously put fourth you’re time and effort into identifying the reaction which occurs, I am willing to waste mine to further our knowledge and understanding of DPPP as well. Just let me know if there is something you would like me to try or test. I have used the last of my acetone and must get more to further the testing.

Sorry for the long post

Edit] I just realized why the yield was so shity. J-scan is off on his measurements and I followed his instructions carefully so while scaling down the procedure I didn’t even notice the error. That tard J-scan is using two parts 35% H2O2 when the patent calls for two parts 30% H2O2, so I wasted precious H2O2 because this fool mis-calculated and I assumed he was right. But still that little miscalculation did not affect my total yield that much. Like I said there are problems that need ironed out.

[Edited on 28-12-2004 by Joeychemist]

[Edited on 28-12-2004 by Joeychemist]

Rosco Bodine - 27-12-2004 at 22:45

That AP / DPPP comparison picture looks very interesting indeed :D

It seems to me that once the synthesis of DPPP is well understood in all its variables and the optimum ratios and temperatures , ect. are established , that it would be valuable to then investigate the possibility of coprecipitation of DPPP with MEKP and perhaps even AP as well , given the possibility of producing a high density product which is a binary or tertiary composition . If DPPP is difficult to obtain as dense crystals , as some have reported , then that is one way to solve that problem . Another idea for slowing the precipitation of the DPPP and improving its crystal density is to dilute the "red oil" with methanol before its peroxidation , and see if dropwise addition of the peroxide with stirring will result in more dense "gritty" crystals of DPPP . Keeping any added HCl to a minimum may also help slow the precipitation and aid crystal growth .

Pyroz - 27-12-2004 at 23:01

cool! Glad to hear that you've had a fairly successful go at making DPPP.

If you want a better yield you might want to try leaving the boiled Acetone+HCL mixture go black then.....
Leave the solution at room temperature for at least 24hours and the liquid volume will decrease quite a bit. Remember you are using 30% or so HCl ---70% water ---there will be considerable amount of acetone left over unreacted. Unreacted Acetone will create dreaded TCAP almost instantly in this procedure when reactants are added. You are looking for a solution that has an oil like consistancy.
Your yield should be pretty decent---- german patent states 90% yield--- that seems a little high for me. I'd say 60% being more reallistic.

100_2543.jpg - 206kB

PainKilla - 27-12-2004 at 23:16

Just a note for everyoone, be careful when working with all this stuff because there is a very good chance it is cancerous, or toxic or mutagenic w/e....

I will be trying this synth most likely thursday, using both Cl and non-cl methods, with luck, I'll be able to get some conclusive results, as the Cl method cannot be used in formation of AP, at least as far as I know.

mr.pyro - 28-12-2004 at 00:00

Pyro z,

How many ml of reagent do you have there in that jar, it seems you have a fairly large yeild of DPPP in the previous pictures. When you heat your Phorone DiHydrogen Chloride, do you do it covered, uncovered? How Long Approx? And you let it sit out, and it changes I presume from Dark Red to Black and thickens up.

My Phorone DiHydrogen Chloride after boiling for an hour or so lost about half the volume and is dark about as dark as red wine, but not black at all. I will leave it out tonight and see what happens.

I also will tommorow do some testing with making this stuff, I shall boil 2 large batches of HCL+Acetone One covered, One Uncovered for 2 hours each. Then I will seperate each batch into 4 equal amounts each One covered into the freezer, one uncovered in the freezer, one covered laid at room temp, and one uncovered at room temperature. I want to experiment to see which one(s) will make the thick black motor oily Phorone DiHydrogen Chloride.

[Edited on 28-12-2004 by mr.pyro]

[Edited on 28-12-2004 by mr.pyro]

Pyroz - 28-12-2004 at 00:32

I have about 1L of phorone dihydrogen chloride in a mason jar.

Phorone diHydrogen Chloride will darken if left at room temperature for several hours. After 24 hours the solution will stop reacting a should be black oily and viscous.
Likely your acid/Acetone mix will continue to be warm well after you've taken the heat off of it--- the reaction is still continuing.
If you are saying that after heating the mixture you have a red-wine like solution it either means you've added too much acid which can be easily corrected by adding in more acetone--then heating the mixture back up again to 80-100C for 30 minutes
---or the reaction needs a little more heat to get it polymerizing into a phorone-- this does happen some times due to acid concentrations. Keep a lid on it while boiling--do allow gas to escape by making some air holes in the contianer lid! When the solution is cooling off leave the lid off of it... it will become darker as the free acetone vapours off.

[Edited on 28-12-2004 by Pyroz]

Rosco Bodine - 28-12-2004 at 00:37

Quote:
Originally posted by Joeychemist
It looks like Rosco is doing most of the work here. I think that you are correct with most of what you said and upon a second glancing of the patent it is actually quite obvious now what reaction is happening. But why the hell don’t they specify and elaborate, I mean why the hell wouldn’t patent specify such important details, I guess they felt it wasn’t necessary. I do however think that the procedure mentioned above is working but it is rather vague and some mistakes need to be fixed but I think we have something to go by now, something to build on. This latest information you have provided is the most crucial piece of the puzzle we needed.
One thing I have considered is that the inventor may not even be certain himself what exactly is the reaction mechanism for the compound he invented .
[snip]
Quote:

Rosco, since you do not wish to waste you’re reagents and you have obviously put fourth you’re time and effort into identifying the reaction which occurs, I am willing to waste mine to further our knowledge and understanding of DPPP as well. Just let me know if there is something you would like me to try or test. I have used the last of my acetone and must get more to further the testing.
Something which I have considered possible is that a phorone monohydrochloride may actually be the precursor desired , ( at least as a first polymerization product ) and that if this is true then essentially twice as much HCl as needed initially may be what has been used in efforts so far . A hint at exploring this possibility is demonstrated when adding some extra HCl to the "red oil" before the peroxidation step . The thing I have wondered is if the initial formation of a monohydrochloride derivative of phorone is preferable for the first step where acetone is polymerized by HCl , and then there is added an equal amount of HCl and perhaps a subsequent heating to complete the reaction in two stages , which forms the phorone dihydrochloride . This strategy may possibly improve the yield by decreasing the formation of undesired higher polymers which could be produced by the higher initial acidity of the present approach . I can't really provide any better justification for testing this theory than it is simply a suspicion which may or may not have any bearing , but it is one variable that did occur to me as possibly worth testing . Another variable is the amount of peroxide described by the inventor seems to be excessive , but the amounts you are using seem more in agreement with theory . My estimate is that it would do no harm to reduce the amount of hydrogen peroxide specified by Mackowiak by about 15% , in its relative
amount in proportion to the acetone . And as I mentioned earlier , the HCl specified by Mackowiak seems excessive by a slight amount also . These proportions and probably the method also could be refined by small adjustments . The details of how Mackowiak achieved a 90% yield may be proprietary , and the result of his own fine tuning of a process whose details are the secret we learn little by little by experiments .

mr.pyro - 28-12-2004 at 00:40

Well good, I was heating that red wine batch at 60 C for about 1 hour, I think it needs more heat? As soon as I took it off the burner it went right into the freezer. Is that stopping the reaction from polymerizing into Phorone Dihydrogen Chloride.

Pyroz - 28-12-2004 at 00:45

It will likely will slow down the reaction to a snails pace if you put it in the freezer--I'd warm it back up and leave it uncovered on a shelf and allow for it to digest. It should be nearly black by the morning---

More pics coming of other syth with explosion footage!

Matsumoto_Hideki - 28-12-2004 at 00:49

Sorry for the long post

Edit] I just realized why the yield was so shity. J-scan is off on his measurements and I followed his instructions carefully so while scaling down the procedure I didn’t even notice the error. That tard J-scan is using two parts 35% H2O2 when the patent calls for two parts 30% H2O2, so I wasted precious H2O2 because this fool mis-calculated and I assumed he was right. But still that little miscalculation did not affect my total yield that much. Like I said there are problems that need ironed out.

[Edited on 28-12-2004 by Joeychemist]





Are we trying to start another war here? Joey that is immature! We understand your pain. errors are what make science a challenge. live with it.
EXPERIMENT #15 Room temp Phorone HCL production.
I just did another batch of Phorone and I am letting that react at approx 20c. I would like to cold form it so that I can study the reaction even further. I will keep you guys posted with pics.
--------------------------------------------------------------
1:1.1 1 part Acetone to 1.1 HCL 35% Muratic acid
flask is sealed shut.

