MDMA Synthesis: How ‘Molly’ is made

So you’ve woken up in the middle of the night, your mind entranced by a singular glorious thought: “Could I just make my own MDMA (molly, ecstasy)??”  Well…it’s possible, but probably harder than you’d think.  (It should go without saying that it’s extremely illegal to do so.  As in ‘government agents with machine guns kicking in your front door in the middle of the night’ illegal.) It’s also not necessarily physically safe; the legends of drug labs blowing up are well rooted in reality!  So don’t try this at home.  Or at work.  Or anywhere else for that matter.

Reaction Overview:

The classic ‘ketone’ approach (certainly not the only possibility, but the best documented one) has a lot of variations, but the basic scheme is the oxidation of the plant oil safrole (1-allyl-3,4-methylenedioxybenzene) into a ketone (3,4-methylenedioxyphenyl-2-propanone), which is then condensed with methylamine and reduced to the final MDMA product.

Step 1: Peroxyacid oxidation (requires isomerization of safrole) or Wacker oxidation (an elegant catalytic oxidation) produces the ketone “PMK” (piperonyl methyl ketone, also known as 3,4-MDP2P, or 3,4-methylenedioxyphenyl-2-propanone.)   There are a lot of oxidization reactions available, but in this case we of course want something that will produce the Markovnikov product, with addition occurring at the more substituted end of the alkene.  An initial oxidation to an alcohol followed by a second oxidation step to a ketone is also a possibility.  Since safrole and PMK are carefully watched and regulated precursors, the current favorite precursor (typically bought from Chinese chemical manufacturers) is PMK glycidate.  PMK glycidate can reportededly be easily broken down into PMK simply by refluxing it with hydrochloric acid.  (But read on about the chemical watch lists!)

Step 2: Reversible imine formation (occurs spontaneously when the ketone is placed in solution with methylamine freebase (not the hydrochloride salt.)

Step 3: Reduction (via hydrides, aluminum-mercury amalgams, or electrical cells) or catalytic hydrogenation permanently converts the imine to MDMA. Since ketones and imines lack a chiral center, they (like a good Buddhist monk) do not project personal desires on the world, so the resulting product is racemic, containing a 50-50 mix of both the stronger S(+) isomer (which releases plenty of serotonin, dopamine and norepinephrine) and the weaker R(-) isomer (which is effectively just a serotonin releaser.)  All MDMA sold on the streets appears to be racemic.  A product containing only one isomer would not subjectively feel the way racemic MDMA does, being either more amphetamine-like or more sedating and mellow (like MDEA, which seems to be primarily a serotonin releaser.)

Safrole is found in various “essential oils”, the most famous of which is sassafras oil, which can contain as much as 90% safrole. Since safrole (and isosafrole, MDP2P/PMK, and sassafrass oil) are “listed precursors” in the US they’re very hard to find.  (Many remaining ‘sassafras oil’ products are now safrole-free in order to avoid regulation.)  Even attempting to order one of these chemicals can bring law enforcement attention.

The most famous route is probably one of Shulgin’s original synths from PIHKAL (third paragraph), starting with PMK (MDP2P) made from isosafrole.  Isomerization of safrole is reportedly an easy operation, as described in the famous Strike synthesis collection.  (A more compact review can be found in this old doc saved from Rhodium.)

Shulgin’s ingenious use of aluminum foil and mercury as a reducing agent opened up a lot of possibilities for hobbyist-scale clandestine labs, but it comes with one ugly downside:  Highly toxic mercury compounds.  The disposal of the leftover chemical waste from clan-labs has always been an environmental and public health problem, with irresponsible chemists dumping waste in ditches or even flushing it down the drain into  sewer systems.

