Recover MDMA from bluebery juice

[blue.magic]

A friend of mine gave me a bottle with approx 100 ml blueberry juice, containing dissolved MDMA.HCl at 100 mg/ml concentration (supposedly).

The juice was not used at the party and it turned bad, possibly infected by mold, containing some unidentifiable chunks in it as well.

He asked me if I could clean it up and recover the MDMA.

I agreed to look into it as this is a great lab practice to improve my skills.

I never worked with this substance, but as far as my knowledge reaches, it should not be too hard to recover it provided everything in the fruit juice is already water soluble.

I am thinking about the following course of actions:

- filter the juice to remove any solids
- add base to convert MDMA.HCl to free base form (water-insoluble)
- separate dirty freebased MDMA
- wash freebased MDMA with solvents in which it is insoluble (water is one obvious option)
- convert back to salt form by precipitating from dry IPA and xylene via adding HCl dropwise
- recovert dirty crystals
- apply BOOFF tek for further cleanup (basically washing with acetone, IPA, recrystallization)

Of course, one concern would be creating some nasty impurities along the way as something from the juice may react with the base.

I will probably try a clean run with normal bluebery juice to see if some problem arise along the way and how the impurities look like.

 

[endlessness]

Not only weird byproducts from the juice, I'd be more worried about mycotoxins..

I cant comment much on the extraction method because im not sure if MDMA freebase precipitates when basing from a solution.. Does it? If not, you'll need to use some kind of non-polar, and not sure what its soluble in, im sure you can find it out though.

That being said, whatever method you go for, test it at the end... At least with TLC. Its simple enough and will give you a good idea whether there is something else in there.

Good luck!

 

[blue.magic]

Not only weird byproducts from the juice, I'd be more worried about mycotoxins..

I cant comment much on the extraction method because im not sure if MDMA freebase precipitates when basing from a solution.. Does it? If not, you'll need to use some kind of non-polar, and not sure what its soluble in, im sure you can find it out though.

That being said, whatever method you go for, test it at the end... At least with TLC. Its simple enough and will give you a good idea whether there is something else in there.

Good luck!

Thanks. Yes mycotoxins are one of my worries. I inspected the bottle and it's definitely common mold floating in it. I thought about boiling the solution prior to filtering, but the toxins may survive the boil.

I've read on some forum that freebase MDMA is water-insoluble, I think it forms an oil which can be thus separated in a sep. funnel.

For backsalting though, one has to use dry xylene and dry IPrOH and the MDMA oil probably must also be dry - this can be another issue. MDMA oil might be impossible to dry and MDMA.HCl won't dry easily either.

Yes I will order some TLC equipment. Fortunately, it's not that expensive from the local lab supply provider. This seems to be a long term project :d

 

[Mindlusion]

Yes the freebase is an oil, but you won't be able to recover less than 100mg of it in a sep funnel.

Your best bet is to dilute the juice, wash with a non-polar, basify and extract.

Dry the extracts over MgSO4, then precipitate the HCl by adding dry HCl dissolved in IPA dropwise, as you would with FASA. You might also try FASA, it might form good crystals too. Sulfates don't crystallize well for this stuff.

To make the HCl solution, you really need to bubble HCl. You might get away with adding some conc aqueous HCl to IPA, maybe 10mLs for 100mLs IPA, and then adding lots of MgSO4 to soak up the water. It won't be completely dry, but it can work. If there is too much water, you will lose yield or crystallization will fail. If you have FASA on hand, id try that first.

---

Good for practice sure, can't recommend consuming it though. Extraction should remove the nasties, its unlikely mycotoxins even if they were there would be transferred over. However, it could. I wouldn't risk it over a few milligrams.

 

[Elrik]

...I wouldn't risk it over a few milligrams.

I misread it at first glance, as well.
Blue is attempting to recover 10000 mg! That would last me multiple lifetimes :lol:
Among other ways, mycotoxins can be destroyed with base [Link] so an isolation using lye and xylene should detoxify it and mycotoxins generally wouldnt be xylene/toluene soluble in a basic environment either.

If you have not done so already, to prevent further damage label it 'POISON' and freeze it until you are ready to process it.

 

[blue.magic]

...I wouldn't risk it over a few milligrams.

I misread it at first glance, as well.
Blue is attempting to recover 10000 mg! That would last me multiple lifetimes :lol:
Among other ways, mycotoxins can be destroyed with base [Link] so an isolation using lye and xylene should detoxify it and mycotoxins generally wouldnt be xylene/toluene soluble in a basic environment either.

If you have not done so already, to prevent further damage label it 'POISON' and freeze it until you are ready to process it.

