Phenylacetones

So let's say, for instance, that some deranged lunatic did the exact opposite of what this book says, and went ahead and got some equipment, a couple of chemicals and some safrole, isosafrole and/or the precursor of their choice. They may very well decide to do something to it to get it farther along the path to final product. Well, currently on the place called Earth, the most widely made precursor for X and amphetamine production is the phenylace-tone. For crystal meth the precursor is called just that: phen-ylacetone (a.k.a. phenyl-2-propanone, a.k.a. P2P). For X the precursor would be called 3,4-Methylenedioxyphenylacetone (a.k.a 3,4-Methylenedioxy-phenyl-2-propanone, a.k.a. MD-P2P). Strike knows it should technically be written as MDP-2-P, but Strike has always written it incorrectly as MD-P2P and that is just how stupid-ass Strike is always gonna refer to it.

MD-P2P P2P

That double bonded oxygen (a.k.a. ketone) is very amenable to attack and replacement and is the ideal stepping stone to final product. There are a variety of methods to accomplish this intermediate. Many of which Strike is now gonna lay on you!

METHOD #1: Strike's sentimental favorite. The one Strike has dreamt about so very often. This method involves taking hydrogen peroxide and formic acid to form a temporary intermediate which is subsequently hydrolyzed with sulfuric acid to give the ever-lovely ketone.

This method is a little labor-intensive because it involves a lot of distilling, but it is so easy to do and the results are absolutely predictable! The production of MD-P2P or P2P using this method has been previously described [8,9] except that Strike is going to describe the little things. You know, those little bullshit things that never seem to work their way into official accounts but always cause a lot of stress to the novice chemist.

Formic acicl/H202 H2S04

Safrole

Formic acicl/H202 H2S04

MD-P2P

Safrole

MD-P2P

A large flask or glass tea jug is placed in a tray of ice on top a magnetic stir plate. Into the flask is poured 340g of 30% hydrogen peroxide (H202, always store this chemical in the fridge or it will degrade over time) and 1500g of 88% formic acid. The formic acid fumes are immensely overpowering when the stuff is being transferred to the flask but as the solution starts to chill the formic won't evaporate so much and will barely be noticed. 324g isosafrole (or 236g propenyl-benzene for meth) and 1000mL acetone are mixed in a PP container and then poured into a separatory funnel which is situated as shown in figure 9. The acetone solution is added drop by drop into the cold formic solution so that the temperature stays between 10-20°C. The temperature will start to rise a little but the ice bath Is well stocked and the dripping is controlled so that the temperature stays below 20°C

[Figure 9]

The color of the solution will start off clear to pale yellow, then will turn orangy as the dripping continues. After about 200ml_s of addition the chemist will notice that the temperature won't rise so much if the dripping is increased. When addition is complete, the thermometer and separatory funnel are removed. A piece of foil is placed over the opening of the flask and the solution is allowed to stir overnight. The solution is reddish orange after the addition. No more ice is added to the ice tray and the solution, as it stirs overnight, will eventually come to room temperature as the last of the ice melts .away.

The next day comes and the hung-over chemist wakens to see a dark red solution stirring away. In some cases where the chemist had made an enormous batch of this stuff, there may be seen a small mass of crystalline precipitate at the bottom of the flask. This is no big deal and will go away in the next step. If the chemist had made this in a flat-bottomed flask (which she really should have for convenience) then the ice tray is removed, the flask returned to the stir plate, a distillation setup attached, and the acetone is vacuum distilled from the flask. After all the acetone has come over the chemist can proceed in two different ways. One way is to just keep on distilling the solution until all of the formic acid has been removed. The chemist knows that just about all the formic has been removed when there is about 300mL of thick black liquid remaining in the reaction flask and hardly any clear formic acid is dripping over into the collection flask. If one were to swirl the reaction flask, the liquid will appear syrupy and kind of coat the sides of the flask. This is more evident when the flask cools. A quick sniff of the flask may indicate that some formic is still in there, but it should be too minimal to be of any concern.

