| Pages:
1
..
20
21
22
23
24
..
37 |
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
DPPP sublimed crystals are Cubical !
There may well be a difference developing in the two samples which I have been subjecting to a slow sublimation in order to visualize any obvious
differences between the sublimed crystals from DPPP and sublimed crystals from AP . Now that the sublimation has continued for a couple of days , the
crystals have grown much larger and are easier to see the difference . While the sublimed crystals of DPPP and AP are both of rectangular shape and
white and shiny reflective appearance , the AP are long rectangular
form crystals which are characteristic of AP , but the sublimed crystals of DPPP are definitely cubical and distinctly different in appearance .
Hot fucking damn !
I am tickled shitless 
Anybody out there please verify me on this . The results take a couple of days to develop . It's a simple slow sublimation test of parallel
samples in test tubes .
|
|
|
Matsumoto_Hideki
Banned
Posts: 103
Registered: 27-12-2004
Member Is Offline
Mood: detonated
|
|
I have to try subliming my DPPP
I am going to sublime my DPPP and see this for myself!
what temperature did you sublime it at?
couple of days ago I tried to see if there was any AP forming with my DPPP so I sunk it in hot water (80-90c) in a bag for approx 15min. Results were
nothing, other than a very acrid smell of what we now know is chlorobutanol.
|
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
Interesting. Pictures please! I take it this sample is the one obtained from the reverse process, i.e. the acetone/HCl being poured into H2O2? Really,
of course this has to be done with putative DPPP prepared the original way.
This also confirms the purity of the putative DPPP, else you wouldn't be getting crystals that grow large. Does it look like there is a small
amount of left-over that doesn't sublime?
Anyway, a word of warning- from protein crystallography I know that a tiny change in conditions, or the presence/absence of tiny impurities or weakly
binding ligands can completely change the crystal geometry, I know of cases that the very same protein, just crystallised in a different buffer,
produces once hexagonal, and once crystal needles. Of course this is less a problem for smaller molecules, but it is an issue that shouldn't be
forgotten.
And from rectangular flat it's not far to rectangular cubic.
Now, this may or may not be a problem - but it definitely needs further confirmation, preferably by power or something. Plus, the fact that the
putative DPPP volatilises is in contrast with what is stated in the original patent.
[Edited on 12-1-2005 by chemoleo]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
For the sublimation test I am using Sarstedt brand clear polyproplylene culture tubes equipped with a two position venting / sealing polypropylene
snap cap , capacity 13 ml . In the bottom of each culture tube is placed a quarter gram sample and the cap is placed on the tube to the first venting
position . The two tubes are placed through holes in a support so that they are supported at their upper portion by the shoulder on the cap which
is too large to pass through the hole , The lower portions of the two tubes hang freely in the air down to the surface of a small water bath kept at
about 70 C , with the lower 2 cm of the tubes immersed in the hot water . Oil would be a better heating medium because the water keeps evaporating
and has to be refilled periodically . Anyway , after the initial heating of an hour or so any residual moisture is driven out of the samples and
condenses on the inside of the cap and inside surfaces of the upper portion of the tube . The cap is removed and the trace of moisture evaporates on
exposure to the air after a few minutes . Then the cap is put back on the tube and the tubes returned to the heating , and after a few minutes the
caps are snapped down to the sealing position . The sublimation then proceeds very slowly over several days as the samples are kept warm in the lower
part of the tubes immersed in the heated bath , and the vapors are condensed and crystallize on the inside surfaces of the cooler upper portions of
the tube . This proceeds very slowly but is a revealing test about the difference in crystal shape for the sublimed materials .
Chemoleo : The sublimation sample is from the first synthesis of DPPP , the yellow colored material which reeked of the irritant impurity , and was
made by the addition of peroxide to the phorone dihydrochloride precursor . The sublimation test was already in progress before I began the reverse
order of addition peroxidation experiment .
I don't have a good enough macro lens for my digital camera to show the samples , but the cubical crystals are clear , reflective , and about
three times the dimensions of table salt . In comparison , the AP crystals are double the dimension at the square cross section and three to four
times that edge dimension in length , a very significant difference , not subtle at all . Also the AP cystals are white and have an opaque lamellar
structure like mica , they are not crisp clear icelike transparent as are the DPPP crystals .
There is indeed a brown residue accumulating from which the light yellow DPPP sample is subliming , so the coloration is indeed an impurity , and the
color of the pure DPPP is white or clear colorless .
