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Hoffmann-LaRoche
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damn.....youre pretty right.....why didnt we come to this earlier!-And again, a nice job on the pictures....what program are u using?
HLR
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vulture
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I use ISIS Draw, a program I downloaded for free and it's very simple to work with.
http://www.mdli.com/products/isisdraw.html
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
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Polverone
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Further info
This patent seems pretty vague on details. It could be a deliberate omission, so that anybody who wants to replicate the work has to guess at the
exact procedures but anyone who infringes the patent can still be prosecuted.
Anyway, the adventure continues:
I found info on the web that indicated that acetone will yield phorone, mesityl oxide, and mesitylene under the influence of strongly acidic or basic
conditions. Organic Syntheses online indicated that mesitylene is formed in appreciable quantities only with dehydrating agents (such as conc. H2SO4).
Another reference indicated that mesityl oxide would be formed by the action of hydrochloric acid on acetone, but only in small amounts.
I, hoping that my mixture would settle down at some nice equilibrium point, applied moderate heat to the HCl/acetone mixture for a couple of hours.
But it passed beyond yellow to yellow-orange and then to orange, and I decided I should finally withdraw the heat.
When the orange liquid was placed in the freezer, nothing crystallized out. A small amount of the cold liquid was mixed with twice its volume of
(somewhat concentrated) H2O2. Over the course of an hour there was a small amount of bubbling in the mix and some sort of platelike solid formed in
small amounts on the surface of the liquid. The reacting liquid had a somewhat unpleasant solvent-like smell, but it did not smell like HCl, Cl2, or
acetone peroxide.
This morning, the small amount of solid that formed had disappeared. I am wondering if I heated my HCl/acetone mix too long and converted the phorone
to something else.
I may try making another phorone batch, this time chilling the flask as soon as the liquid starts to get an orange tinge.
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Hoffmann-LaRoche
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I agree with you about the vague patent description of the process.
I came across lots of patents obviously written as vague as possible...
Did you add a small amount of H2O2 in the first reaction?-The patent-drawing of the reaction shows the note of H2O2 being necessary as catalyst.
Maybe it would be better, if only moderate heat (40-50°C)was applied in the first reaction as secondary oxidation reactions possibly get more
important....but i`m no expert though.
HLR
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Hoffmann-LaRoche
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sorry....forget what i said in the last post...it was just talking out of my stomache.
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Polverone
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The first reaction?
The one where phorone is formed? I didn't see that mentioned but didn't look at the patent too closely once I saw that it was all in German. I would
be wary of adding H2O2 at that stage because I would expect it to form acetone peroxide, and I don't care to heat a flask containing acetone peroxide
(even in solution). But if it's a truly small amount that is required, I might try it. Does the patent specify how much H2O2 to add in the
phorone-creation stage, or is it vague there too?
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BrAiNFeVeR
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Well, todayI also took a throw at DPPP.
At the same time, I prepare some regular AP using 20 ml acetone, 12 ml H2O2 (35%) and 8 ml HCl (10%).
I'm not gonna describe the preparation of AP, since that's a dead giveaway ...
To 25 ml acetone, I added 25 ml of 35% HCl (a slightly exothermic reaction occurs), and then I slowly heated this until bubbles reached the surface.
By this time, the solution was nice and yellow ...
I cooled it, in the hope that crystals would ppt out, but no such luck 
I then took 5 ml of this supposedly phorone solution, placed it in a test tube, and added some snow from the freezer, hoping, that due to it's pretty
bad solubility in H2O , I would get crystals.
Again, no luck
I took another 5 ml of this yellow solution (evolving HCl vapors btw) and to it, added an equal volume of 35% H2O2. instantly, white crystals started
to form, and the test tube heated up a little bit too.
This was left for 2 hours, after wich 90 % of the solution was packed with a very fine crystaline product.
These fine crystals where filtrated, neutralised and dried.
The smell is allmost exactly the same as the (at this time) still crystalising AP.
When hit by a hammer (not very hard) it detonates with the release of the very unpleasant smell of detonated AP.
Which was especially unpeasant in this case, because it indicates that what I have, is mostly regular acetone peroxide, since DPPP would have
different detonation products, right ?
So now all my hope lies in getting the phoron out of that solution in a crystaline form, wash it, and peroxidise that ...
Maybe I'll try to dehydrate 5 ml in a dessicator tomorrow in case heat would destroy phorone in some way.
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Hoffmann-LaRoche
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Here are the stoichiometric mixing proportions, which i calculated using the molar amounts in the reaction equations, which are surprisingly much
different from the proportions given by the patent:
1)
21,75mL 2-propan-on (D=0,8)+ 70,88mL 30% hydrochloric acid(D=1,2)
which is kept at 50°C for some hours, until the solution turns yellow
(referring to polverone).