The problem with removing large amounts of formic acid by distillation is that it takes a long time to do so. Really big batches can take an entire day to distill. So a second option [10] after removal of the acetone would be to cool the formic acid solution then extract the whole thing with ether. The black ether layer is then washed with an ice cold 5% sodium carbonate (Na2C03) solution to neutralize any formic acid that was carried over, then washed

once with clean water. The ether is distilled off to give a black heavy mass just as would have been attained by removal of formic acid by distillation except that it was done in a fraction of the time. One thing to add about this alternative is that it does not always work for everybody. There can be some heavy emulsions and, sometimes, the product forms some weird, heavy ball of tar. This is best tried under strict adult supervision. But it may not all be bad. The following is a Hive post by 'Quirks' letting people know what the goods are regarding a successful (Strike guesses) ether extract:

"If you netralize the formic acid mix with 25% NaOH the layers separate out nicely. It takes 75 I of 25% NaOH to neutralize the soln for 150grm 88% formic, so you'll need a big sepatory funnel. After you hit ph 4.5 add it very carefully cause it'll run away to 9+ real quick. You can then back extract the water with DCM, or I guess preferably ether. If you use too much DCM when extracting it sinks to the bottom and some product floats on the top, so you end up with three layers... But then my lab tech SUXSH (not that I'd partake in illegal activities :p"

Either way, the chemist is going to be staring at a black syrup in the bottom of her flask. Into it she pours 500mL methanol and 2500mL 15% sulfuric acid solution. If the chemist does not have a big enough flask the stuff will need to be halved or thirded and processed in batches. As soon as the sulfuric Solution hits the methanol/product (oxime) layer the heavy black oil will form beads and sink to the bottom. The solution itself will get kind of milky and hazy. Now all the chemist does is slap a condenser into the flask just like fig. 7a and reflux for three hours. After such time, the solution is allowed to cool down to room temperature. Now, in large batches like this and those that are even larger than this one, its just not feasible to extract all that liquid with solvent to remove all the oil. Just about all the oil is sitting at the bottom of the flask. So the chemist decants (pours off) as much of the water as possible, adds fresh water, stirs, decants the water, adds new fresh water, etc.. Three washings of water should remove any traces of H2S04 left in the oil.

Technically, if the chemist wanted to do things by the book, she would extract the whole H2S04/oil solution with ether, then wash the ether with water. So the oil (which is now MD-P2P, by the way) is transferred to a small flask using ether and vacuum distilled (The oil is still very black with contaminants which need to be removed). After all the ether and water have come over and the receiving flask has been exchanged with a clean, new one, it may seem like an eternity for the oil to get hot enough to come over. But, eventually, the clear yellow oil front will start creeping up the glassware and into the condenser. About 250g (60%-70%) of MD-P2P will come over. The chemist knows its time to stop distilling when the oil flow starts to get a little orangy.

The MD-P2P produced here is very pure and is suitable for use in any of the final product conversion recipes.

Distillation is always the most reliable way of separating things from complex mixtures such as relieving our P2P from its annoying black contaminants just like what was done above. But wouldn't it be nice if there was another way to do it for those without a distillation apparatus or who just didn't have the time to distill? Well, there actually is such a way, and it works fabulously!

For years chemists have been using sodium bisulfite (that is BISULFITE not BISULFATE) to actually crystallize a ketone out of solution in order to separate it. As it so happens, our happy little MD-P2P is a ketone. And when an oil mixture containing it is mixed with a saturated solution of sodium bisulfite (NaHS03) the MD-P2P crystallizes out as a 'bisulfite addition product'. It can then be easily separated by filtration. Here's how it goes...

When the MD-P2P/crap oil has been isolated and is at the point where one would normally apply distillation, this is the point where the chemist will use the bisulfite. One should not try this method unless the oil is rid of most solvent. In the Method #1 above, one would apply it after the ether from the final extraction has been removed by boiling or distillation (Yes, some distillation still ap

plies!). In the methods to come, Strike will let you know when it can be done.

Anyway, one has the P2P/crap oil, right? Right. Next one makes a saturated sodium bisulfite solution by dissolving as much sodium bisulfite as will dissolve in a given amount of water (say, 1000mL). Now one adds the MD-P2P oil into some of the saturated solution and stirs for 30 minutes. The temperature of the reaction will rise and a big old mass of P2P crystals will form. People often say that the crystals look like chicken fat. Those crystals formed because the bisulfite from the sodium bisulfite latched onto the ketone of the P2P to form a precipitate. And since the P2P is probably the only oil component with a ketone, it is gonna be the only thing of any consequence that crystallizes.