Warning

vulture - 28-12-2004 at 08:23

You are again using different usernames to talk to yourself. Schizophrenia is treatable, go see a neurologist. Otherwise be banned and this time by IP.

Vulture WTF?Not this again, short memory?

Matsumoto_Hideki - 28-12-2004 at 09:30

Nope... Please pleaseeeeeeeeeeeee, understand the concept of the router.
The IP adress being the same is because I am on a LAN. You are a gatekeeper so I assume you know computers.. ie) Local area network. I am one of 3 compters. :mad:

[Edited on 28-12-2004 by Matsumoto_Hideki]

vulture - 28-12-2004 at 11:42

You just don't get it, do you? Do you really think everybody on this board is stupid?

If you are on a LAN, you don't need to talk to and ask people that are on the same LAN, because you can speak to them IRL. I know sock puppets when I see them.

[Edited on 28-12-2004 by vulture]

Pyroz - 28-12-2004 at 12:49

Hey vulture--- you mind if we keep topic on track. Rather than lashing out at a particular user lets start cooperating and share some valuable information here.

Thanks.

PS. for someone who is a gatekeeper you sure don't get the concept of sharing a network connection. I am the host for hideki and I've talk to the admin of this site--- you may contact me if you have problems understanding this. Thank you for listening.


[Edited on 28-12-2004 by Pyroz]

mr.pyro - 28-12-2004 at 15:32

I tried today boiling 200mL Acetone + 300 mL HCl at 100 C. After about 15 min it was vaporing off alot of white vapor that smelled of chlorine. Also, It boiled off about 100 mL of reagents in that time, I tried to keep a cover on it, but it would have burst the saran covering it. After about 20 min or so it was a little darker then piss yellow, but I couldnt stand the fumes so I dumped it down the drain. What is going wrong. PyroZ how did you manage to make 1L of Phorone DiHydrogen Chloride? It seems like I was loosing way to many mL by vapor then I was supposed to.

Pyroz - 28-12-2004 at 16:01

Quote:
Originally posted by mr.pyro
I tried today boiling 200mL Acetone + 300 mL HCl at 100 C. After about 15 min it was vaporing off alot of white vapor that smelled of chlorine. Also, It boiled off about 100 mL of reagents in that time, I tried to keep a cover on it, but it would have burst the saran covering it. After about 20 min or so it was a little darker then piss yellow, but I couldnt stand the fumes so I dumped it down the drain. What is going wrong. PyroZ how did you manage to make 1L of Phorone DiHydrogen Chloride? It seems like I was loosing way to many mL by vapor then I was supposed to.


...you had the reaction going, and you should have continued to heat the material for at least another 20-25 minutes. You would have seen a major colour change--- and it would have gone much, much darker.
Punch a few holes in the top of your saran covering to prevent the saran lid from bursting. As for loosing a large volume of liquid-- this is unavoidable. I started off with 2L of acetone+HCL ----I have 1 L left and its really concentrated material. It is so dark light does not pass through it. It also has a flowery smell to it unlike acetone.

hope this helps,
feel free to send me an email message and I'll see what I can do to help.

Joeychemist - 28-12-2004 at 16:21

Quote:
Originally posted by Pyroz
Punch a few holes in the top of your saran covering to prevent the saran lid from bursting. As for loosing a large volume of liquid-- this is unavoidable.


It is avoidable with a slow hot water bath on a hotplate. As long as you are careful not to let the acetone/HCl/phorone solution boil your loss will be minimal, this has already been said;)

just concentrated more Phorone HCL

Matsumoto_Hideki - 28-12-2004 at 17:23

I am starting a slightly different Phorone HCL
synth using 100ml Acetone to 110ml HCL 40-42% vol muratic acid.

We will see what comes from this.
QUESTION FOR ALL OF YOU WHO HAVE ATTEMPED TO MAKE DPPP... Has anyone been able to get the dark orange material that I have fetured on webshots? Has anyone had that as a precipitate yet? What properties did you notice about it?


BTW... Agreed Joey in the last batch one container that pyro did actually polymerize, I guess this is due to him getting the solution too hot to fast. ( a brown/yellow plastic formed on top of the Phorone HCL. A slow boil 60-90c on low is better idea. Good suggestion, as I had my best results from this heating method.
---Pyroz, no the black liquid that you are reffering to has a hidious smell to it and reminds me of the worst tar smell you could imagine.. putrid.


Pyroz is away and won't be back until tommorrow early. I am using his computer right now.

[Edited on 29-12-2004 by Matsumoto_Hideki]

[Edited on 29-12-2004 by Matsumoto_Hideki]

[Edited on 29-12-2004 by Matsumoto_Hideki]

[Edited on 29-12-2004 by Matsumoto_Hideki]

Rosco Bodine - 28-12-2004 at 20:39

An experiment was begun today to perform the acetone polymerization to phorone dihydrochloride , using a closed
pressure vessel to prevent escape of vapors and maintain the proportions of reactants . A sparkling wine bottle 750 ml capacity , having a threaded aluminum cap with a poly sealing gasket has safely contained the reaction mixture for eight hours so far . In the bottle is 225 ml acetone to which was added 200 ml of HCl 31.45% , and the bottle sealed firmly but not overly tight using the threaded bottle cap . The mixture warmed spontaneously to about 60 C and the gentle exotherm continued for 45 minutes
as condensation on the upper portion of the sealed bottle formed and trickled back down the inner surfaces returning to the reaction mixture . At 45 minutes the temperature began to fall and refluxing vapors ceased to condense on the inner walls of the bottle . The color of the mixture had changed from being clear to a pale yellow . Supplemental heating was applied using a small electrically heated water bath of the sort used to steep spices to produce fragrances , a potpourri "crock pot" into which the lower third of the bottle fits with a bit of clearance at the sides . A coffee mug warmer would probably work as well for
gentle heating for hours unattended .
I estimate the temperature of the bath is about 80 C . On the upper portion of the neck of the bottle is wrapped a moist layer of paper towels secured with a rubber band , to provide some evaporative cooling if needed . At 2 1/2 hours the color is deepened to a bright yellow and at 6 hours the color is a red orange tea color . At 7 1/2 hours the color
has darkened further to a dark reddish brown and the mixture is becoming opaque , taking on a dark milky appearance as if there was suspended colloidal material as contrasted with simply a dark tint . The scattering effect on a light beam can be observed by shining a flashlight beam through the mixture . It is planned to let the mixture
continue reacting overnight . One observation I did make is that even with supplemental heating , there has been no condensate of vapors observed since the
original spontaneous exotherm tapered off leaving a pale yellow mixture which evidently at that point experienced an elevation of boiling point due to the reaction product . So I am inclined to believe there is already a reaction product of some sort present in significant amounts even as early as the end of the first hour , before any supplemental heating is applied . If the mixture was still chock full of unreacted acetone at the end of the first hour , then it would seem likely that the refluxing would continue to be observed , and because it isn't refluxing then the acetone must already be substantially combined to form some higher boiling point material . It would be interesting to monitor the pressure drop using a gauge or manometer which would detect the sudden elevation in boiling point for the mixture , and try to determine what exactly is the predominant product at that point . Except for the slight vapor pressure of the acetone which decreases to nothing at the end of the intitial exotherm at about 45 minutes , the reaction produces no further vapor pressure of any significance thereafter . I loosened the cap on the bottle from time to time to check for and release any pressure and there isn't any acetone pressure evident after the spontaneous exotherm ends . I suspect that this point marks the conversion of the acetone to triacetone dialcohol , and the slight tinting is due to
the early presence of some phorone dihydrochloride which appears later in increasing quantity and gradually darkens the color of the mixture . A yellow dyestuff will appear darker and darker red as its concentration increases and its state of subdivison is decreased . The same effect can be observed for picric acid where a boiling hot concentrated solution is very dark red , but one drop added to a liter of cold water will color it bright yellow . The same for sodium polysulfide , dark red in the beaker , but bright yellow in a thin layer on a white surface . I think this is possibly the same story for the phorone dihydrochloride . It's yellow for sure , so yellow it looks red ,
and even darker depending on its concentration .