Yeah it's a lot. The guy makes healing "meditation" retreats for 100+ people, so it's not that much if you consider that

The solution was filtered and transferred to a reagent bottle labeled "MDMA JUICE - DIRTY, approx. 100 mg/ml" - I store this with poisons in a secure cabinet.

Okay so the new protocol would be:

- dilute the juice with dH2O
- base with lye (desired pH? or just enough for basic solution? ... I will try to look it up)
- extract with dry xylene
- precipitate with dry HCl/IPA solution

I have dry IPA (over CaCl2), originally 99.5%. Also dry acetone (over CaCl2). Not sure if MgSO4 would make a difference in this case as long as both solvents are dry.

Unfortunately, I don't have gaseous HCl. I have only 35% aq. HCl, reagent grade.

I've consulted "BrightStar's MDMA Synthesis" - he used 31.45% muriatic acid for pools (not ideal but seems to work). In the crystallization step, the wet HCl is added dropwise to dry xylene/IPA solution while stirring until pH reaches 5-5 (barely acidic). Then the solution is distilled under vacuum and constant stirring, until crystals appear. The solution is filtered, crystals recovered and the filtrate is left to evaporate to yield more crystals.

Now I am not sure how he measures pH in alcohol, never knew this is possible, but maybe from the little water there is brought in by the muriatic acid.

 

[downwardsfromzero]

Your best bet is to dilute the juice, wash with a non-polar, basify and extract.

I second that.

If you have not done so already, to prevent further damage label it 'POISON' and freeze it until you are ready to process it.

Also sound advice.

Among other ways, mycotoxins can be destroyed with base

Base will destroy reactive electrophiles quite nicely, as well as peptides.

(In a hurry, would post better info otherwise!)

 

[Jagube]

Any idea how high the pH has to be to destroy the mycotoxins?

It's good to know that if you leave your unreduced Aya brew for too long and it goes bad you can still easily retrieve your alks.

 

[blue.magic]

Okay so here is the stuff I was going to deal with:

I filtered the juice through paper filter but two days later, more clumps appeared so I filtered again using Celite and proceeded with extraction:

Approx. 150 ml of filtered juice loaded in 1l separatory funnel:

In the first lab session, I diluted the juice to approx. 500 ml, added approx. 50 ml of 50% NaOH solution (i.e. 25 g NaOH total). I have added the base in small amounts observing clouding but soon no further clouding appeared and the solution stayed white-ish and opaque.

I did three pulls with 75 ml of xylene and three pulls with 50 ml of DCM. The reason for using DCM is that I knew from one forum that DCM should pull MDMA freebase from the basic aqueous solution, so I used it just to be sure I get everything out.

The opaque solution got more transparent after the xylene pulls, which gave me confidence that something - hopefully MDMA freebase - is pulled by the solvent. It got even clearer after the DCM pulls.

Here are the intermediates: exhausted juice, combined xylene pulls (with some emulsion in it) and combined DCM pulls (no emulsion since I ran the combined pulls through 250 ml separatory funnel:

In the second session, I distilled off the DCM using water bath. Unfortunately, I was not able to distill absolutely everything since DCM wouldn't come over distillation head even at 90 °C. What was left was a yellowish oily liquid, which can be just something from the juice or MDMA oil or both.

While distilling the DCM, I prepared dry IPA and dried the xylene pulls (both with magnesium sulfate). This also removed the emulsion from xylene:

I plan to combine the DCM and xylene extracts and cover it with dry IPA. Then add aqueous HCl drop-wise until measuring acidic pH (5-6) in the now wet alcohol.

The solvent mix should be distilled at slightly over 100 °C (just enough to remove water and DCM in my case) until crystals appear, then the solution is filtered and the rest of it is left to evaporate to get the rest. Finally, the wet MDMA paste is washed with anhydrous acetone few times. This will suck up the residual water, impurities and should leave reasonably pure and hopefully consumable MDMA.HCl crystals.

Of course, it is possible to bubble dry HCl gas through the alcohol instead. I found one simple setup for this and one more elaborate. I never did this and I don't have a washing bottle nor a flow hood to deal with HCl gas, so I will stick with the acid titration.

 

[Mindlusion]

You should have washed the diluted juice with the DCM before adding the base, to avoid extracting anything from the juice.

Celite was a good idea.

Using aqueous acid should work fine for your purposes, but I recommend that you dilute the muriatic acid with IPA, and then add that solution dropwise to the xylene. Use some anhydrous MgSO4 too if you have it to at least remove some of the water.

Distilling out the DCM, water, and IPA at the end is also definitely a good idea, DCM dissolves HCl salts well as well as IPA. Xylene forms an azeotrope with water it should do a good job at removing the water. Use a water/steam bath to heat preferably with stirring.

 

[blue.magic]

You should have washed the diluted juice with the DCM before adding the base, to avoid extracting anything from the juice.