The solution is allowed to cool and the crystals of the P2P-bisulfite addition compound are then separated by vacuum filtration, washed with a little clean dH20 then washed with a couple hundred mLs of ether, DCM or benzene. The filter cake of MD-P2P-bisulfate is processed by scraping the crystals into a flask and then 3Q0mL of either 20% sodium carbonate solution or 10% HCI solution are added (HCI works best). The solution is stirred for another 30 minutes during which time the MD-P2P-bisulfite complex will be busted up and the P2P will return to its happy oil form. The P2P is then taken up with ether, dried and removed of the solvent to give pure MD-P2P. Whaddya think of that?!

This procedure can be applied to most P2P mixes but is especially effective on the methods to follow. However, in super clean methods, such as the PdCI2 below, where lots of isosafrole is produced, the iso byproduct can interfere with crystal formation. Someone-Who-ls-Not-Strike once found that when an appreciable amount of isosafrole was formed to the detriment of MD-P2P, the oil screwed up the crystal matrix disallowing it to form. Confused, the chemist tried to rescue the uncrystallized oil from the aqueous solution by extracting out the oil to try other things. But when the solvent hit the solution, the P2P crystallized out. Go figure? The chemist felt that it may have been due to the solvent solvating out the isosafrole which gave the P2P a chance to form more crystals.

Strike sees a point to this in Vogel's text 'Practical Organic Chemistry' (3rd ed.)[37]. In it, Vogel crystallizes his ketones using a saturated sodium bisulfite solution that alscf contains a little solvent. This is in contrast to the straight up aqueous (only water) solution that Strike described above. Here is what Vogel said on page 342:

'Prepare a saturated solution of sodium bisulfite at the laboratory temperature from 40g of finely powdered sodium bisulphite: about 70ml. of water are required. Measure the volume of the resulting solution and treat it with 70 per cent, of its volume of rectified spirit (or methylated spirit) [ethanol or methanol or both, dude] ; add sufficient water (about 45mL.) to just dissolve the precipitate which separates.'

Either pure aqueous or aqueous/solvent solutions work. It is entirely up to the preference of the chemist as to which one they use. Just to make one feel more secure, there is a little test one can do with the bisulfite solution to see if they got it right. Just put a little of that ketone known as acetone into the saturated solution and watch the crystals grow. Isn't it nice how chemistry works?!

Now then, there are some chemists that rely on bisulfite as a tool to physically separate all of their ketone from an oil mix. But some chemists, using some methods, are rightfully sure enough that their ketones were produced in such high yields, and so cleanly, that separation isn't necessary at all. But even they, like anyone else, would still like to know for sure that what they made was P2P. This bisulfite procedure works in this regard as well. If one wants to know if what they made is P2P all one has to do is just drop a mL or so into the saturated bisulfite solution and see what happens. If crystals form, one has ketone. If not, one has fucked up.

One can even use this test as a quantitative measure. The chemist can weigh 5g or so of their P2P product, crystallize it and weigh

the subsequent P2P oil that results to get an idea of how much of their product is honey, and how much is not. Get it?! As Strike hopes you can see, this simple sodium bisulfite tool has an enormous amount of potential for helping the evil chemist out.

One final thought. Strike found that there are a lot of companies that do not sell sodium bisulfite (NaHS03). In fact, a lot of companies list 'sodium bisulfite' in their catalogs but tell the reader to see 'sodium metabisulfite' instead because that is the only form of this compound they carry. In other words, a lot of companies sell sodium metabisulfite (Na2S205) as an acceptable alternative to the other. The Merck Index even says about sodium bisulfite that"the [sodium] bisulfite of commerce consists chiefly of sodium metabisulfite, Na2S205l and for all practical purposes possesses the same properties as the true bisulfite". What this meant to Strike was that metabisulfite would work just as well. So some was purchased and tried. And it really does work just the same!

METHOD #2: Without a doubt, this is the current world favorite for making P2Ps. This method is known as the Wacker oxidation and involves mixing safrole (or any other allylbenzene), palladium chloride, cuprous chloride and dimethylformamide in an oxygen atmosphere to get MD-P2P very quickly and in a totally clean manner [11, 12]. There's also a very nice review in ref. #13.