[Edited on 12-1-2005 by Rosco Bodine]
|
|
|
$0meb0dy
Harmless
Posts: 13
Registered: 17-12-2003
Member Is Offline
Mood: No Mood
|
|
Tried DPPP again today.
I used dark red aceton/HCl mix from a few weeks old, so I think the chance that it still contains aceton is pretty small, it's very dark at this
point witch a green tint in it, you see the green when there is a very thin layer on the glas after moving it.
I cooled it to around 0C, then I added H2O2(30%) till the reaction stopped and keeping the temp. under 7C.
The mix was bright yellow and there were pretty much fine crystals.
I filtered it and the crystals were white and the filtrate was bright yellow.
It's drying now, I will do some test compared to AP.
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
One thing I can tell you is you don't want to keep the phorone dihydrochloride precursor "for a few weeks" even in the refrigerator the
polymerization continues slowly . It should be used for the peroxidation within a couple of days after preparation , and probably stored in the
freezer or refrigerated at least .
Otherwise filtering it before peroxidation would be a good idea , because if not , you will have insoluble material in the mixture which won't
peroxidize and will precipitate as a globular impurity with the crystals . The proportions and time of reaction for the precursor are tenatively
worked out at 93 ml of 31.45% HCl to 100 ml acetone , in a sealed bottle self reacted for 1 1/2 hours and then supplementally heated at about
65 C for 2 1/2 hours to development of a deep red but transparent liquid which appears bright yellow in thin layers swirled against the inside of the
sealed bottle . The details have been described in preceeding pages where we are trying to standardize the method . For anyone reporting results ,
please give all relevant details so that we can all make reasonable conclusions of what the data means .
[Edited on 12-1-2005 by Rosco Bodine]
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
| Quote: | Originally posted by rogue chemist
| Quote: | Originally posted by Rosco Bodine
Are you going to weigh your yield and do the math to get the percentage ?
( 27.57 grams would be 100% of theoretical ) 24.8 grams would be 90% of theoretical .
|
11.6 g of pale yellow DPPP + 1.2g pure white DPPP recovered from filtrate=12.8g
46.4% yield
Very little DPPP was lost during the procedure. At max a gram of DPPP. But even taking that into account a terrible yield for a procedure that is
reporting 90%. Is it possible that some DPPP sublimated during drying. Damn, and just when we think that a appropriate procedure has been worked
out.
Anyone else have yields using a procedure like Rosco's on p19? |
The dried *unknown* product from my reverse order of addition peroxidation experiment has been weighed and the yield calculated at 79% of theoretical
based upon acetone if the product is DPPP.
The dried *unknown* product smells distinctly different now from the AP like odor it had when still damp . After a couple of days of airing out the
odor seems to have stabilized on the dry white material , and the odor is very faint , an inseciticidal odor which smells like the natural pyrethrin
based sprays such as are used to spray sleeping bags and tents to clear mosquitoes . That is exactly the smell of the dry crystals , like pyrethrin
based bug spray not irritating and a very faint odor .
79% is more closely aligned with the figure of 90% stated by the patent so I am hopeful I may be onto something here but it is too soon to have any
solid conclusions because no tests have been done yet on the product .
The precursor had been made from 112 ml acetone and 105 ml HCL 31.45% as described earlier , in a sealed bottle self reacted for 1 1/2 hours , then
heated gently for 2 hours at 65 C to obtain the ruby red solution , allowed to stand overnight , and then refrigerated for keeping until the
experiment a day later .
A 100 ml portion of the above precursor was added dropwise over the course of 2 hours to 130 ml of H2O2 26.6% , well stirred in a beaker sitting in a
salted ice mixture , at a temperature range of -5 to a peak of -2 C . The detailed real time description of the experiment was posted earlier absent
these details . I won't retype the entire experiment description that was posted earlier , but you can refer to the earlier posts for all the
other details . The weight of the dried material is 41 grams .
UPDATE : A quarter gram sample of the material from this experiment has been placed in a culture tube and added to the other tubes partcipating in the
sublimation test . A fair amount of moisture was driven out of what I supposed was a dry sample after it was warmed so it is evident that some gentle
heating for a day or so should be used to complete the drying of these samples before they are considered completely dry . The moisture content has
skewed my yield calculation also , so the 79% yield I first reported is likely closer to 74 or 75% .