[Edited on 29-12-2004 by Rosco Bodine]

Right on

Matsumoto_Hideki - 28-12-2004 at 21:37

Yes, before coming back to this form I was discussing my "success" with others on Rogue science. All I did was heat the red Phorone HCL to black and then left it to settle for a few days. The solution darkend even more until it became oily. You should be able to clearly see the formation of Phorone/ Phorone HCL on the top of the black liquid as a slick of sorts. This was my signal that digestion was nearly complete.
What you are describing is exactly what I saw before my "success". I am eager to see what happens when to try and peroxidate your pressureized PHCL
*****I would also do a pH test to be safe..
****

I was just checking on my two containers of PHCl and one of them was red at the bottom knowing that i added more acid to acetone.. I added 1ml more acetone and the solution beagn to reheat... aha..
my other container was almost completely black..

[Edited on 29-12-2004 by Matsumoto_Hideki]

[Edited on 29-12-2004 by Matsumoto_Hideki]

Rosco Bodine - 28-12-2004 at 22:18

I did notice some small thin rafts of solids floating on the surface of the reaction last time I checked to see how it was proceeding . I suppose the mixture is oversaturated with whatever it is producing and some of it is precipitating .
After evaporating some of the water by
use of a shallow heated glass tray , I may
end up having to add methanol to get a good clean solution for the peroxidation .

Update : After the mixture has continued heating overnight , at 17 hours from the start of the reaction there is clearly an oil separating and floating upon the surface , a small amount perhaps 1 or 2 ml , too little to form a separate continuous layer , but enough to be certain it is an oily precipitate . The mixture is extremely dark red en masse , but when swirled so that a thin film can be viewed as it sheets across the walls of the bottle , the solution is very bright yellow in layers thin enough for light to pass through .

And about the pH , I was going to hold
a strip of pH paper in the vapor above the hot solution and see if it would indicate any residual HCl vapor coming off the surface . I used just a tiny bit excess of theory of acetone hoping to tie up as much of the HCl as possible and not have excess HCl to cause problems later over-catalyzing the reaction and causing too rapid precipitation for good crystals to form . I am trying to implement some of the ideas which have developed as I read these other posts , and try to discover any potential refinements , since the reported yields aren't yet squaring with the 90% reported by the patent . Sheesh , I havent even added up the mole weight of DPPP yet to know what
to expect and calculate yields . My H2O2 is so old that I will have to do a specific gravity test to determine its strength and I know it's down below 25% so that won't help , but maybe by drying out the excess water good from the phorone dihydrochloride , I can help make up the difference for the extra water in the slightly diluted peroxide .

[Edited on 29-12-2004 by Rosco Bodine]

Sounds good so far.

Matsumoto_Hideki - 28-12-2004 at 22:57

I think you are probably going to have a decent batch,
you are getting soild masses which sounds good to me. I think that evapouration method is one i should give a go with increased surface area. Although I didn't do that last time and I managed to yeild a full 1.5g.. I guess I just got lucky? The liquid I removed was from the top of the solution that seemed to yeiild the product. As I said again it looked like "wulfenite"
red-brown clumpy crystals but would dry to finer product, the colour though stayed and never changed. In a flame a small amount would deflagrate with a big wooomp and a small puff of black smoke. IF the crystals were held above a propane flame they would melt and then detonate with a terrific force and no soot would follow. There was absolutly no smell either after detonation.






BTW...I get my H2O2 at the local hydroponics store for $32-35 CDN per 4L . I get a student discount of 10% though. It ranges from 35-36%vol.
My HCL is dirt cheap.. 35% for $15 CDN /4L
Acetone is $13CDN/4L

By the way could one use calcium peroxide to make organic peroxides? My organic chemisty is weak I know..

Woops, I can't get better than 42%, ohk.. solves that problem/






[Edited on 29-12-2004 by Matsumoto_Hideki]

[Edited on 29-12-2004 by Matsumoto_Hideki]

[Edited on 29-12-2004 by Matsumoto_Hideki]

Joeychemist - 28-12-2004 at 23:04

IICR, there is no such thing as 70%HCl. You can use calcium-peroxide in most cases, but why? I don’t know if it’s cheaper of not. You would be left with Ca and H2O as a by-product, this could complicate some procedures.

My orange red product deflagrating

Matsumoto_Hideki - 28-12-2004 at 23:42

Well here is some video of a microsized amount deflagrating in a candle flame.
this amount is maybe 1-2mg? about the size of drop of water

slow the video down and you may be able to seet the black soot.

[Edited on 29-12-2004 by Matsumoto_Hideki]

Attachment: 100_2533.MOV (239kB)
This file has been downloaded 1129 times

Joeychemist - 29-12-2004 at 08:51

Check this out.

http://members.fortunecity.de/potatoguns/DPPPSyn.html

Pyroz - 29-12-2004 at 09:07

It would be interesting to know what colour DPPP is in its true-pure form. This would cetainly help to quickly identify DPPP from other peroxides :)

Rosco Bodine - 29-12-2004 at 09:51

There is for me some uncertainty that the compound DPPP and its precursors are even correctly designated in the patent . It seems entirely plausible that there could be some variations upon the structures specified by Mackowiak , and I am curious as to what lengths the process of accurately identifying the precursors and end product was taken ,
and how accurate is the reaction scheme stated by the patent .

I wonder

Joeychemist - 29-12-2004 at 09:57

Well that’s just it pyroz, pure phorone can be any color ranging from a light yellow to a dark green, so I would imagine that the derivative compounds of phorone and similar or other related chemicals (phorone dihydrochloride, pentachlorophorone) could be any color as well, therefore there might not even be a pure color of DPPP. But from what I have gathered it’s not white like AP.


Rosco, just a thought, but if you heated the Acetone/HCl until a very thick pure layer of phorone is left. You could used a separatory funnel to separate the two layers, Then you would have the pure sample of phorone and the bottom solution of…phorone dihydrochloride and triacetone dialcohol??-is this right?) left over, you can then experiment much more efficiently and be more conclusive in you’re testing and results.
:D

Rosco Bodine - 29-12-2004 at 10:57

Quote:
Originally posted by JoeychemistRosco, just a thought, but if you heated the Acetone/HCl until a very thick pure layer of phorone is left. You could used a separatory funnel to separate the two layers, Then you would have the pure sample of phorone and the bottom solution of…phorone dihydrochloride and triacetone dialcohol??-is this right?) left over, you can then experiment much more efficiently and be more conclusive in you’re testing and results.
:D
In my estimation there is *never* any phorone itself produced , but a phorone related derivative , phorone dihydrochloride , which forms from the further reaction of HCl with triacetone dialcohol . In a basic system the triacetone dialcohol might yield phorone by dehydration , but in this acidic system the reaction blows right past phorone to form the dihydrochloride of phorone . I believe the separated layer is not a different substance from what remains in solution . When and if enough of it separates so that the color of the layer can be observed , this will be further information of possible value . Another possibility is that the oily precipitate is a monohydrochloride derivative of phorone ,
or some "ether" of triacetone dialcohol ,
or possibly some other minor polymerization product . I may leave the reaction mixture for a week to digest at 70 C , simply to observe any changes and so long as changes are occuring , let the reaction run its course until no further reaction is evident . This reaction mixture reminds me greatly of the condensation reaction of benzaldehyde and nitroethane in the presence of a small amount of butylamine , to form phenylnitropropene , with the expulsion
of water which then floats on top of the
hot reaction mixture . That digestion is
steady for several days , even up to a week before it completes . And it is just my guess that this condensation may follow a similar course . Driving these sorts of reactions with heat can make them finish more quickly , but reduce the yield and cause increased formation of undesired byproducts of the "highly colored higher polymers" variety . Whether that applies in this case is unknown . But I am in no hurry so I will
probably just let the mixture "steep" ,
incubating it to see what will "hatch" :D

vulture - 29-12-2004 at 12:27

Quote:

PS. for someone who is a gatekeeper you sure don't get the concept of sharing a network connection. I am the host for hideki and I've talk to the admin of this site--- you may contact me if you have problems understanding this. Thank you for listening.


Don't push your luck by getting cocky mister. I do understand the concept of LAN sharing as I am the network admin in two such cases, for a total of seventy users, thank you.

I therefore also know, that those users usually are in the same building and happen to talk to eachother, certainly if they share interests. Funny you don't address this point, which I mentioned earlier. Maybe you don't understand the concept of reading?