Mercury-aluminum amalgam is an interesting little reagent.  Aluminum has a low electronegativity, which suggests that it would react very readily with anything mildly electron-hungry (such as the carbon atom of an imine, or the hydrogen atoms of water.)  And yet, aluminum is considered corrosion-resistant under most conditions, to the point that it’s even used as shipping containers for nitric acid!   That’s because, although aluminum does react readily, it tends to form aluminum oxide.  This aluminum oxide forms a tightly interlocking crystalline layer over the remaining aluminum, sealing it off and protecting it from further reactions.  Mercury is able to penetrate this protective oxide layer and prevent it from re-forming, which allows the aluminum to continue to react, contributing electrons to reduce whatever suitable chemical (oxygen, water, imines, etc.) happens to be handy.  This ability is the reason that you aren’t allowed to take or ship mercury on jets, which are usually made from aluminum.  A spill of mercury could create a chemical ‘rot’ in the structure of the plane as the now unprotected aluminum continues to react with moisture and oxygen in the air.

Well, to brass tacks.

A not-so-theoretical ‘recipe’ for MDMA:

1. The daring (and perhaps soon to be incarcerated or incinerated) cook gets ahold of a little bit of real sassafras oil (not that easy to do these days in the US, but a thoughtful and clever person could likely figure out how to come up with perhaps 50 ml to play with at minimal risk/effort.)  He vacuum distills it (or perhaps uses fractional freezing) to isolate the safrole, yielding about 40 ml of safrole.   Sassafras oil is suspicious in ‘significant’ volumes; don’t try to order a liter of it. In fact, it’s best if you don’t order sassafras oil at all. Purified safrole is suspicious in any quantity and should never be ordered.

2. Next, let’s say they’re going to attempt a Wacker oxidation to get from safrole to MPK.   This would normally be done with oxygen gas, but a less hardware-intensive method is to use benzoquinone as the oxidizer.  So, in a 500 ml round bottom flask the daring cook mixes together:

40 g p-benzoquinone

100 ml methanol

0.5 g PdCl2 (palladium chloride)

12 ml distilled water

Generally these reagents aren’t hard to get, although benzoquinone purchases may be reported by some sellers.  As an exercise for students, try synthesizing PdCl2 from palladium metal with aqua regia.

After throwing in a magnetic stir bar, they stirred this mixture for at least an hour (preferably longer) to dissolve the benzoquinone.   At this point, the flask would be fitted with a reflux condenser and the 40 ml safrole slowly added over the course of an hour.   The addition funnel might be rinsed down with methanol to ensure he got all the safrole out.

Once all the safrole was added, the solution was kept heated to a gentle reflux with stirring for at least 8 hours.    After cooling, the solids were filtered off (and are a waste product).  The ketone produced by the reaction was extracted with DCM or another organic solvent and purified through vacuum distillation, giving perhaps 25 ml of a light yellow colored oil.  It’s been reported that the ketone will distill over at about 25 C higher than safrole at the same vacuum.

 3.  Assuming everything worked so far, the foolish, reckless chemist now has some precious ‘PMK’ ketone.  All that’s needed is to reductively aminate it.  After mixing the ketone with some methylamine freebase, a responsible (and well equipped) chemist would likely just use a hydride to reduce it to MDMA.  But for historical curiousity, let’s talk about Shulgin’s amalgam reduction, as interpreted by several generations of bees.

First, they would need to prepare a solution of methylamine freebase.  Since the amalgam reduction isn’t water sensitive, this can be done simply by dissolving 35 g methylamine hydrochloride crystals in 35 ml (or more) of distilled water, then slowly pouring in an ice-cold solution of 20 g NaOH in 60 ml of water.  This reaction is very exothermic and must be done slowly with an ice water bath to cool the solution.   Some methylamine will escape the solution, which smells very bad (a bit like rotten fish) and isn’t healthy to breath in.  The colder the solution is, the less offgassing.

Methylamine is, to use the legal terminalogy, suspicious as holy fuck.  It’s watched, regulated, and pretty much impossible for an individual to simply buy.

 In a 1,000 ml round bottom flask, place 12 g of pieces of heavy duty aluminum foil (the stuff used in the kitchen.)  Toss in a large stir bar.