[Edited on 12-1-2005 by Rosco Bodine]
|
|
|
Mickhael
Hazard to Self
Posts: 65
Registered: 17-11-2004
Location: B.C. Canada
Member Is Offline
Mood: Terrificlawful
|
|
Wow...long thread, and execelent work being done! I'm very glad you are doing these tests Rosco, since I know myself at least would not have the
inclination for taking the time to make apperatus for these fairly conclusive results. I think my max yield so far has been around 60%, but I think
my precursur has sat to long, and was heated to long for much better results then that. Its also very nice to read clear and concise results and
methods...since there far to many dummies making statements without backup or method. My crystals I have left (about 25g) have lightened alot but
still have a yellow tinge, in the camera flash they look white, however in normal light the yellow is still there.
I have tried about 0.6g in duct tape and that made a decent bang alright, left a hole in the snow bank about 8" across...I'll be trying a
mix of MEKP/DPPP tomorrow...I'll post the results. I'm also very much looking forward to hearing what the lab analysis will be, if it
can't b gotten for some reason, I may be able to get some myself through a couple contacts...what was the 100% liquid it was said it should be
desolved in for lab tests? deuterated methanol. Where might it be possible to find that? thankyou
[Edited on 13-1-2005 by Mickhael]
|
|
|
Matsumoto_Hideki
Banned
Posts: 103
Registered: 27-12-2004
Member Is Offline
Mood: detonated
|
|
alright I have one result to share, THIS IS MAJOR
The colour red-black is NOT being caused by Phorone itself but by a precusor to phorone called mesityl oxide as it stands at room temp or higher
colour degrades from clear to yellow to red then to black at
this then becomes Phorone HCl when the peroxide is added. The mesityl oxide starts to digest into Phorone & related HCl's then into
Pentachlorophorone and then finally crystallizes into DPPP with the release of Cl2 with some chlorobutanol as byproducts . The yellow colour is due to
a chlorinated byproduct? not sure yet..
http://www.cdc.gov/niosh/ipcsneng/neng0814.html
This result was forwarded to me from a chemist at my university!!
BTW this proves that the extreamly powerful explosive peroxide is indeed a PEROXIDE OF PHORONE and not a simple trimeric actone peroxide!
[Edited on 13-1-2005 by Matsumoto_Hideki]
[Edited on 13-1-2005 by Matsumoto_Hideki]
[Edited on 13-1-2005 by Matsumoto_Hideki]
|
|
|
Pyroz
Hazard to Self
Posts: 76
Registered: 27-12-2004
Member Is Offline
Mood: curious...
|
|
yeehaw...
*information from labratory test so far*
I gave a chem grad a challange to make the infamous D.P.P.P explosive to synthasize and here is what he found out:
"Adding Acetone to equal parts of HCL(aq) gives the product MESITYL OXIDE after the material is left to digest. When further HCL is added as a
cataylist and conc. Hydrogen peroxide is added to the MESITYL OXIDE. MESITYL OXIDE turns into a PeroxyPhorone when conc. Hydrogen peroxide is added.
During the addition--- crystallization occurs instantainously with a bright yellow chloride by-product which settles in with the very pale green
crystalline mass.
Further filtering of the crystals is needed to purify the product in a solvent. The yield is very high --- upwards of 70%, and in larger batches could
be in the high 80% range. The theoretical explosive properties (while unmeasured) would put peroxyPhorone in a very powerful class of explosives well
beyond that of a regular trimeric-Peroxyacetone due the complexity and strength of its molecular bonds and mass. Further testing needs to be conducted
here to determine true VoD."
[Edited on 13-1-2005 by Pyroz]
|
|
|
Joeychemist
Hazard to Others
Posts: 275
Registered: 16-9-2004
Location: Canada
Member Is Offline
Mood: Sedated
|
|
Hmmm...
Could you guys maybe show some proof to back these theories or at least tell us what leads you to believe this is mesityl oxide?
What exactly have you told the "people" from you're school about this? Have you given them the work that we have so far or are you
makeing them start from scratch? Do they know that it might be another explosive?, they might want to test samples of AP next to "DPPP" side
by side.Do they have a copy of the patent, both original and translated versions?
And hideki, when you gets those results from school please scan all the work onto you computer, so you can attach it as a file for all to read.
[Edited on 13-1-2005 by Joeychemist]
|
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
Mesityl Oxide
Interestingly, in the MSDS of mesityloxide ( (CH3)2C=CHCOCH3), it says it is a colourless viscous liquid of bp 130 deg
C, and a liquid that darkens on standing that has a characteristic odor.
The fact that the solution is indeed dark, or gets increasingly darker seems to support this. In addition, it mentions it is only barely soluble in
water ( g/100 ml at 20°C: 3.3 (moderate)), and specifically that its density is LESS than water, i.e. 0.86 g/cm^3.