Rosco Bodine - 29-12-2004 at 12:30

It can get confusing who is who on a LAN .

It is sort of like being at a convention for cross dressing multiple personality bisexual Wiccans , very difficult at any particular moment to know for sure just which witch is which ;):P:D

Vulture give it up! please/ new discovery?

Matsumoto_Hideki - 29-12-2004 at 14:31

enough with that same IP = same person crap.
Roomate is my main host though the LAN. He is away notice PYROZ is not logged on at the moment.

... I think I just made a new discovery about DPPP... I think there may be derivatives? After letting my Phorone HCL sit overnight I then took 30ml of the dark red liquid out and added 0.8ml of HCL and let the entire solution settle. The solution layered and a thick black liquid shot to the surface after about 2mins. I then proceded to peroxiate it, and this material smells a hell of a lot like woops not camphor but Acetone.. aha there are lumps of AP in my DPPP that is why... , however the yellow crystalline material has exactly the same characteristics of the stuff featured on my webshots account (dark orange). You can see there is a white material mixed in the form of lumps. These I think are not AP as they do not resemble anything like it. I have yet to test these lumps to see if they will behave like AP in flame, yup they did. yellow stuff deflagrates with a sharper snap ... weirdness


[Edited on 30-12-2004 by Matsumoto_Hideki]

100_2555.jpg - 515kB

Rosco Bodine - 29-12-2004 at 14:38

The oily material which is floating on top of my acetone / HCl after 24 hours @ 70 C is a water clear material , unlike the highly colored mixture from which it is precipitating . Anybody care to venture any theories on what the clear oily precipitate may be ?

There is also a very strange looking sort of barely perceptible motion on the surface of the dark red liquid , almost as
if there were thousands of tiny bubbles
effervescing from the liquid , but the liquid is so darkly colored that the cause of the surface "animation" cannot be seen even in direct sunlight , the surface of the liquid seems to be "vibrating" is the only way I can describe the effect , and I have never before seen anything like it . There is no vapor pressure being produced , so I have no idea what to make of this "Brownian motion" on steroids !

[Edited on 29-12-2004 by Rosco Bodine]

Video and thoughts

Matsumoto_Hideki - 29-12-2004 at 15:10

Well I think you might have some H2O if your reaction totally finished???

Here is a video of that yellow material deflagrating. Notice it makes a real whoomp whereas AP deflagrates with little noise at this amount, at least in all the batches I have made.

Attachment: 100_2557.MOV (553kB)
This file has been downloaded 1456 times

Rosco Bodine - 29-12-2004 at 16:03

Quote:
Originally posted by Matsumoto_Hideki
Well I think you might have some H2O if your reaction totally finished???


There is already about 158 ml H20 present from the 200 ml of HCl 31.45% which were added at the beginning , plus 36 ml more of water formed from the dehydration of triacetone dialcohol , and the clear preciptated oil is more viscous than water , more like "white mineral oil" in appearance . I am thinking perhaps it is a bit of unreacted triacetone dialcohol or an ether thereof .

I have been thinking more about the strange vibrating effect I have been observing on the surface of the reaction mixture , and perhaps it is something like what a "lava lamp" does with two immiscible liquids which are close in density but that changes as they heat and cool . What I am thinking is there may be an emulsion that is being circulated by the heat , and I may get a phase separation if I let it cool , so I am going to do that and see what happens .

[Edited on 30-12-2004 by Rosco Bodine]

Another DPPP breakthrough?

Matsumoto_Hideki - 29-12-2004 at 20:56

it looks as though major breakthough has occured on rogue science in the synth of DPPP.
I need more evidence that this is really DPPP and not phoronated Triacetone Peroxide. i do think this is the target chemical however...
Member by the name of The_Rsert has done it!!
http://members.fortunecity.de/potatoguns/DPPPSyn.html

He is cooling his material down, this is what happened to me when i did mine on top of a cool fridge in a wide container and this is probably why I was unable to reproduce my success. If the temp goes above 5c the reaction overheats and TCAP %ile increases with a lower Diphorone Pentaperoxide yeild. I think finally someone has a properly documented method of making DPPP. I would be very interested in knowing the detonation/deflagration and other physical characteristics of this material R_Sert has produced.... It looks so simular to the material I obtained that I took a picture of on (webshots)
I am sooo interested!!!! :) Boy oh boy this is like Xmas all over again. :D

[Edited on 30-12-2004 by Matsumoto_Hideki]

[Edited on 30-12-2004 by Matsumoto_Hideki]

Tweenk - 30-12-2004 at 08:28

The rxn proceeds not quite as stated on this site... IMO this sholud happen only in alkaline conditions like all aldol condensation reactions :/ No idea why this sholud work

?oh What do you mean.?

Matsumoto_Hideki - 30-12-2004 at 08:43

You don't think it worked? not sure what you said?
I am just making a batch at about -32c and it seems aOk so far.

Tweenk - 30-12-2004 at 09:18

Well I'm wondering why this procedure works (or seems to work) when the reaction conditions are totally different from those supposed. Everything that should be happening is chlorination of acetone to monochloroacetone.

[Edited on 30-12-2004 by Tweenk]

Pyroz - 30-12-2004 at 10:18

You can't get chloroacetone from heating HCL with acetone. Chloroacetone is formed with raw Chlorine bubbled through acetone---its quite a different process. HCL will digest the acetone into a Phorone. Once the Phorone appears it will go from a clear yellow liquid to a red, then it will darken until the liquid no longer passes light. At this point, the liquid begins to thicken as unreacted acetone is vapoured off. Phorone diHydrogen chloride is left behind.

Yes. Please go see R_Sert's page

Matsumoto_Hideki - 30-12-2004 at 10:36

R_Sert has proven the power difference as well although he was unable to measure due to the fact his scale has a minimum of 0.5g he provided some AVI's showing the power difference between DPPP and AP. The results are quite what I had expected and should provide evidence to those who doubted my orignal conclusion about DPPP "before I was banned from here."
Does anyone remember those videos of DPPP I posted several weeks ago? ie) like the one with the exploding foil?

Tweenk - 30-12-2004 at 11:10

Chloroacetone is made by bubbling Cl2 gas through a solution of acetone in HCl, the process is not similar to chlorination of alkanes (it involves addition of Cl2 to a double bond of enolized acetone, and not the addition of atomized chlorine).

This must be one of those reactions which go completely other way than most people think.

agreed this is a strange reaction.

Matsumoto_Hideki - 30-12-2004 at 11:42

Well all i can tell you is if I had made Chloroacetone I would know about it as it is incredibly volitile and deadly. As I said it was used as a blister agent in WWI and in WWII by the Japanese. "I have heard this"
Also i don't think chloroacetone is a liquid at room temp... Correct me if I am wrong.
Black liquid is phorone HCL without a doubt.

Tweenk - 30-12-2004 at 11:56

To make something clear: I do not doubt if it has formed, but how has it formed :) It's very strange.

Is HCl driven off from the mixture during evaporation of unreacted acetone, or is it still there when you add hydrogen peroxide?

[Edited on 30-12-2004 by Tweenk]

[Edited on 30-12-2004 by Tweenk]

Rosco Bodine - 30-12-2004 at 12:03

The time is approaching 48 hours on my sealed bottle experiment . And a new development has appeared , a slight pressure was evident the last time I loosened the cap , giving that pffft sound of escaping gas when the cap was loosened , and then I saw immediately a slight refluxing of vapor on the inside walls of the neck of the flask . The temperature of the liquid measured 66 C ,
and no free boiling was noted when the pressure was released . This is the first appearance of any pressure or refluxing since the end of the first hour when the
spontaneous exotherm had ended . I believe the extended heating for 47 hours at 66 C has possibly reached a point of diminishing return , and this development of slight pressure is possibly
a marker , and indicator of some decomposition of the product of earlier reaction , or further conversion perhaps to some ether or halogen-ether derivative . More simply , perhaps there
is a reversion to acetone or an alcohol of
some kind . I will end the supplemental heating now at 48 hours and allow the
mixture to stand for further observation .
The drop of material left as residue on the thermometer tip stained a white paper towel an orange brown color almost identical to the color of fresh iron rust .
In thin layers which sheet across the glass when the bottle is swirled the liquid remains bright yellow , although en masse it looks ink black with a dark red tinge , to the surface . The mixture seems to have a physical property and viscosity more like an emulsion than a solution , but it does not separate into 2 phases except for a slight oily slick which has remained only a few ml , floating on the surface . It appears that it could possibly be separated by centrifuging or chromatography . But that may worsen the ability to get it to react in the peroxidation reaction , if concentration should result in a water imiscible product .