Dissolve 100 mg of HgCl2 (mercury chloride) in 300 ml methanol.  Add this solution to the flask containing the aluminum.  This will start the reaction that forms the mercury-aluminum amalgam.   The foil will turn gray, then start to release bubbles of hydrogen gas.   At this point there’s no turning back; the amalgam will completely decompose over time.

HgCl2 (mercury chloride) is regulated and watched (being both suspicious and very, very poisonous.)  Mercury metal isn’t watched, but can be a bit hard to find.  Tiny amounts can be obtained by breaking open mercury tilt switches.  Mercury metal, like palladium, can be oxidized to a chloride salt with aqua regia.

Once the amalgam started to bubble (see video), they would add the methylamine solution and their 25 ml of PMK.   This is reported to be a moderately exothermic reaction; it may want to boil without adding any heat, but should be easily contained by the reflux condenser.   Once the reaction calms down, heat can be added to gently reflux the solution for another 4 hours.

Once the reaction is done, the reaction flask is flooded with 100 g of sodium hydroxide dissolved in 250 ml distilled water and the whole mess extracted with a non-polar solvent (such as a few hundred ml of toluene.)   The extraction solvent is washed with distilled water, then saturated salt solution, and finally dried with some (perhaps 5-10 g) dehydrated magnesium sulfate (epsom salts.)

If everything has worked out, the lucky chemist now has perhaps 15-20 g of MDMA freebase (an oil) dissolved in toluene or some other solvent.  The classic next step would be to bubble hydrogen chloride gas through the solvent to form MDMA hydrochloride (the crystals you see sold on the market.)  But HCl gas is dangerous and a bit inconvenient to work with, so Shulgin’s solvent crystalization seems like an easier way to go for the hobby scale chemist:

 The solvent is distilled off, leaving the crude MDMA freebase in the flask. It could be further purified by vacuum distillation, but that seems unnecessary.  This crude product is dissolved in 80 ml of dry isopropanol (isopropyl alcohol.)  Concentrated hydrochloric acid is added a drop at a time until the solution turns slightly acidic.   At this point, MDMA hydrochloride has formed.   To get it to crash out of solution, 150 ml of dry ether is added.   After letting the solution sit (and perhaps cool in the freezer), the crystals that formed could be filtered off and dried.  And that would be it; MDMA crystals.   Molly ahoy!   The pot of gold at the end of a long, difficult, legally (and otherwise) perilous road.

Assuming the cook has gotten all of the reactions to work correctly, of course.   In the organic chem lab, there’s no promise of success.

 I hope, dear reader, that you’ll find all this interesting and perhaps inspiring for some academic or other legal purpose.  I also hope you won’t try to set up a drug lab of your own.  The balance of risk to reward isn’t very good.   If you want drugs, buy them.  If you want a good income source, stay in college and get a decent professional job.

Understanding the DEA “listed chemical” system

There are three sections to the list of regulated precursors.  List 1 might be thought of as the ‘hot as hell’ list of suspicious precursors, like safrole and psuedoephedrine.  If you try to order any significant amount of these substances, there’s a good chance law enforcement will come for a visit (either by sniffing around quietly or outright kicking in your door, depending on what you tried to get and how much of it.)  It’s perfectly legal to buy and possess List 1 chemicals.   By itself (with no evidence that you plan to make illegal drugs) it’s not a crime to have a gallon of sassafras oil or some red phosphorus.   If you can find somebody willing to sell you either (within the US) you aren’t doing anything illegal by buying them.   Instead, the law applies to importers, manufacturers, and distributers.   It is illegal to produce, import, or sell List 1 chemicals without the proper government permits and documentation.  So, it’s legal for you to have sassafras oil (which is regulated as if it was pure safrole.)  However, you aren’t allowed to import or sell it or make your own without a permit.   The import restriction can trip people up.  It’s tempting to think that the easy way to get some sassafras oil would be to order some from a willing seller overseas and have it shipped to the US.  But in doing so you’ve broken the law if you don’t have the paperwork to import it legally.  Unless the seller has deliberately mis-labeled the oil as something unregulated, US Customs will notice your little purchase as it enters the US and pass on the information to the Drug Enforcement Administration.  And now you’re potentially back to getting your door kicked in.  Any time you mail-order a List 1 chemical the seller is supposed to report your purchase to the DEA.  Supposed to.  Whether that happens reliably on, say, eBay is another question, but hobbyist chemists should give it some serious thought before ordering a List 1 chemical.