So- this seems something that MUST be tried and tested!
1) incubate the HCl with the acetone, until the colour is black/dark red.
2) Add water, mix thoroughly and for some time, and see if you can separate an upper insoluble layer, which should be mesityl oxide.
This should be fairly viscous!
Also, bring a small amount of this upper insoluble layer to the BOIL, and measure the temperature - it should be at 130 deg C or thereabouts (once
water & unreacted acetone has boiled off- so boil for a good while!)!
3) If 2) works, add more HCl to get the dichloro version, and add H2O2 to see if this is what is needed to get a precipitate!
Furthermore, I checked Orgsyn.
It gives a method straight from diacetone alcohol, but more importantly, it lists several references on the production of mesityl oxide from
acetone! It says 'the yields are poor and considerable quantities of phorone and similar substances are invariably
produced'. It might be good to look up some of those references and see which ones produce most mesityl oxide and phorone. See for instance:
Fitting, Ann. 110, 32 (1859); Heintz, Ann. 178, 343 (1875); Claisen, Ann. 180, 4 (1875); Freer and Lachmann, Am. Chem. J. 19, 887 (1897); Currie, J.
Am. Chem. Soc. 35, 1061 (1913); Couturier and Meunier, Compt. rend. 140, 721 (1905); Mannich and Hâncu, Ber. 41, 574 (1908); Bodroux and Taboury,
Bull. soc. chim. (4) 3, 829 (1908); Yllner, Svensk. Kem. Tids. 37, 227 (1925) [C. A. 20, 739 (1926)]; Gasopoulos, Ber. 59, 2188 (1926); Brederick,
Lehmann, Schönfeld, and Fritsche, Ber. 72, 1417 (1939).
I am sure one or two of these should be accessible for you. Please be sure to post a scan!
However, there is also a proper preparation of diacetone alcohol in OrgSyn, which employs Ba(OH)2 and acetone, and which is used directly for the production of mesityl oxide , which in turn can be peroxidised to hopefully give DPPP or some peroxidised derivative thereof!
There's plenty do do and to test!!
[Edited on 13-1-2005 by chemoleo]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
Before I put forth my own theory about the polymerization of 3 acetones to a trimer called triacetone dialcohol and its subsequent condensation with 2
HCl's to form phorone dihydrochloride while freeing
2 H2O's , the route through mesityl oxide was considered . For reasons I don't recall now it did not seem to add up . It has been a month
ago now and I didn't make notes , but did read that organic synthesis article along with several patents which are related . What I do recall is
that I became certain that phorone itself is not a reactant in the synthesis as Mackowiak has it written ,
but that the triacetone dialcohol which Mackwiak does show , reacts as it forms directly with the HCl in a condensation reaction to form phorone
dihydrochloride , as the product of that condensation , without any intermediate formation of free phorone itself . I still hold to this theory .
And it will take more than a contradictory opinion from a PHD with no citations or proofs to convince me otherwise , since it is already stated in the
literature generally that polymers of acetone are known to be reactive to chlorination , and other reactions , as well as to continue formation of
higher acetone polymers ultimately resulting in materials which are solid plastics at room temperature .
And one thing I do recall is that the process of acetone polymerization is definitely affected by the severity of the conditions , aqueous versus
anhydrous , low temperature versus high , and pH and catalyst sensitive . It is not a process where a simple reaction mechanism stated for one set of
conditions applies to what happens with the same reactants under different conditions . The conditions for the formation of the precursor for DPPP
are at the mild end of the spectrum for reaction conditions which would lead to mesitylene
at higher temperatures and anhydrous conditions , for example 150 C with concentrated sulfuric acid and distillation of the product would produce
substantial amounts of mesitylene , but not likely for an aqueous reaction mixture af acetone and HCl ~ 30% at 65 C for 2 to 3 hours .
Mesityl oxide is something I will look at again and try to recall why I also considered it unlikely , but I believe that it was for the same reasons
that the reaction conditions were unfavorable for its formation .
|
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
Well, whoever prepares the next batch, could you please check whether the dark solution is soluble in water, and, if possible, the boiling point? If
it is soluble, at least that will rule out mesityl oxide, and peroxidation products thereof. Case closed. Experiment proves theory, not vice versa.
Damn, I will try this myself later this week.
As to whether the formation of mesityl oxide is likely or not - I'd be delighted to have a look at these references to see what conditions these
authors employ to obtain mesityl oxide (and what conditions specifically exlude the formation of mesityl oxide). As I said above, it seems difficult
to get clean mesityl oxide by acetone condensation and consecutive dehydration (see orgsyn reference), as multiple byproducts, including phorone are
produced.