Update on sealed bottle experiment :
After cooling and standing for six hours an upper layer about 3 mm thick is visible , and its color appears darker and
more consistent than the majority of the
mixture below . The color difference is distinct , but barely perceptible because
both layers are so very dark colored . To see the interface between the layers requires bright sunlight . Swirling the bottle so that the mixture flows upwards across the inner surface of the bottle and then flows in a thin sheet across the glass as it drains back down , it is evident that a complex mixture which is an emulsion has formed , containing at least two and perhaps three liquid phases which are so very near to each other in density that the mixture is mostly a dispersion of very small blobs . There is a distinct separation of colored and clear oily phases visible in the thin sheet of liquids flowing across the glass after the mixture is swirled . But the separation is not clearly so visible in the dark liquids mixture en masse . After observing that this upper layer of more consistent and dark color is growing in thickness , I have decided to return to heating the mixture for a further time to see if the conversion of the lower layer continues . I am uncertain whether there is any difference between the upper layer and the lower layer , except for the water content , or if the upper layer is a actually a different compound accumulating as an end product of the reaction proceeding in the mixture below . This mixture is complex , and so very darkly colored as to test the observers skill at distinguishing what are differing shades of "blackness" so small in contrast as to strain the eyes to see the difference , which is never the less , visible there . The progress of this reaction is
important to understand , in identifying which component of the complex mixture is indeed the actual precursor for the DPPP , and how to optimize its yield in this step in order to get the highest yield of DPPP in the subsequent peroxidation .
And even if it is not necessary to isolate the active precursor , it would be good to determine the markers for the reaction which indicate completion of the formation of that precursor and where is the point it has formed in highest yield , or at which point its form , whether emulsified or separated will afford the highest yield of DPPP upon peroxidation . Understanding these variables will be necessary for optimizing the process for synthesis of the DPPP .

Another curious observation regarding this very strange mixture concerns the rust colored stain which a drop of the mixture made upon a white paper towel .
After sitting overnight , the dark red orange stain faded away leaving only a light tan colored spot on the white paper .
Go figure !

[Edited on 31-12-2004 by Rosco Bodine]

acetone peroxide vs DPPP

Pyroz - 30-12-2004 at 14:23

here is a movie I made to show the difference of the two materials... the sound is poor but notice the sharp cracking as the yellow power ignites.

---this is DPPP without a doubt.

Attachment: deflagration.mov (810kB)
This file has been downloaded 1533 times

Just finished a low temperature DPPP syth from totally digested Phorone HCl

Matsumoto_Hideki - 30-12-2004 at 16:46

The colour of DPPP is bright yellow almost green-yellow and not red-brown. Red brown colouration is unreacted Phorone HCl crystals tinting the DPPP. This was giving me the black smoke last time I had a sucessful synth and tried some out. There was also an unusual odor of phosgene-like smell, sort of like when methyl chloride burns. This bright yellow stuff has no odor after detonation or deflagration. :D

btw also I tried a test against AP and there is a much noticable difference in detonation characteristics.

Movie of detonation 0.1mg TCAP/ DPPP

Pyroz - 30-12-2004 at 17:09

Aliright first movie is of TCAP detonating via compression in Al foil on top of a copper strip 2mm thick. A flash is visible, notice that the strip moves quite abit and no crater is created in the copper. The detonation temperature is higher than that of DPPP.
I wasn't about to mesure surface temp next to it.. As I would like to keep my fingers.

Video #2 DPPP. No flash! In fact there actually was one but it happens so incredibly fast the camera didn't pick it up. My camera is set at 15fps movie mode. Notice the crater on the metal surface.

both The TCAP and DPPP were mesured out very very carefully on an electronic scale.

[Edited on 31-12-2004 by Pyroz]

Attachment: detvideo.mov (662kB)
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PainKilla - 30-12-2004 at 18:11

I am not sure...all those vidoes look pretty similair, we need a lead block test realyl to see what's better. There might have been no flash as it might have just been in between frames... I will hopefully do some conclusive testing soon...as soon as I stop being lazy.

Of course, I am not sayign what you have is fake or anything, just not anywhere near the power of the patent. Unless this has a VoD of 6000 or is consideribly less sensitive I will still be using AP as my primary, until I get a still anyway or some well, no just a still :p.

Can you perform some sensivity tests? Dropping a weight from varying hieghts? This would be much more conclusive. This could be some of AP possibly too... here is another idea....what happens when you add perxoide to chloroacetone?

[Edited on 31-12-2004 by PainKilla]

Rosco Bodine - 30-12-2004 at 18:41

A fairly easy to do brisance test might be possible by making a putty of a weighed amount of AP and weighed amount of binder , compared with another putty
with DPPP subsituted for AP . Each could be detonated on a witness plate and the damage compared . A soft aluminum sheet metal such as used for roof flashing is ideal for small charges . A more brisant material will show a cutting effect upon the metal , while a lower brisant sample will do a lot of tearing and banana peeling
of remaining attached shards on the underside of the material , if the witness plate is placed over the open end of a coffee can for example . The fragments will leave their signature on the bottom and walls of the can also giving witness to
velocity of the fragments , which is related to the brisance of the sample charge . Whether or not DPPP would make a similar putty with nitrocellulose made into a thick syrup with acetone , as does AP , and whether or not it would be reasonably stable like AP putty is unknown . Using dextrin as a binder is another option for making such test pellets . These should detonate easily from a touch with a glowing splint or spark from a fuse .

[Edited on 31-12-2004 by Rosco Bodine]

Testing DPPP

Mickhael - 31-12-2004 at 05:46

Although I am very enthused about trying DPPP out, I'm still relatively new to working with peroxides and I want to be very careful with them. So suffice it to say, I'm waiting on a more solidly tested synth, before mixing it up myself. Also because I don't have much lab equipment beyond a mixer, thermomiter, freezer, glassware and safety wear. If anyone thinks they have a fairly safe synth (not likely to form AP) I will happily try it out, I have a digital camera and such that will make documenting easy.

Rosco Bodine - 31-12-2004 at 12:58

Quote:
Originally posted by Mickhael
Although I am very enthused about trying DPPP out, I'm still relatively new to working with peroxides and I want to be very careful with them.
Thoughtful regard and study of such reactions is the credential of those who are still living after much time experimenting with energetic materials , and there are no "old" fools left to tell of their experiences speaking from their golden years , since mistakes are inconsistent with longevity in this area of scientific interest :D
Quote:
So suffice it to say, I'm waiting on a more solidly tested synth, before mixing it up myself.

That work is yet in progress
Quote:
Also because I don't have much lab equipment beyond a mixer, thermomiter, freezer, glassware and safety wear. If anyone thinks they have a fairly safe synth (not likely to form AP)
The presence of AP should not adversely affect the safety at moderate temperatures , and there is likely no significant amount of AP going to be produced by the current method .
Quote:
I will happily try it out, I have a digital camera and such that will make documenting easy.
None of those things being lacking is the impediment now , it is just a matter of time and charting experimental results to pin down the details of an optimized synthesis . Have patience as it could take some time to analyze all the data from different experiments and arrive at the definitive conclusions for what works best , even if it is never completely understood exactly why .

There have been some uncertainties I believe for some to believe that three acetones polymerize and then further react with two HCl . And yet the same doubters surely know that in the case of AP , there are what else but three acetones condensed in the presence of HCl under different conditions and peroxidized to form the *trimer* of acetone then peroxidized . The dimer , trimer , tetramer *are* themselves acetone derived polymers , so the matter that acetone derived polymers do exist is substantially already proved by AP itself .
The peculiarity of DPPP is that it is a variant on the same theme , but having a reaction scheme made to follow a different course , resulting in a quite different "polymerized acetone peroxide" variant .

I am going to do lead block tests tonight! maybe

Matsumoto_Hideki - 31-12-2004 at 15:30

I figure what the hell, I will do some tests tonight as my neighbourhood is going to be full of fireworks tonight anyway.:P
I will keep you guys posted about anything that happens tonight.