2)
68,74mL 30% hydrogen peroxide(D=1,3)
are added to the above mixture and left at room temperature, or i suppose, better on an ice bath for 24-48 hours.
slowly precipitate forms.
dilution with cold water may precipitate some additional DPPP.
Compared to the patent, a mixing ratio of approx. 1:3:3 (acetone:conc. HCl:30%H2O2) results, while the patent says 1:1:2(if the ratios are by volume)
........Confusing!
HLR
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Hoffmann-LaRoche
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Try adding EtOH or MeOH, as it could well be possible, that phorone is not soluble in alcohol or methanol.
Maybe the phorone/phoronepentachloride precipitates.
Id say it`s worth a try.
HLR
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madscientist
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Phorone dissolves in alcohol. It's essentially insoluble in water.
I weep at the sight of flaming acetic anhydride.
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Hoffmann-LaRoche
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Doesnt anyone have access to beilstein?
- There HAS to be a procedure for it.
Philou, our hero......what´s up?
Furthermore, no one tried to make the peroxidation-step with proper cooling.
I suggest this would give bigger crystals and better yields.
If the crystals are then still that much smaller than AP-crystals, this would be a clear indication that DPPP, and not AP is the major product of the
reaction.
The detonated peroxide smells a lot like AP?-Well, why not?-To me it is very likely that AP could be a by-product in the reaction.
Can`t wait for the next weekend, when i can start some similar batches myself.
HLR
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Hoffmann-LaRoche
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Summary of differences to AP:
1)Phorone-intermediate is yellow and water insoluble, soluble in EtOH, and very likely also in acetone and Et2O
2)Crystals are supposed to be smaller than AP-crystals
3)Purified DPPP is said not to smell
4)It has a giga-brisance for an organic peroxide(only if compressed to near crystal density, for sure)
5)It has a density much much higher than AP (0,8g/cc, if i´m right), this could be measered easily, as i proposed in one of my posts..
6)The peroxidation of the pentachlorphorone yields 10mol HCl per mol DPPP, so the pH will drop SIGNIFICANTLY.
Notice: if u dont start from purified pentachlorphorone, it will be very difficult to see the pH dropping any further when using ordinary
pH-indicator, as your solution is already strong acidic.
7) DPPP is very storage stable, and i suppose, because of its high molecular weight, it is not sublimizing like AP.
That´s all so far.
HLR
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rikkitikkitavi
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my chemical dictionary states that phorone is formed when acetone saturated with HCl is left standing.
This could mean that it will not work with
HCl in aqeous solution. Maybe the reaction time needs to be extended to...
/rickard
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Hoffmann-LaRoche
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That´s interesting...this would complicate the process a bit....but no problem so far!
I´ll try that as soon as possible.
A good prep.-method for dry HCl-gas is heating H2SO4 + HCl.
And maybe then, with emphasizis on anhydrous reactants, the acetone could be thouroughly dried by adding by adding small amounts of anhydrous K2CO3 or
CaCl2 (ref. CD-Roempp chemistry lex., Thieme 1995).
But the best would still be if somebody could download the procedure(s) from the Beilstein database...
HLR
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Hoffmann-LaRoche
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äh.....sorry for the messy equation.....ya know what i mean
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madscientist
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About two-thirds of the way through this thread there is an attempt to synthesize acetone peroxide that is of interest to this discussion.
http://pub9.ezboard.com/fxinventionspyrotechnics.showMessage...
I weep at the sight of flaming acetic anhydride.
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Hoffmann-LaRoche
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vulture
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Better keep the kewls ignorant of what they might be making....
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
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Hoffmann-LaRoche
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DPPP research.....another attempt
Finally, i had some time for experiments.....
1) tried making phorone:
A)50mL of 30% HCl + 50mL acetone, (flask was warming up a bit).
Then heating of the mixture for more than 12 hours: the colour went from yellow to orange and finally it went black(maybe decomposition occured, and
carbon was the result..).
B)Then i tried the same again, but this time, i covered the flask with another glass container, so that fewer acetone and other reaction products
could volatilize.
After some hours, the outside temperature being quite low, i noticed some crystals on the inside of the covering glass container, which must have
sublimized out of the acetone/HCl solution.
Probably phorone?...or just traces of AP which were left in the glass from previous experiments....Has anyone tried to make phorone, and experienced
the same??
As phorone seems to be very volatilizable and also seems to be easily devastated to leave only carbon, maybe there is a possibility to recover phorone
on a cold surface above the flask...
C)tried the one with dissolving dry HCl gas in acetone.
Well, i made a saturated solution of HCl gas in acetone and i have let stood the flask at 15°C since 3 days.