It's only a question of how much phorone, acetone alcohols, mesityloxide, chlorinated derivatives and mesitylene are produced in a
given set of reaction conditions, as these things are all in equilibrium.
Anyway. Let's just test it shall we. If the black viscous oil is completly and easily soluble, we KNOW that mesityl oxide itself does NOT produce
the precipitate lateron. If it forms a separate layer, we KNOW it COULD be mesityl oxide. It could be other things too, of course.
But please, do quote those conditions of those papers that you looked up that are required to PREVENT the formation of mesityl oxide. If those
conditions are identical/similar to ours, then I guess it's unlikely that mesityl oxide is a major player. But the experiment could ultimatley
confirm this too (solubility test).
[Edited on 13-1-2005 by chemoleo]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
Joeychemist
Hazard to Others
Posts: 275
Registered: 16-9-2004
Location: Canada
Member Is Offline
Mood: Sedated
|
|
Solubility test;
I took the Phorone Dihydrochloride precursor I would normally use in the synthesis to be peroxidized to form the “DPPP”, not the over heated week
old decomposed precursor like with Rosco’s first bottle test, so there was only a few ml of the upper oily layer in the solution.
I poured 50ml of Phorone Dihydrochloride down the side of the beaker into 100ml water at room temp.
I received 3 layers in my beaker,
The bottom layer was a cloudy orange color, I could tell that some of the precursor had dissolved in the water which increased the bottom layers
volume slightly.
The second layer was water, slightly tinted orange but was over all clear water,
The top layer (the clear “oily” layer, that floats atop the Phorone Dihydrochloride) is *NOT* soluble in water, It also slowly “sheets” across
the glass as opposed to water which runs down the side very fast so it is viscous.
It took a little stirring to get the two lower layers homogonous, but it has 1 hour since and the two still seem to be an homogonous mixture. The
upper oily layer remains un-fazed by all of this.
I don’t have enough of the top layer to test the boiling point but I have started another batch and we’ll see then.
|
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
Interesting. Is it possible you can take a picture and attach it, i.e. the original sample and what it looked like after mixing with water and
settling?
Also, what's the smell of the upper layer like? Acc. to the MSDS it is fairly strong and characteristic. If it barely smells presumably this
won't be mesityl oxide.
Anyway - it would be interesting to see if each of these layers could be peroxidised, after adding a bit of HCl.
[Edited on 13-1-2005 by chemoleo]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
Joeychemist
Hazard to Others
Posts: 275
Registered: 16-9-2004
Location: Canada
Member Is Offline
Mood: Sedated
|
|
Nope, no pictures, No camera and no scanner, someday perhaps.
The upper layer is pungent “sweetly acidic” if that makes sense, but I can’t really tell a big difference between the lower layer and the upper
insoluble layer when it comes to smell. As I said I have another batch brewing and will try to separate the two layers, then I will try the boil test
and I will try to peroxidise both layers as well.
|
|
|
Matsumoto_Hideki
Banned
Posts: 103
Registered: 27-12-2004
Member Is Offline
Mood: detonated
|
|
Full report about DPPP synth will be posted ASAP
I will post the report form my universities team of organic chemists on DPPP synthesis, so far as I said the darkening colour (clear to thick
black-red) is mesityl oxide that is a known fact, Phorone is also produced along side this reaction as well at much much higher amounts.
what is known at present
1) DPPP is being formed as the peroxide
2) Mesityl oxide is responsible for the initial colouration (black red) before peroxidation
3) Smell of crude DPPP is caused by Chlorobutanol (camphor like).
Unknown
1) how is DPPP forming exactly
2) yellow colouration of DPPP is ?
3) Exact DVol we do know that it detonates extreamly fast and is 6x more powerful than TCAP.
4) best temperature for sythesis?
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
Theoretical
In the first and only synthesis of DPPP which I have done so far using the conventional order of addition of the peroxide to the precursor , I was
applying a certain rationale which is suggested by the Mackowiak patent where he shows that H2O2 is "catalytic" in the formation of the
phorone dihydrochloride from phorone . I disagree that the reaction proceeds exactly as Mackowiak has written , but I agree that H2O2 may be
catalytic in the formation of the phorone dihydrochloride , only not from phorone .