Mickhael - 31-12-2004 at 17:07

Thankyou for the excelent response, being as I have now read about a dozen slightly different synths over the course of this 12 page forum, what "current method" are you refering to?
Because if like you say there is minimal worries of creating to much AP I will go ahead with my own experimentation, I have everything I need for small synths, so why not contribute to the overal tests :)

Rosco Bodine - 31-12-2004 at 18:26

The current method is forming the polymerized acetone addition product with HCl and then peroxidation of that
product using a catalytic amount of additional HCl and H2O2 . There are variations on the quantities , times , temperatures , orders of addition by people trying to discover the method which gives the highest yield of purest product with the greatest ease . I am working on that aspect myself by my experiment with low heating of a mixture of acetone and HCl for an extended time , so that I may observe the changes occuring in slow motion , seeking knowledge of how the precursor is formed . There are distinct stages through which the reaction develops and that series of reactions has not been really explained . It is possible that this polymerization scheme for acetone has never been described in the literature .
There is much published about the aldol condensation under basic conditions and a whole lot of references , but not much in the way of description of acid catalyzed condensation and addition products for acetone and HCl . If anyone should find any pertinent literature references for phorone dihydrochloride by that name for the compound which I have designated for it , or any other reasonable name for the same structure , please share the citation or the article itself . It is difficult to break new ground in chemistry , and we very well may be doing so if no such citation exists . Often if a literature reference exists in support of a patent designated reaction , the citation will be noted in the patent . And since no such
literature citation is noted in the Mackowiak patent , then it reenforces my suspicion that phorone dihydrochloride may never have been named and characterized . It could also be that because of the lack of details in the Mackowiak patent that the significance of
his invention was unappreciated by others who were unable to confirm his findings . Thereafter anything related to the patent including the precursor and the end product , also the intermediate pentachlorophorone , may have received no professional recognition nor scrutiny .
Sad for Mackowiak , if this is the story , but this sort of thing happens too often where an invention is rediscovered thirty years or more later from an inventor who never received that reward he had been deserving .

Cold formation sounds much more efficient

Matsumoto_Hideki - 31-12-2004 at 19:42

Ok. I have done cold formation before although slow it is
often best for observation of the chemical processes.
One direction I may steer you in is adding HOT fuming HCL to cool acetone and this creates an instant chemical change and a green-yellow hue to appear almost immediatly. Then take your phorone HCl and keep heat on it for 24hrs @ 60c.. after this test for remaing HCl and freeze to -20c or so.. the liquid should be like toffee and solid masses of PHCl crystals should be forming at the bottom of the flask.
I got my best yeild with this method. See my webshots acount.

BTW... Could find the crystal structure of DPPP and contrast it against AP? maybe sketch it or something.

I think you will be impressed with your results.

[Edited on 1-1-2005 by Matsumoto_Hideki]

Rosco Bodine - 31-12-2004 at 21:16

The sealed bottle in which I have been slow heat digesting 225 ml acetone and 200 ml HCl 31.45% , has been at 66 C for 72 hours , and an upper layer is separating slowly from the mixture below .
The upper layer is about 8 mm thick now and it appears to be single material of extremely deep yellow color in thin layers , and absolutely ink black en masse . The lower layer appears that it may be a fairly stable emulsion of the same material as the upper layer , along with water or some other clear oily material . It is the separation of these materials into separate phases I am seeking . It probably isn't necessary to separate the mixture for the benefit of making DPPP , but at this point I am trying to identify what exactly are the components contained in the strange mixture to satisfy my curiosity , and perhaps test the components reaction to peroxidation separately to see what results for each , if anything . The formation of DPPP may require both components of the mixture , or it may require the mixed components used before the point of digestion to which I have extended the reaction . I intend to cover all the obvious possibilities in studying this reaction . I suspect that the product from the slow digestion I am performing is the same as what is gotten by use of shorter times and higher temperatures like others are doing , but the slow progress of the reaction is allowing for me to observe what changes cannot be seen in a boiling mixture . Has a phase separation been observed in the mixtures which have been refluxed and at higher temperature , or is this a peculiar development in the slower digestion of the mixture which I am watching occur ?
Later I am going to monitor the temperature on a refluxed mixture in a stir mantle , ramping the temperature and
perhaps comparing the result both with and without water removal during the reflux . I also intend to examine the possibility of a monohydrochloride of phorone , and some other possibilities because I am not entirely certain that the reactions which Mackowiak has designated are necessarily correct , although it does seem likely they are correct . One thing I want to resolve entirely is whether the coloration of the DPPP is indeed due to the DPPP or if it is a tint which results from a byproduct or impurity . Recrystallization , and some activated charcoal in the solvent could resolve that question . I am curious also
about the color fade which I saw occur overnight where a drop of the precursor was left as a stain upon a white paper towel , whether the colored material simply evaporated , or if the material changed composition on contact with air .
There is a very slight chance that the precursor could peroxidize itself in contact with air , which is an interesting possibility . There is simply more we don't know about the process and the materials involved than we do know . But it is damn good that at last it appears experiments are producing the desired product , which ends the long frustration of trial and error experiments which were
not producing much answers before except proving what did not work :D
Now we are getting somewhere in nailing down the details of the process and understanding more what Mackowiak was doing . Having his lab notebook would save a lot of needless duplication of work ,
and "reverse engineering" the process , which has been something of a riddle to be solved . Have to wonder what other stuff this fellow may have invented , and filed or never filed applications concerning .

Ahhh only 31% I see..

Matsumoto_Hideki - 31-12-2004 at 23:03

I don't know if it is going to make any difference but I strongly suggest you get some concentrated muratic acid (35%) as the yeild is going to be better. My guess is that when you are finished your reaction you will have a dark red layer (unreacted acetone) and a black red layer to contend with as I do think you may run into partial digestion of the acetone therefore resulting in dimers, Trimer's and Tetramers of Acetone as suggested by some on Rogue science forums. It does seem to make sense.

And don't forget that DPPP seems to like to form at temperatures below 0c.

Rosco Bodine - 31-12-2004 at 23:32

I would be surprised if it makes any difference whether 36% or 31.45% HCl is used in this reaction , other than perhaps
changing the time of the reaction slightly .
Look at it this way , the difference between the two is that the weaker is 68.55% water , while the "stronger" is 64% water , a difference in water content of 4.55% , not much in the scheme of things .
So far as I can tell there is no unreacted acetone after the first hour , perhaps two hours at the most in terms of polymerization , and thereafter the reaction is probably 90% or more complete in 24 hours . I think the phorone dihydrochloride product
is likely all there as an unstable emulsion with water , and further heating and standing simply leads to separation of the
mixture into phases having lower water content from higher water content . Possibly all I am doing by extended heating is destabilizing the emulsion and no further chemical changes are occuring .
What you say about "unreacted acetone" if you mean not free acetone , but polymerized acetone not yet converted to phorone dihydrochloride , because I used no excess of HCl to drive the reaction , well I agree that is a possibility . Actually I had wondered about that myself and thought about adding 20 ml of HCl and seeing if this led to any reduction of the volume of the upper layer . If that does occur , then it would confirm an excess of HCl is needed , in the molar ratio of 2 moles HCl to 3 moles acetone . This is one of the parameters I am evaluating so I will probably set aside a small sample of the upper layer and then see if some added HCl will result in any change .
The upper layer is so densely colored that I really do think it is phorone dihydrochloride , and not unconverted triacetone dialcohol . I have been reviewing the observations made earlier ,
and it would seem possible that the phorone dihydrochloride has been completely formed at 16 hours from the beginning of the mixing of the acetone and HCl maintained at 66 C , and the appearance of traces of a floating oily slick as an upper layer is a marker for
what is the completion of the chemical reaction producing the phorone dihydrochloride . All subsequent observations may be attributable to the physical destabilization of the emulsion
of phorone dihydrochloride in water on continued heating . It would be reasonable to test this theory on the next batch by proceeding with the peroxidation after
the acetone and HCl has reacted at 66 C for 16 hours .

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

Not emulsion...