Yes I washed the juice three times with toluene prior to extraction. I forgot to mention that.

I avoided DCM at this point since I've read it solvates MDMA.HCl as well as free base.

Distilling out the DCM, water, and IPA at the end is also definitely a good idea, DCM dissolves HCl salts well as well as IPA. Xylene forms an azeotrope with water it should do a good job at removing the water. Use a water/steam bath to heat preferably with stirring.

Thanks for the HCl in IPA idea. Yes I made lots of anhydrous MgSO4, so I will prepare the acid solution.

I found one reference showing p-xylene forms azeotrope with water, b.p. about 365.1 K (few degrees below b.p. of water). I haven't found entries for other xylenes in azeotropic tables. I will see how it goes temperature-wise as I will can add thermometer to the RBF distillation flask. I am afraid higher temperature would be needed to drive off enough solvents for crystals to appear, but who knows...

I think I will also evaporate as much DCM as possible from the oil before adding the oil to xylene as it dissolves MDMA.HCl as you noted. It could be distilled off but there is no reason to further contaminate xylene in the receiving flask even though the two solvents are immiscible.

 

[leratiomyces]

Hi blue magic.
You have many options available to you as already pointed out by the other guys.

Once you have your mdma freebase oil, free of solvent, one of the simplest methods to convert to the hcl salt would be the method that shulgin commonly used,

Erowid Online Books : "PIHKAL" - #109 MDMA

Entry #109 MDMA from PiHKAL by Alexander & Ann Shulgin.

erowid.org

Isopropanol, ether and conc. hcl.
Doesn't get much easier, although a little bit of product is lost as it remains dissolved in the solvent (due to the bit of water present).

 

[Mindlusion]

I avoided DCM at this point since I've read it solvates MDMA.HCl as well as free base.


I found one reference showing p-xylene forms azeotrope with water, b.p. about 365.1 K (few degrees below b.p. of water). I haven't found entries for other xylenes in azeotropic tables. I will see how it goes temperature-wise as I will can add thermometer to the RBF distillation flask. I am afraid higher temperature would be needed to drive off enough solvents for crystals to appear, but who knows...

Yes it does solvate salts, but it's still ok to wash with DCM since DCM won't extract the salts out of the aqueous, the intermolecular bonds with water are much much stronger than with DCM. Either way good to know you washed it.

The azeotrope is probably not listed because it's so close to 100C. It should be no problem to remove the water, xylene being high boiling. I don't think you will have any problem getting crystals. It's only important to remove the water, IPA, and DCM. Everything else is non polar enough. Shulgin does a quick and dirty procedure that sometimes works, but loses a lot of yield. In my experience, it is always best to keep things as dry as possible. Even in anhydrous conditions, IPA can keep a lot of hcl product dissolved even in the excess of ether. Depending on the molecule.

 

[blue.magic]

I am oven-drying and flame-drying everything. It's quite a pain since the solvents need to be dried and filtered. I hope it will work in the end.

I prepared about 5% HCl in IPA solution and dried it over MgSO4 as well so hopefully this will help.

Unfortunately, the paper filters nor glass filter are not able to remove all the MgSO4 so I will probably leave it there. It's not too much and it's food grade anyway. Some will be probably removed by the last washing step. I am not patient enough to re-distill every solvent. Some time I have to make special bottles with pre-made dry solvents.

OK, going to distill off the xylene/IPA/DCM/H2O mix and see... I will post pictures then.

Hi blue magic.
You have many options available to you as already pointed out by the other guys.

Once you have your mdma freebase oil, free of solvent, one of the simplest methods to convert to the hcl salt would be the method that shulgin commonly used,

Erowid Online Books : "PIHKAL" - #109 MDMA

Entry #109 MDMA from PiHKAL by Alexander & Ann Shulgin.

erowid.org

Isopropanol, ether and conc. hcl.
Doesn't get much easier, although a little bit of product is lost as it remains dissolved in the solvent (due to the bit of water present).

Thanks. Yes I often read Shulgin's notes. He often uses less available solvents (e.g. diethyl ether) and it's outside my skills yet to prepare them myself.

Unfortunately the MDMA is dissolved in quite a lot of xylene and the only option to remove it without harming the compound is either vacuum distillation or backsalting. I can only do the latter option.

Having a rotavap, I would just remove all the solvent, get MDMA oil and it would make life much easier.

 

[Mindlusion]

Hi blue magic.
You have many options available to you as already pointed out by the other guys.

Once you have your mdma freebase oil, free of solvent, one of the simplest methods to convert to the hcl salt would be the method that shulgin commonly used,

Erowid Online Books : "PIHKAL" - #109 MDMA

Entry #109 MDMA from PiHKAL by Alexander & Ann Shulgin.

erowid.org

Isopropanol, ether and conc. hcl.
Doesn't get much easier, although a little bit of product is lost as it remains dissolved in the solvent (due to the bit of water present).