What I guess is occurring is that triacetone dialcohol is being produced and then condensing with HCl to produce phorone dihydrochloride from the
initial self reaction which then slows because water being produced dilutes the acidity which has been catalyzing the polymerization of the acetone ,
and the amount of HCl present is actually being reduced at the same time as it ties itself to the triacetone dialcohol to form phorone dihydrochloride
. The self reaction starts intensely and then quickly tapers off because of the unfavorable equilibrium increasing with the reaction which quenches
the self reaction in its own product mixture . Then we have to add supplemental heating to make the reaction continue at a reasonable rate .
Heat increases the rate of polymerization of the unreacted acetone to triacetone dialcohol in the mixture in spite of the lower acidity and more
phorone dihydrochloride forms until we have that deeply colored ruby red but still transparent mixture . However some free acetone and free HCl still
remains in the unreacted state even in the "matured" phorone dihydrochloride mixture . Now this is where the first drops of hydrogen
peroxide added to the precursor mixture have their catalytic effect , in much the same way as peroxide catalysts are used as a polymerization catalyst
for styrene and polyester resin , the addition of a small amount of peroxide further kicks the polymerization of any unreacted acetone to form the
trimer , triacetone dialcohol and subsequent condensation with the available HCl remaining , completing the
conversion of the precursor mixture to phorone dihydrochloride during the initial addition of what many are calling the "peroxidation" step
. The so called peroxidation step is actually 3 sequential and partially overlapping reactions , with any actual "peroxidation" occurring
only in the third stage of the reactions which occur over the course of the peroxide addition . Initially , the first addition of a small amount of
H2O2 has the effect of completing the formation of the phorone dihydrochloride , which prior self reaction and supplemental heating has not fully
driven to completion . That is precisely the theory which made me believe that it is perhaps best to run the initial part of the
"peroxidation" warm , not cold , in order to complete the polymerization of any unpolymerized acetone in the presence of H2O2 in catalytic
amount , along with gentle heating of its own exotherm , much the same way as one would employ a heat lamp to speed the curing of polymerizing
fiberglass resin , knowing that gentle heating and the catalyst both help to complete the polymerization . As the addition of peroxide continues ,
the phorone dihydrochloride is converted to pentachlorophorone , and I am uncertain
as to whether this "second stage" may also be a reaction
aided by warm temperature , or if it is a simultaneous reaction involving the formation of DPPP by immediate decomposition of the transient unstable
species which pentachlorophorone may be , never existing as a stable and distinct intermediate precursor , to which the entire batch of phorone
dihydrochloride is fully first converted before any DPPP begins to precipitate , so I am uncertain about what is the most favorable reaction
temperature . I strongly suspect that these reactions all three overlap to an extent and the optimum thermal curve is something which begins warm at
the beginning of the addition of peroxide and then supplemental cooling is optimally coordinated with the peroxide addition to ramp the temperature
*downward* lower and lower as the addition of peroxide proceeds , and that this is the *only* way that any 90% yields would ever be possible , by
driving the reaction along an optimized thermal curve , where the reaction temperature corresponds with the amount of peroxide having been added at
any point in time , the whole time the temperature is dropping . Now that's what my theory on this reaction is and why it would take some fancy
equipment to ever get any 90% yields .
It would be my guess that using any standard lab method , non-industrial process , will likely be doing good to get
60-70% yield .
In my next experiment I plan to test this theory by starting the peroxidation slowly and allowing a gentle exotherm at first , and then regulating the
addition so the temperature of the reaction is actually falling over the course of the remaining addition , as the beaker sits in a salted ice bath .
Then I'm going to let the reaction mixture sit there in the cold until loss of color , and hopefully loss of the disgusting irritant impurity
which complicated my first experiment with an impure product from a reaction not allowed to proceed to completion .
I think I'll also make a fresh batch of precursor for the next experiment to
remove that variable . I have suspicions that our unidentified nose and eye stinging irritant may be unperoxidized pentachlorophorone .
chemoleo :
The upper layer of acetone HCl advanced reaction polymerization condensate is not mesityl oxide . It is a yellowish brown transparent oil which has
a smell like scorched vegetable oil or linseed oil , only milder . It is alcohol and water insoluble , soluble in acetone . It solidifies to a hard
residue upon exposure to air for a day or so . If mixed with concentrated HCl and heated , it reforms the ruby red solution from which it
precipitated .
Matsumoto : Please share my post here about the "Theoretical" with your scholarly friends . Also have them look at various HCl to acetone
ratios for the preparation of the precursor , including the ratio I like at 93 ml HCl 31.45% to 100 ml acetone in a sealed bottle self reacted for 1
1/2 hours and then heated at 65 C for 2 hours .