And again, the colour turned slightly yellow, then golden yellow, and at this moment, it has an orange colour.
Let´s wait ....
2)Tried to make DPPP without isolating phorone first:
mixed 25mL of 30% HCl with 25mL acetone and immediately, an exothermic reaction ocurred.
After the mixture had chilled down, i added 50mL 30% H2O2 and put it into the refrigerator at 5°C.
After a couple of hours, i noticed that the bottom of the flask was covered by a 3mm layer of small crystals.
Then i washed the crystals, which had the same size of AP crystals, with water and dropped a little quantity of them into a lead nitrate solution,
which had a measured density of 1,3g/mL,..........the crystals did not sink.
Thus the obtained substance had to have a density between 1,0(sunk in water) and 1,3g/mL.
I dont believe, that a substance with such a low density could have a Vdet of near 9000m/s, so i dont think DPPP was the product.
Furthermore, a yield of 90% was mentioned for the DPPP process, which certainly wasnt the case as raw quantities of reactants were introduced, and
only a small layer of crystals could be recovered.
This made me think a lot....if the inventor mentions an overall-yield of 90%, it is very likely that the process is really a simple one, and last but
not least, he also mentioned that it is the purpose of the patent, to make blasting operations cheaper; not a single word about distillation
operations, none about heating/cooling!
It´s simply a fact that we know too little about phorone and DPPP.
HLR
10 fingers present.
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Hoffmann-LaRoche
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japanese patent
This is a japanese patent, found by rc from the E&W-forum:
PURPOSE:To obtain phorone in high yield by subjecting acetone to aldol condensation in the presence of an alkali catalyst to give mesityl oxide,
dehydrating a residual oil an acetone trimer in an acid catalyst such as phosphoric acid base under heating and distilling.
CONSTITUTION:Acetone is subjected to aldol condensation in the presence of an alkali catalyst, mesityl oxide is distilled and separated, a residual
oil containing acetone trimer is dehydrated in the presence of 1-10wt.% acid catalyst (preferably phosphoric acid base) under reduced pressure at
50-130 deg.C, preferably 90-120 deg.C so that other acetone trimers are converted into phorone and distilled to give phorone shown by the formula. A
reactor is equipped with Dean Stark separator or oil-water separator and formed water is taken out from the reaction system so that equilibrium
relationship is transferred to a formation system to give phorone. The acetone trimers are economically not abandoned. Phorone is useful as a raw
material for agricultural chemicals, coating compound for ship bottom, antistatic agent, polyamide resin, etc."
The main reaction is 3 C3H6O--->C9H14O+ 2 H2O
Maybe there are other patents too.
HLR
10 fingers present.
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Polverone
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Phorone fun
I've made a couple of other attempts to prepare phorone. Once I added aqueous HCl to acetone and heated as before but only let it react to form a
light yellow solution. This material didn't seem to yield anything but ordinary acetone peroxide when combined with H2O2.
Then I did another batch with aqueous acid that I heated until I got a very dark solution. I poured the dark solution into sodium carbonate solution
and it lightened considerably. The bulk of the solution went to a pale yellow, and there was some oily substance that floated on the surface of the
water without mixing. On prolonged standing some fluffy yellow solid appeared as well.
I meant to try saturating acetone with anhydrous HCl this weekend but I got distracted by other things. It sounds like it gives a similar product in
any case. I may try the first part of this Japanese patent, but I don't have vacuum distillation equipment so I can't try all of it.
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Polverone
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Phorone fun
I've made a couple of other attempts to prepare phorone. Once I added aqueous HCl to acetone and heated as before but only let it react to form a
light yellow solution. This material didn't seem to yield anything but ordinary acetone peroxide when combined with H2O2.
Then I did another batch with aqueous acid that I heated until I got a very dark solution. I poured the dark solution into sodium carbonate solution
and it lightened considerably. The bulk of the solution went to a pale yellow, and there was some oily substance that floated on the surface of the
water without mixing. On prolonged standing some fluffy yellow solid appeared as well.
I meant to try saturating acetone with anhydrous HCl this weekend but I got distracted by other things. It sounds like it gives a similar product in
any case. I may try the first part of this Japanese patent, but I don't have vacuum distillation equipment so I can't try all of it.
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BLAST_X
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I've tested preparation of DPPP and i can say it`s a very interesting and varied explosive.
You can use it as a primary explosive and as a high energetic secondary explosive.
You can never classify DPPP in the same category as AP or HMTD.
The question is, at which density you use DPPP and at which method you use to ignite DPPP.
preparation:
To a 1000 ml erlenmeyer flask add 185 ml of 20% HCl (i don`t
have 35% HCl at this time). To a second flask add 100 ml of aceton.