Tweenk - 1-1-2005 at 06:01

Have anybody read about two-phase systems? Those are systems of two partially miscible liquids. For every such system there are two temperatures, lower critical temperature (minimum temperature below which the system is always homogenous no matter the ingredient content) and upper critical temp. (above which system is also always homogenous). In most cases though both of them cannot be observed as before it happens a boiling or freezing point of one of the ingredients is reached. We might have such a system here and when you start heating Rosco you might be just decreasing the solubility of phorone derivative in water and therefore dark crystals precipitate out of the soln.

A friend of mine is doing this rxn on a small scale in a jar and after ca. 30 hours in a warm place (near the computer) the soln turned very dark red. When the jar is tipped, some tarry residue is left on its wall. I think it is because phorone derivative content is now higher than that which can be dissoluted in water (this is one of the clues to prove the 2-phase system hypothesis).

[Edited on 1-1-2005 by Tweenk]

Rosco Bodine - 1-1-2005 at 09:37

The "tarry residue" which you are seeing when the liquid is sheeting across the glass is something I have observed too , but it is not as simple as it seems . Observe the droplets of the "tarry residue" closely in bright light , and use a magnifier if you need it to see that the residue droplets separate into two phases
as they slide slowly across the surface of the glass , each droplet is a small globule of a darkly colored material which is surrounded by a clear layer of water clear material , something like an egg yolk sitting in its surrounding egg white liquid which is more fluid than the "yolk" . Then there is an even more fluid and mobile third liquid present which sheets into a film across the surface of the glass as a bright yellow material which flows away quickly from the more "sticky" droplets of "tarry residue" . It appears to me that
a three phase system is present . From my past experience with doing liquid-liquid extractions , the appearance of the complex mixture squares with what is called a "persistent" emulsion , or an "intermediate boundary layer"and heating is one of the things that drive a phase separation . This complication occurs when organic materials have a great solubility but not a complete miscibility with water and is aggravated by the presence of some solvent which may have a similar limited water solubility while being miscible completely with the organic phase . But often the deliberate addition of a yet another material can
cause the phases to separate cleanly into two phases an organic phase and water .
Salting out with some salt highly soluble in water but insoluble in organic liquids can cause separation , or the addition of a low density solvent like toluene can cause separation . Sometimes simply changing the pH by adding a few drops of acid can facilitate separation .

But here is the potential fly in the ointment with regards to use of the mixture in further reaction to produce DPPP , where it is likely best that the emulsion be as homogeneous as possible
so that the very small globules can have great surface area for further reaction during the chlorination / peroxidation step to follow . I suspect that the highest yields of DPPP will be obtained when the
mixture containing the phorone dihydrochloride has a highest content of that material in terms of conversion of the original acetone , *but* that the material should be unprecipitated , maintained in a finely dispersed emulsion where it is available for further chlorination and peroxidation to DPPP . This may be the
built in limiting factor which determines the maximum yield , and could also account for tinting of the end product , should it be found that pure DPPP is actually white , although I am not declaring that it should be white , but only that it is conceivable . I will have more insight into this after observing the peroxidation and doing recrystallizations using charcoal to attempt decolorization .

For me everything is speculative at this point but I share these ideas as they may have bearing and others may be thinking along the same lines . A thing I have considered is that perhaps some sort of detergent or dispersion agent or emulsifier which is totally inert to reaction with the materials present in the system ,
should increase the quality of the emulsion and the yield and purity of the DPPP produced from the improved emulsion of phorone dihydrochloride .
Candidate dispersion agents would need to be stable in acidic medium , perhaps one of the sulfonic acids for example or
a soluble acidic phosphate are things which come to mind . By use of such a dispersion agent , it should be able to drive the initial reaction further to completion forming a higher concentration of phorone dihydrochloride in stable suspension , before any precipitation of that product as a separated phase . This may or may not have any usefulness , I cannot say until experiments are done to see if this has any effect or not . Another thought which I almost don't want to share is that it seems possible that the triacetone dialchol , phorone dihydrochloride , pentachlorophorone , and DPPP , are *all* entirely colorless products themselves and that the color changes which have been observed may be due to perhaps the presence of 10% of an unknown byproduct impurity which has no bearing on the reactions we are observing , other than to create total confusion by a presentation of color changes which are meaningless except in our own mistaken belief they have significance :D

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

Atom - 1-1-2005 at 10:11

Can phorone dihydrochloride be made with only a small percentage Hydrochloric acid, like 10 %.

Rosco Bodine - 1-1-2005 at 10:18

Just a guess , but I would say probably so , it will just take longer for it to form with the more dilute acid .

Atom - 1-1-2005 at 11:03

Okay, it's in the freezer for about 2 hours now and it still didn't change colour. Does anyone know how long this will take?
To change colour I mean.

[Edited on 1-1-2005 by Atom]

mr.pyro - 1-1-2005 at 13:04

I just tried the written synthesis by Rsert. The oily substace appeared after heating for 2 hours at 50 C and then heating for 15 h at 30 C. I cooled it to -10 C and Added 50Ml H2O2. IT was cooled back down to -10 C but no black crystals came out, because there was already a heavy yellow precipate. I waited for about 1/2 hr to see if any balck crystals would precipitate out, none did, so I added 200 ml more H2O2 and the precipitate was similar to Rserts pictures.

Edit

I just filtered what ever precipitated out and after neutralization, can not be more then 10g of DPPP. This seems like a shitty yeild from more then 400 Ml of Reagents.

[Edited on 1-1-2005 by mr.pyro]

Rosco Bodine - 1-1-2005 at 13:57

Quote:
Originally posted by Matsumoto_Hideki
My guess is that when you are finished your reaction you will have a dark red layer (unreacted acetone) and a black red layer to contend with as I do think you may run into partial digestion of the acetone therefore resulting in dimers, Trimer's and Tetramers of Acetone as suggested by some on Rogue science forums. It does seem to make sense.


I think you are correct about the upper layer being a separation of unreacted or not fully reacted acetone polymer , if that is what you mean . A few minures ago I attached a teflon capillary to a syringe and transferred a 1 ml sample of the top layer to a clean test tube . The oily material is a slightly yellowish brown , mostly dull brown colored liquid which is imiscible with water , and imiscible with denatured alcohol . A spot test on white paper towel leaves a light brown stain .
To the dull colored sample of unknown oily material was added an equal volume of 31.45% HCl and the test tube is swirled a few times to mix the imiscible liquids . In a few minutes the color brightens , and an emulsion is forming having the same bright red yellow color as is seen in the initial reaction mixture from which this sample has been withdrawn . After heating for a few minutes , the effect increases and a more and more finely dispersed and highly colored emulsion forms , actually it appears it may be going completely into
solution , without any of that opaque dark "milky" or solid pigmented appearance of suspended matter or
liquid in liquid dispersion . From this observation I think it is reasonable to
conclude that at least some excess of HCl to acetone is indeed required to drive the reaction to completion for producing the phorone dihydrochloride , and that this slight excess of theoretical requirement HCl is necessary for keeping the phorone dihydrochloride product in good solution in the reacted mixture . If the HCl amount is deficient , then an emulsion is going to be the result from digestion of the acetone HCl mixture , and some incompletely reacted acetone polymer , which will not only reduce the yield of phorone dihydrochloride , but produce a reacted mixture whose properties are inferior for the further reaction to be performed in the peroxidation step to follow . This mixture is pH sensitve , and needs the acidity of a little extra HCl to be fit for use . This observation is in agreement with the patent specification ,
so it would seem that the patent is correct on the molar ratio of HCl to acetone which is going to be useful .
I am going to add 25 ml of HCl to my
sealed bottle mixture and continue that experiment to see if everything goes into
solution again as hopefully the emulsion
and phase separation vanishes . That amount of added HCl should bring the
mixture up to the equal volumes of HCl and acetone referenced by the patent .

Yes, I agree

Matsumoto_Hideki - 1-1-2005 at 16:15

This is what I have to end up doing just to make sure all the acetone is converted to Phorone HCl
and then to Pentachlorophorone. However don't add too much or you end up overheating the reaction.
I used a modified version of R_Serts peroxidation technique.

Another thing... slowly add your H2O2 over the course of serveral hrs while the mixture is -20c -30c
in a cold freezer. I find this works very very well.