Strike ranked it #3 in the Top Ten from the first edition because Strike didn't think people would bite at the idea of using such an expensive catalyst as PdCI2. Street chemists are often tightassed when that is the last thing they should be when it comes to production. But this has not been the case with this procedure as Strike has happily found out. At $7.00-$9.00/g, PdCI2 is still pretty pricey but this has not been a deterrent as many chemists have found. Nor should it be. This procedure works so well that it would, in fact, be stupid not to do it should one happen to work in an accredited, licensed research lab. The following is what Strike first wrote about it.

Safrole

PdCI2/CuCI/DMF

PdCI2/CuCI/DMF

Safrole

Isosafrole

The reaction proceeds via the above schematic. And as one can see in the above schematic, the major side product of the reaction is not tar or junk but is the very useable isosafrole. This is just another illustration of the desire of the safrole double bond to migrate to the isosafrole position when given the chance. The cuprous chloride (CuCI) and oxygen are there to promote and keep the PdCI2 in a +2 state (don't ask). There are two different apparatus setups that a chemist can use to complete this recipe depending on the equipment available. Figure 10a shows a setup using a three-neck flask and figure 10b shows how the same system can be attained using a single neck flask. Also, one can use the single neck flask by placing the Claisen adapter from one's distillation set into the flask's neck.

No matter which flask is used, an addition funnel is required. An addition funnel is just like a separatory funnel except there is an extra side arm that allows for addition into a system that has pressure (which this one is going to have). Strike knows! Strike knows! Pressure sounds complicated but this one isn't. You'll see. The addition funnel can be bought, made from a separatory funnel as explained in the How to Make section of this book, or

can be made entirely from scratch as suggested in the same section.

The pressure is going to come from oxygen that is applied to the system using a balloon. Pure oxygen is easy to get. The chemist can get it from the neighborhood specialty gas cylinder company or she can plow through the grannies down at the local pharmacy and get a small, personal use bottle there. The oxygen is then used to fill up one of those thick walled carnival balloons that can be bought at any toy store.

The idea is to have everything in place before the oxygen is applied So 100g of safrole is in the addition funnel and stirring around in the reaction flask are 10.6g of PdCI2, 60g CuCI and 500mL of aqueous dimethylformamide (made by mixing 62.5mL dHzO and 437 5mL DMF). Dimethylformamide (DMF) is not the same as the watched chemical known as N-methylformamide.

DMF is a common, legal solvent. If a three-neck flask is being used then the openings on top of the addition funnel and the unused neck of the flask are plugged with stoppers and the stoppers secured in place with wire or strong tape. With everything all set the chemist fills up a balloon with oxygen, pinches it closed with her fingers, wraps the end over whichever opening is appropriate and releases. This setup can look pretty cool depending on what kind of balloon the chemist chose. Maybe one of the three foot elliptical kind or one with a ducky printed on it.

Anyway, all that pure oxygen has infiltrated every part of the enclosed system and the solution in the reaction flask is allowed to stir, exposed to all that oxygen for 1 hour. At first the solution is brownish black, but as it absorbs the oxygen over that hour's time it will turn an olive green. After 1 hr it's time for the chemist to add the safrole slowly over a 30min period. As the safrole is being added it will start to take up all that oxygen causing the palladium to turn black again (shows that things are working) but after the addition is complete and the safrole has been converted to MD-P2P the palladium will again start to soak up the remaining oxygen and turn green once again. The solution remains stirring at room temperature for 16-24 hours. If the balloon loses significant volume during the reaction, one just fills it up again. Nothing bad will happen.

The next day the chemist takes a PP container of 1500mL cold 3N HCI out of the fridge and pours the contents of the reaction flask into it. The mixture is stirred a little and extracted 3 times with 100mL portions of either DCM or ether. The one thing that needs to be added here is that the DCM extract needs to be washed 2 to 3 times with water. Many bees have reported that this reduces/prevents an emulsion from happening in the next step. The solvent is then washed with 200mL saturated sodium bicarbonate (Na(C03)2) solution then with 200mL saturated NaCI solution. Technically the washings can be skipped, but either way the solvent is going to be dried through sodium sulfate in filter paper and the sodium sulfate washed with a little extra solvent just as is described in the methodology section of this fine book. The solvent is then removed by distillation leaving what should amount to

about 70-80% MD-P2P and 20-30% isosafrole oils still left in the distilling flask.