[Edited on 14-1-2005 by Rosco Bodine]
|
|
|
Matsumoto_Hideki
Banned
Posts: 103
Registered: 27-12-2004
Member Is Offline
Mood: detonated
|
|
Range test of filtered DPPP coming this saturday
I will be conducting BIG tests of DPPP this weekend at a range. I will be testing the DPPP detcord as well as a shaped Al charge. It should be
interesting. I am borrowing a pro digital movie camera to capture the video to 30fps DV.
I am going to try and edit/compress the movies into MPG4 to get them to fit them on this forum. we will see !
|
|
|
Mickhael
Hazard to Self
Posts: 65
Registered: 17-11-2004
Location: B.C. Canada
Member Is Offline
Mood: Terrificlawful
|
|
MEKP/DPPP Tests
Now I don't know all the proper methods, but I'm attempting to test a MEKP/DPPP 4/1 = 1.25g mixture, sealed in tubing, detonated by
fuse...in just a min.
Results: I think I should have had the mixture more contained and sealed in, because an air bubble formed around the fuse, which caused a small
explosion - delay - second larger explosion, this is all pretty tiny, but with a decent pop. Container is nowhere to be found, all I could find was a
small piece of fuse that had been burnt on the outside before the detonation. Obviously a plate test of some sort would be helpful and I'll work
on that. Do I have to use a shell casing for that?
The DPPP seems to mix with the MEKP ok, making the liquid cloudy and thick with crystals, although they stayed clumped up a little. I'll try some
more, but let the mixture sit and see if there are further reactions and if it remains stable.
[Edited on 14-1-2005 by Mickhael]
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
The sublimation experiment has reached endpoint on the first DPPP sample which had the light yellow color , and a brown nonvolatile residue remains in
the tip of the culture tube , which appears to have been maybe 2% of the volume of the original sample , while all of the sublimed crystals are
colorless . Towards the end of the sublimation , a very few of the rectangular crystals having the white opaque appearance of ordinary AP crystals
appeared , estimated at maybe 3 or 4% of the sample , while the bulk of the sublimed crystals are cubical and colorless . A similar result is
developing for the reverse order of addition experiment where the precursor was added to the peroxide , cubical crystals are the sublimate , and the
crystals are clear colorless , and different in appearance from the crystals subliming from the garden variety AP control sample . From this initial
experiment with sublimation I have a few preliminary conclusions . DPPP is colorless when pure . And DPPP sublimes to form cubical crystals upon
condensation of the vapors .
The DPPP condensed crystals are clear colorless cubes , while AP condensed crystals are white opaque rectangular having a length 3 to 4 times the
square edge dimension . In the DPPP samples is
a small quantity of material which appears
to form a minority of crystals which are consistent in appearance with the crystals
sublimed from the AP control sample , but the large majority ~ 95% of the sublimed crystals from the DPPP samples are of different appearance from the
sublimed crystals of the AP control sample .
[Edited on 14-1-2005 by Rosco Bodine]
|
|
|
The_Davster
A pnictogen
Posts: 2861
Registered: 18-11-2003
Member Is Offline
Mood: .
|
|
Has there been any difference in the ammount of "non-DPPP" crystalls between the sublimate of pale yellow DPPP and DPPP produced in the
reverse order of addition?
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
The sample of DPPP from the reverse order of addition experiment has not yet completed sublimation and it will be probably another three days before I
will know what sort of mix there may be from that cleaner sample . I am setting up an experiment today with the conventional order of addition ,
letting the reaction run warm at first and then letting the temperature fall steadily as the addition of peroxide proceeds . There has been some
discussion lately about the upper layer that separates after long reaction of the precursor mixture . It seems people forgot that I did test the
response to peroxidation of the upper layer in my original sealed bottle experiment , when I later stirred the two layers into an emulsion and
peroxidized the emulsion , finding that the lower layer was selectively peroxidized while the upper layer separated unreacted . That was the result
which led to efforts at optimizing the procedure for producing the precursor optimized in yield for the red soluble material which does peroxidize ,
even without ever really knowing for certain what was the actual composition of the upper layer , we could know it wasn't what we needed for the
peroxidation .
Update : 47 ml HCl 31.45% and 50 ml acetone were placed in a sealed bottle and after standing 1 hour was then heated at 65 C for 3 hours . A 500 ml
tall form beaker
was placed in a plastic bowl sitting on a magnetic stirrer and a stirbar placed in the beaker . The beaker was surrounded by ice cubes to half its
height and the ice was sprinkled with a handfull of mixed sodium and calcium chloride salt .