Thanks. Yes I often read Shulgin's notes. He often uses less available solvents (e.g. diethyl ether) and it's outside my skills yet to prepare them myself.

Unfortunately the MDMA is dissolved in quite a lot of xylene and the only option to remove it without harming the compound is either vacuum distillation or backsalting. I can only do the latter option.

Having a rotavap, I would just remove all the solvent, get MDMA oil and it would make life much easier.

You don't need to remove the xylene. You don't need the ether, they can be used interchangeably. The purpose of the ether is just to dilute the isopropanol so the hcl salts crystallize out. Ether is the choice solvent because its very volatile so its easily removed, and as well almost all salts are insoluble in it. Xylene works exactly the same in this case, and removing it is simple you can just wash with anhydrous acetone after filtration like you suggested. You could even use anhydrous acetone instead of ether.

That is why I say just distill to remove the DCM, isopropanol, and water. You will probably already have crystallization even with the DCM, isopropanol, and water present, but by removing them you can ensure complete crystallization. After you are finished you can put the xylene in the freezer overnight to ensure it further.

 

[blue.magic]

Thanks, Mindlusion, for the insights. This is very helpful for a non-chemist working with organic substances.

So I finally prepared the HCl/IPA solution (on the left) and the xylene/IPA solution (on the right). I have added the residue from DCM pulls and it readily dissolved in the xylene. If there was any water or DCM left, it must have dissolved since there was no bottom layer formed in the RBF:

I proceeded adding small amounts of acidic alcohol via a pipette while taking readings using lithmus paper:

At one point, I got impatient and added few drops of concentrated HCl since I felt like there was too little water present to get pH reading correctly and I already added a lot of the diluted acid with no effect.

It took few more drops and the solution stayed acidic. I found a good way to measure pH is to use the glass thermometer adapter - simply touch the glass end to the paper.

Now the solution also got the typical light amber colour:

One issue I found is the MgSO4 that fell to the bottom of RBF. I am thinking about filtering that is it might be hard to remove it later.

 

[Mindlusion]

That looks good, that is the same way I titrate the solution as well dabbing it to the pH papers. Also, The initial concentration I suggested for the IPA/HCl was very dilute, since I thought you were working with much less, so sorry about that.

Either way, no difference since now you can distill out the remaining DCM, IPA and water. And DCM is soluble in xylene hehe.

I would not attempt to to filter out the MgSO4 just yet, since the cloudiness is your mdma hcl salt, you will lose some in the filter, or if its small enough to go through, then it might clog filtration will be slow. The best way to remove that would be to collect your product, and purify it by simple re-crystallization, which should be done anyways, so no problem.

 

[blue.magic]

That looks good, that is the same way I titrate the solution as well dabbing it to the pH papers. Also, The initial concentration I suggested for the IPA/HCl was very dilute, since I thought you were working with much less, so sorry about that.

Either way, no difference since now you can distill out the remaining DCM, IPA and water. And DCM is soluble in xylene hehe.

Okay, no problem I calculated my dirty stoichiometry and came with something like 30 ml of the dilute solution or 4 ml of the concentrated HCl to salt the full 10 000 mg of MDMA (the expected original amount, but god knows how much was there). I've used something in that range so it feels good.

I think I filter it once more in dry flask just to feel good about that residual MgSO4 and let's start distilling (getting excited).

 

[blue.magic]

So I've set up a simple distillation and most solvent went off before 100 °C, so I assume this was DCM and IPA:

By the end of the distillation, the temperature raised dangerously close to the melting point of MDMA.HCl, about 140 °C, so I stopped the distillation as this would hurt the product. No crystals formed so I removed the heating mantle and discovered a viscous brown layer at the bottom of the flask:

I assume this is aqueous MDMA.HCl. Unfortunately, I haven't expected so much xylene to be left there and there is no way I can safely evaporate it (and I don't want to, it's not environmentally friendly).

So I've put the whole flask in an ice bath to crash any more MDMA from the xylene and probably leave it in the freezer overnight:

Now I would separate the layers and try to dry the xylene with acetone to possibly crash the remaining MDMA out of it.

The brown layer will be also washed with acetone to get crystals.

It seems I salvaged maybe gram of MDMA, which is very low yield, but better than nothing, considering I did this first time not knowing all the intricacies of amphetamine chemistry.

 

[Mindlusion]

The majority of your product is in that brown aqueous, that's fine. You can try to crash it out by adding acetone to that aqueous, or you can evaporate the water in a pyrex pan and then recrystallize it.