Oh boy! Here's another case where there is a couple of similar boiling oils that the poor chemist is going to want to separate. Again Strike is going to say that the best way to do this without fancy separation columns is going to be to allow that the first 5-10mLs of oil that distills over is going to be mostly isosafrole and the rest of the clear oil that comes over is going to be the MD-P2P. Strike has never been a believer in predicting the precise temperatures that something comes over at relative to the pull of vacuum or the size of the distillation apparatus. It varies too much and is never applicable to any given circumstance. Strike knows three things in instances like this: 1) solvent always comes over first at low temperatures and in a very rapid manner, 2) the isosafrole starts to slowly roll over at about 170°C at regular vacuum (who the hell knows what that is?), 3) after about a 3-5 degree increase in temperature (usually no increase is noticeable) or, more importantly, after about 5-10mLs of oil has collected then it's time to switch flasks and start to collect what is assumed to be the MD-P2P. In the end, the chemist should just follow her nose. Does the first few mLs of oil smell strongly of licorice? Does all the rest of the oil not? Strike cannot answer this either. The isosafrole fraction will smell like licorice but MD-P2P always smells different relative to the type of reaction it is borne from. Pure MD-P2P doesn't have that strong a smell and can usually be overpowered by impurities that will always carry over with it from the reaction it came from. So MD-P2P that comes from a reaction using formic acid or mercury compounds is going to smell a little differently than one that came from a reaction using palladium. However, the distinction between isosafrole/safrole and MD-P2P is quite evident. In the end, a little of one in the other is not going to hurt things much.

' Of course the chemist may wish to forego purification and separation of the two remaining oils by distillation and opt for the sodium bisulfite procedure described earlier. That particular method is perfectly suited for this situation. Perfectly.

If using oxygen balloons is not one's cup of tea, then there are ways to supply the oxygen without it. It has been demonstrated that using quinone (benzoquinone) can accomplish the same thing [12]. To do this one has all the ingredients, including the safrole and quinone, stirring in the reaction flask except for the water that was mixed with the DMF. That water is going to be the thing that is placed in the addition funnel and added to the reaction mix. Another oxygen source can be that of 30% hydrogen peroxide [14]. This procedure is done exactly as the regular method except that the aqueous DMF is made with 30% hydrogen peroxide instead of plain dH20.

Other alternatives for this procedure can make it even more versatile. To decrease that 24hr span of incubation/stirring one can run the entire reaction at 60-70°C from the beginning of addition. The reaction need only proceed for about 3 hours. The downside is that a three neck will have to be used to accommodate a thermometer and reflux condenser. Another switch can be made by using cupric chloride (CuCI2) instead of cuprous chloride (CuCI). Both work equally well except that CuCI2 has a tendency to chlorinate the product slightly. Strike has since learned that any and all of these alternatives work well! Keep reading farther down the chapter for all the goods on it!

So anyway, that was what Strike told everybody in the first edition. People then ran with the idea and came up with some very interesting observations of their own since then. The following is an account of the PdCI2 method contributed by our good friend TDK. From what Strike knows of TDK she seems to be a very accomplished, careful and intuitive chemist in her own right. Nothing illegal of course. But she always seems to be coming across evil methodologies that others produce.

"/ contacted my sister's friend and went over to her compound for a complete run down on what she dreamt... Her dream was of an educational nature and so should the following be construed as just that...

The Wacker Oxidation a.k.a. #3 of 10 (most fool proof of the lot)

The following is her interpretation, simplified to its MOST BASIC FORM, for the layman with little experience:

First she lists the equipment, next the reagents.. Also, noted are the book's quantity and her dream of a 5x scale up:

Equipment for 5x scale:

Phase One - Equipment

6-liter fíat bottom flask (single 24/40 neck)

1 claisen head adapter (24/40)

1 1-liter addition funnel (24/40)

1 Teflon stir bar

1 heavy duty balloon

1 roll of electrical tape

Magnetic stirrer

Support stand and clamps

Ohaus triple beam scale

1 plastic funnel

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Responses

  • fatima
    Can you extract formic acid out of n dimethylformamide?
    8 years ago

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