A thermometer was placed in the beaker , and an addition funnel containing 130 ml of prechilled H2O2 26.6% was set in a support clamp above the beaker
. The still warm precursor was poured quickly into the beaker and the stirrer was started . The addition of cold H2O2 was begun immediately when the
temperature of the precursor had fallen to 24 C and the addition was regulated at about 1 drop every two seconds to maintain a steady temperature of
20 C until about half the peroxide had been added . The mixture was bright orange soon after the addition first began and quickly lightened to a
bright yellow color growing even lighter to a pastel yellow as the addition proceeded . No noxious fumes or vapors were noted . After the first half
of the peroxide had been added , the rate of addition is slowed to allow for the temperature to gradually fall so that by the end of the addition the
temperature is 5 C . By this time the color has faded to just slightly off white ,
very pale yellow . About an hour has been required for the addition of the peroxide . The temperature continues to slowly fall until it stabilizes at
- 7 C . Stirring is continued for an additional hour and then stopped . The beaker is a thick slurry of nearly white crystals which do sparkle in the
solution and sink forming a clear layer of supernatant liquid , with more than three quarters of the volume of the mixture being crystals . This
reaction proceeded very smoothly with no surges in temperature nor instability noted . The mixture will be allowed to stand for likely several hours
to see if complete loss of color will occur , indicating an endpoint for the reaction . But it appears 99% complete at 3 hours from the beginning of
the peroxidation .
After 8 hours from the beginning of the peroxidation , the color is just barely off white , slightly yellowish green , so pale that I cannot be sure
if the color is simply a shade due to the color of the pyrex glass . The bath is half melted and the temperature is - 5 C . Most of the melted
icewater is suctioned off and fresh ice is added and the mixture allowed to stand overnight , for an additional 8 hours . The bath is nearly melted
by morning and the temperature is -2 C . The crystals have faded in color slightly and appear to be white , and the crystals have lost their
glittering effect and have taken on a matte white appearance , as well as now the crystals have formed a floating raft over a clear lower layer of
liquid . The mixture is stirred at a moderate speed for a half hour as 100 ml distilled water is added to thin the slurry for filtering .
The mixture is filtered and rinsed well on the filter with distilled H2O , and the filter is twisted into a ball to squeeze out remaining liquid .
The damp crystals are rinsed into a clean beaker with 200 ml distilled H2O and stirred rapidly . 10 ml of NH4OH diluted to 200 ml with H2O is added
in portions to the rapidly stirred mixture . After 10 minutes the mixture is filtered , and again rinsed on the filter with
distilled H2O , the filter twisted down to squeeze excess water , and the ball of squeezed cystals is blottered for a few minutes , and then spread
out in a thin layer on a fresh blotter for drying . A very faint odor of ammonia confirms the neutralization . Considerable moisture remains in the
crystals after drying for 6 hours spread in a thin layer upon a sheet of inkjet paper . The offwhite color is apparent against the ultrawhite color
of the 110+ brightness inkjet paper . The crystals are about 95 brightness of white by comparison . The same faint insecticidal odor of pyrethrin is
barely detectable on these crystals , as was the same result for the reverse order of addition experiment . The odor is different from AP , more
faint and a lighter aromatic odor . And the crystals do not glitter like AP . The yield appears lower than the yield for the reverse order of
addition for the peroxidation , but the crystals have not yet been weighed for calculation of yield . The yield figure will be provided in an update
here after the crystals are dried and weighed .
UPDATE:
The crystals are well dried now and the yield is not good , only 23.2 grams of dried crystals which is 47.1% of the theoretical possible yield from
50 ml acetone . This is a far lower yield than the ~75% yield from the reverse order of addition peroxidation experiment run at low temperature from
beginning to end . Therefore it would seem the reaction is favored by low temperature . The precursor for the earlier experiment had been
refrigerated for a couple of days following preparation and that may also be a factor . Hmmmm. More work to do on the preparation . I see Pyroz has
just posted a procedure below .
[Edited on 16-1-2005 by Rosco Bodine]
|
|
|
Pyroz
Hazard to Self
Posts: 76
Registered: 27-12-2004
Member Is Offline
Mood: curious...
|
|
:::
The lab sythesis has shown the validity of the german patent.
Attachment: chemlabsynth.doc (29kB)
This file has been downloaded 1214 times
|
|
|
| Pages:
1
..
20
21
22
23
24
..
37 |
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