Rosco Bodine - 1-1-2005 at 16:46

From what I have observed with my sealed bottle experiment , it definitely is
important to get the acetone to HCl ratio just right , with a bit in excess for HCl , to discourage separation of the product into water soluble and insoluble phases , and to avoid incomplete conversion of the polymerized acetone to phorone dihydrochloride . It would seem desirable to settle for a lower yield of the phorone dihydrochloride , but have it in a strong solution or stable dispersion which can be
diluted by the peroxide without that dilution causing a phase separation , as opposed to driving the reaction with high heat and long reaction times to get a higher yield of phorone dihydrochloride , but have it separate as an undilutable and water imiscible oil , or as a coarse emulsion . The reaction is best run with the right proportions of acetone and HCl from the start , and then it is my guess that when the reaction reaches that dark red orange color where it looks like freshly brewed very strong tea , barely transparent to a strong light but not yet cloudy , that is probably the point
where the heating should be ended and the product should be allowed to cool and peroxidized . Has anyone tested the mixture to see if this "cloud point" where
it begins to lose transparency , is a good marker for the point where good yields of DPPP will be obtained by the peroxidation ?

Looking back on my notes , it was only about 6 hours into the reaction at 66 C
when the dark red orange tint was developed and then at 7 and 1/2 hours
the mixture began clouding . So it looks like somewhere in that time window the
reaction was possibly mature . You follow what I am thinking , the mixture may produce more phorone hydrochloride with passing time , but it appears in a form which is less and less dispersed so it may give poorer response when diluted by the
water content of the peroxidation mixture . Does this sound reasonable ?

[Edited on 2-1-2005 by Rosco Bodine]

Holy shit... I just did a velocity test and look at this pic

Matsumoto_Hideki - 1-1-2005 at 17:22

Everyone ... drop your shit and look at this picture of my .223 shell velocity test against 4mm steel.

Both mini shaped charges were full of AP and or DPPP..
You can clearly see which subtance has more power.

1# AP charge with exactly the same # of grains as DPPP
detonation was strong enough only to nipple the primer and propell it and the base of the shell into the metal. primer was still in the bottom on the caseing which was retrieved later. :(


2# DPPP charge was strong enough to punch a BIG crater in the steel and propell the primer almost completely through the target. BIG blast marks are visible in the target surface indicating a MUCH higher velocity and energy signiture. I have pictures of the recovered metal fragments from the AP, whereas there was nothing left of the DPPP casing. The primer in the DPPP charge was atomized as well, but only the very bottom case rim although mageled was left! :) YES !!! THIS PROVES THE PATENT'S CLAIM!!!

[Edited on 2-1-2005 by Matsumoto_Hideki]

[Edited on 2-1-2005 by Matsumoto_Hideki]

100_2580.jpg - 469kB

Rosco Bodine - 1-1-2005 at 17:46

That radial pattern spray of impact welded
fragments of brass is not something typical for the velocity of AP , more like usual for picric acid or better . That sort of surface gouging and or perforation by small fragments is an evidence of a brisant explosive , paricularly in the case of a softer metal like brass doing that to a harder metal like steel .

Axt - 1-1-2005 at 22:02

Quote:
Originally posted by Matsumoto_Hideki
test against 4mm steel.


Did you actually measure that, It looks like something hacked from a filing cabinet. 4mm is quite heavy steel and small, high velocity, brass fragments are unlikely to bend the plate at that angle, rather it will crater, pit and gauge the steel. The cut marks look like ~1mm plate, through 4mm it would be straighter and less scrappy. Unless its prefabricated like that, those bends are very unlikely as well.

Sorry to those that would rather be misled and lied to, but I'm yet again calling bullshit. Credibility is everything, if one cant be trusted to report the true parameters of the experiment, how can on be believed that the results arn't fabricated to show what they <i>want</i> it to show.

I'm prepared to be proven wrong with a picture of the plate, side on, with a ruler for scale.

Rosco Bodine - 1-1-2005 at 22:38

LOL

Yes that scrap of tin isn't any 3/16" plate ,
and as a former metalworker I did recognize that 18 gauge ( if that much ) for what it is , along with Quasimoto's habit for exaggeration other wise known as bullshitting in most circles :D

But you know , that doesn't change a thing about the impact welds in that starburst pattern .....even if there was no
"shaped charge" involved either (which there wasn't )

Now the exaggerations aren't cool at all ,
no not impressive trying to read through and separate the shit from the shinola .

You aren't talking to novices here , not by a long shot . So take a hint from Axt ,
underscored by yours truly and knock it off
with the bullshit . Save us the work of
guessing how much of what you say is true and how much is your idea of humor or an estimation on your part of the IQ of your audience . Science is about facts ,
not charisma and tale telling skill . Engineering is by the numbers , numbers that can't be faked . So get it or get on down the road . You'll be happier there
where nobody knows the difference and you can seem to be the smartest of all to
all your gullible and naive true believers .
You'll find no cult following here , just a gang of dedicated proof testing skeptics .
Everything gets analyzed here , so spare youself the discomfort of a thorough proctological , by keeping on the level .

Mickhael - 1-1-2005 at 22:58

Quote:
Originally posted by Rosco Bodine
Everything gets analyzed here , so spare youself the discomfort of a thorough proctological , by keeping on the level .


I have to agree with that...if he could just make more solid statements it would certainly help...and hey...why not take the picture with the ruler and prove what is what? I'd love to see that.

Also Rosco, what % of Acetone and HCl are you using that has the excess HCl needed? One of the numbers I heard was something like 300ml Acetone to 200ml HCl, was that even close to what your using, or am I way off? Also have you had any more tests with adding the extra HCl just before the H2O2 to restart the reaction? Thanks

Woops, backtrack a bit... This is serious!!

Matsumoto_Hideki - 1-1-2005 at 23:26

Go look for yourself , alright I may have miscalcutalted on the measuremant... turns out it is 2.5mm thick car flooring woops... Ok... So I though the gaugue in question ment 4mm woopdy shit! This is high strength painted metal flooring guys, not flimsy filing cabinet crap metal.
Seriously you have to try it out.. i am not kidding here.

GO DO SOME TESTS INSTEAD OF SITTING BEHIND A DESK A WAITING FOR OTHERS TO DO THEM FOR YOU!
Rosco, Radial patterns for AP is quite typical for a rounded shell charge they just don't create deep gouges since the dvol is low.

DPPP on the other hand is quite a different story.

Lets start the banning crap all over again guys, that will really help, HAPPY FUCKING NEW YEAR!!

[Edited on 2-1-2005 by Matsumoto_Hideki]

100_2594.jpg - 645kB

Rosco Bodine - 1-1-2005 at 23:32

The equal volumes of acetone and HCl 31.45% would seem close to correct for
providing the slight excess of theoretical
requirement of 2 moles HCl per 3 moles acetone . You can do the math . A mole of acetone is 73.53 ml . A mole of HCl is contained in 100.06 ml of 31.45% HCl .

3 X 73.53 = 220.59 ml acetone
2 X 100.06 = 200.12 ml HCl 31.45%

If the amount of HCl is increased to be equal the amount of acetone the amount of HCl in relation to theoretical requirement will be 220.59 / 200.12 = 1.10 or 110% of theory , 10% excess of HCl required by theory provided by equal volumes .

From my observations of an acetone lossless reaction in a sealed bottle , a slight excess of HCl helps the solubility of the reaction product . There is an unstable "phase equilibria" affecting the polymer solution past a certain concentration where it reaches a "cloud point" and the
polymer solution degrades to an emulsion
and then futher develops phase separation of a water imiscible product .
It seems logical to me that for reaction with a peroxide solution which is 70% water , you are better off to have a reactant which is still a stable solution so that the components can be mixed intimately for reaction and not separate into imiscible phases which generally react only with difficulty and slowly . So
I think it is likely that the precursor needs
to be prepared according to a controlled
scheme and then very soon subjected to the peroxidation step to get reliably good yields .

Got anything you want to say rosco?

Matsumoto_Hideki - 1-1-2005 at 23:36

Hey, you wanted evidence , now you have it !!What the fuck to you means shaped charge? It fucking well was!
Give me your definition rosco?

[Edited on 2-1-2005 by Matsumoto_Hideki]

Joeychemist - 1-1-2005 at 23:48

What evidence are you talking about Hidiki? I hope you're not referring to that shity picture you posted above because I can't even tell what I'm looking at:P

What type of material did you use for the liner (the cone) of the shaped charge? How was the charge placed on the witness plate, was there any stand off, if so how far away was the charge from the witness plate???
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