List 2 is some more common chemicals that are regarded as ‘potentially suspicious’ but not blatantly precursors.   The restrictions are similar to List 1, with the big difference (from an end user’s standpoint) being that purchases don’t have to be reported to the DEA (but might be anyway if the seller thinks you’re suspicious.)

There’s also the Special Surveillance List, which in spite of it’s name isn’t nearly as restrictive as, say, List 1.  If your company makes or sells an item on this list, you are expected to report on your inventory, etc. and to make a reasonable effort to identify your customers.  So, if Bob’s Super Supplement Company wants to buy a pill press from you, the government expects you to make some effort to make sure that’s a real business/customer and not just a fake name with an address at an abandoned warehouse.  Do the guys selling pill presses on eBay (or the many other markets) actually do this?  Maybe, maybe not.  However well the system is being observed, there’s no shortage of drugs in America.

Just because a chemical isn’t on one of these lists doesn’t necessarily mean it can’t get you in a world of trouble.  For instance, PMK-glycidate isn’t regulated or officially watched in the US.  But it’s so damn suspicious that if you have those nice lads in China ship you a keg of it, you can be sure to get the undivided attention of law enforcement after it passes through US Customs.  One might be tempted to just ask the seller to mis-label the shipment as something innocent (and anybody selling PMK-glycidate knows damn well what it’s for and would no doubt be happy to oblige with a forged customs declaration.)  But…a package of powder coming through customs is always at risk of drawing attention, and it’s very easy to have something analyzed.

Although many chemicals are closely watched, glassware and most lab equipment is generally unwatched and unrestricted, although there are some local exceptions.  (Texas has particularly crazy laws on glassware.  Apparently nobody told them that most of their meth comes from Mexican super-labs.)  Ordering a chemistry glassware set (even from China) probably won’t attract any attention, but the truly paranoid young chemist might feel better having it shipped to a friend’s address just in case.

The takeaway point should be that getting the materials needed to run a drug lab can be a complicated, expensive process and a legal landmine.  Even very smart, very well financed criminal organizations get caught now and then.  For the average person (say, an enthusiastic young chem major) it can verge on a death wish.  Success (that is to say, a nice little load of gleaming MDMA crystals slowly drying on filter paper in your lab without attracting the attention of law enforcement) requires a lot of caution and/or a lot of luck.  And that’s without even getting into the dangers of exposure from selling drugs, should a profit be your motivation.

Small ‘hobbyist’ MDMA labs were once popular in the US (and some discussion sites like The Vespiary are still around) but with the growth of the darknet markets and plunging drug prices from established superlabs, it’s difficult to justify undertaking such a legally (and physically) dangerous project. Chemical reactions can produce large amounts of strong, suspicious smells and vapors, making a lab very difficult to hide.  The chemicals involved can be very toxic, corrosive or flameable.  Reactions can be violent, running out of control like a wildfire.  And law enforcement is always on the lookout for suspicious purchases of equipment and chemicals.  I would strongly advise any reader to not go down this particular path.

Still, if you’re interested in chemistry in general there are some great resources out there.   To see some neat ‘respectable’ chemistry in action, check out Nile Red.  If something a little more brilliantly ghetto is your thing, Chem Player has some great stuff.  Even mountain men like chemistry; genius geologist Cody’s Lab throws down some fascinating physics/physical chem work (like flushing a toilet with hundreds of pounds of mercury!)   For something more interactive, you might like the forums over at Science Madness (where openly discussing making illegal drugs is not allowed, but all sorts of other things are.)