To an third flask add 200 ml of 30% H2O2. Cool all to 5 C.
After cooling, slowly add the aceton to the HCl and stir the mixture
for 5 minutes.(very slight yellow colouring over a few minutes)
The patent don`t say heat at this time and the patent don`t say
some product (poron) should precipitate from the solution at this time.
If you heat or not, the content of AP are always present at end of the synthesis. On the contrary, if you heat to much or to long, the reaction fails.
Cool the mixture to 5 C for 2 hours and stir occasionally.
After standing, set the mixture to magnetic stirring at room
temperature and slowly (over 10 minutes) add the H2O2 to the
aceton/HCl mixture. The temperature can rise over 40 C and
the mixture become a sligth green colouring.
(second reaction-step, formation of pentachlorporon and free
Cl with H2O2 as catalyst)
The DPPP should precipitate on top of the mixture and some fumes bubble of.
You can distinguish this of AP crystalls, which formes in the reaction-mixture and which are a bit larger than crystals of DPPP.
I`ve look at the crystals exactly through a microscope.
(look at attachment DPPP.jpg)
After all H2O2 is adding, continue stirring for 2 hours an more till the liquid on the bottom of the flask are clear and no fumes bubble of.
Filter out the crystals, wash them with 1 L of 10 % sodium bicarbonate solution, and again with water.
Dry crystals of DPPP at room temperature for 48 hours.
The next step are very important to remove all traces of acid and AP in the product, that you can handle safe with DPPP.
Dissolving the crystals in minimum amount of hot ethyl alcohol (60 C),
let cool to 5 C, filter, add a large volume of cold distilled water, let sit for 1-2 hours below 10 C and filter again.
Let dry DPPP at room temperature for 1-2 weeks to decompose and evaporate the rest of AP on the air.
final yield: 65 g
(at this reaction temperature and with delute 20% HCl, i think you can get much more yield with reaction temperatures below 10 C and a longer reaction
time, the patent say around 90%)
Be careful with large quantities because DPPP is somewhat sensitive
to friction, shock and heat.
I`ve tested the DPPP in 3 different charges.
1. I`ve made a blasting-cup (hard-paper) with 5 g charge low pressed
DPPP and ignite with a match.
No detonation, only flash, the blasting-cup bursts only.
Consequently, if you ignite DPPP at powdered density or with flame,
it`s flashes only, you can use it as a primary explosive similar
to AP and HMTD, it detonates only at this density when strongly heated.
(very storage stable and lower sensitive to friction and shock)
2. I`ve made a stable blasting cup (hard-paper) with 50 g charge high
pressed DPPP and ignite with a match.
It datonates hazardous and i`d feel strong the detonation pressure
still the distance of over 50 m between the blasting-cup and me.
3. I`ve made a stable blasting cup (hard-paper) with 10 g charge high
pressed DPPP and ignite with a match.
It datonates correctly as well.
Consequently, in high pressed density or under pressure in a
stable blasting-cub - DPPP is a high qualtity and high energetic
explosive, it detonates without a primary igniter.
Disadvantage:
- somewhat sensitive to friction and shock
- low detonation temperature, ~ 200 C
- density of DPPP are not very high
Advantage:
- required chemicals for synthesis are cheap
- it`s easy to produce (no expensive lab-equipment required)
- large volume of gas and high explosive velocity, ~ 9000 m/s
(conditioned military usage, cut of steel ...)
- storage stable and great chemical stability
DPPP is my new favourite peroxide. It`s safer to handle as AP or HMTD and more powerful and brisant.
It`s a very good primary explosive to ignite very insensitive explosives (hexogen,octogen,TNT,HNIW) or a energetic single explosive.
all you need is C - H - O - N
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madscientist
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Success with phorone preparation!
I mixed 35mL of 31% HCl with 25mL of CH3COCH3, and held the temperature at 0C for two hours. Since nothing obvious was happening, I heated it up to
17C for an hour. Still, no signs of reaction. I heated it to 50C for another hour. It's now a beautiful, urine-yellow, and crystals are precipitating!
Not in large amounts - they form at the surface of the liquid, sink back into the liquid, re-dissolving. More news surely to come!
I weep at the sight of flaming acetic anhydride.
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madscientist
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I added 50mL of 27.5% H2O2, after letting the phorone solution cool to 25C. The temperature jumped to 40C, and the solution turned clear - for a
moment. It soon turned milky, and within a minute, there was a visible quantity of a white precipitate collecting on the surface of the solution. I
probably should mention this - I covered my reaction beaker in which I prepared the phorone with aluminum foil, which was covered with a white solid
that had a solvent-like odor, but did not smell like anything I have ever handled before.
I weep at the sight of flaming acetic anhydride.
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