TEK Ethyl acetate approach [CIELO]

[Loveall]

Yeah could be faster in everclear not it dissolves. I would just wait for the water to evaporate for now.

And yeah, maybe the second jar just needs more time.

Edit: the second jar has more ethyl acetate (more diluted product) and was warm EA. Both go against xtalization, so it could take longer. It should xtalize eventually. More citric acid should help if nothing happens with time.

 

[Loveall]

"Cover paste with ethyl acetate, mix well for 60s, allow to rest for 120s and decant into quart jar through a coffee filter. Do not squeeze with the french press, its purpose is to only hold back the paste from falling into the filter and squeezing can push unwanted material into the extract. Repeat until quart jar is full (~5-6x)."

While reading this sentence I am thinking that it could be misunderstood.
For example when putting the paste like a lump of clay into a big round bowl and then fill with EA that could result in way to much EA. Maybe the text could suggest a more narrow jar and give advise to fill the jars floor so that it fills all the volume to the jar walls?

Maybe like this? :
"Make sure the paste is evenly stretched over the bottom of the jar without any bigger holes of air."

Do you know what I mean? Maybe I am overthinking...

Thanks for the feedback. I added the that covering the paste should be around 150g of ehtyl acetate in the TEK.

 

[Loveall]

Update on the microwave paste option as done in the Tek.

All as expected. 1.2% yield of white sparkly product with a trace of tan.

Used ethyl acetate is tan and clear, will reuse after a quick sodium carbonate wash.

All is working as expected and repeating.

My favorite path is the microwave paste and room temp 3 minute pulls. It's personal taste, but I like how easy it xtalizes (more robust to different plant material?) and that the solvent seems very reusable. Also the paste congeals a lot less over time. I think this is a more "all purpose path" (e.g. whole plant or new untested type of cactus).

The raw and direct non microwave path is great too. If there is no plan to reuse the solvent, and a non-fussy outer skin rich in alkaloids is being used, this path is less work.

I'm happy with the TEK and its options as it stands now after several iterations. I'm sure it can be improved, but the current revision is good enough for general consumption in my opinion. Feedback always welcome.

Cheers.

 

[grollum]

Thanks for the feedback. I added the that covering the paste should be around 150g of ehtyl acetate in the TEK.

perfect :thumb_up:

 

[Loveall]

There is a thread on mycotopia with some comments/questions about our process. I cannot get their site to work properly (validation email never gets to me). I'll try to answer here, I imagine other folks will have similar questions.

I could be and often am wrong but it seems that if mescaline citrate just fell out of ethyl acetate by dumping citric acid into a solution somebody would have mentioned it before now.

I don't know why it hasn't been mentioned before (or at least why we haven't found mention of it). There is a related example with acetone, citric acid, and bufotenine and I believe that mostly unknow until fairly recently. Perhaps it is because standard LLE A/B works on general, and these specific shortcut plant-dependent TEKs take a lot of trial and error to find (it's 95% errors for me ). For example this same process is not working well for DMT from root bark. It makes sense for a research to just apply a more general approach and not spin their wheels optimizing for one compound in one type of plant. I could be wrong though, this is all speculation.

What raises my suspicion is how detailed the chemistry and theory is and how sparse the actual process is.

I received the same feedback here. Process details have been added in response. It was my mistake to not include those, I thought the TEK would be easier to read if it was less "wordy", moving the details elsewhere for those interested, but I was wrong based on people's feedback.

The ethyl acetate, could it be subbed with other known solvents or is there a special need for this solvent in this experiment?

Not sure this is a very hard question to answer, but we can say a few things. Tried acetone and it did not work well. Also tried IPA and several other solvent/salt combinations. Could be because it is infinitely soluble with water and a lot of plant stuff comes through interfering with xtalization. Limonene and Xylene would pull mescaline, but cannot be salted directly with citric acid since it is not soluble. Limonene + FASI have worked for some in the past and that process is similar to this one, but in my experience and biased opinion CIELO is less work and more robust (main issue I found with limonene + FASI was product being unfilterable/undefeatable wisp. MEK was tested briefly, but it absorbs more water than ethyl acetate and focus of experiments shifter towards ethyl acetate (MEK may also work ?).

Keep in mind that the citrate salt is almost 2x heavier per molecule than the hydrochloride. A 2% yield of the citrate salt mathematically converts to an approximately 1.2% yield of the hydrochloride.

I disagree with this. Citric acid has 3 protons with pKa < mescaline's pKa, so three mescaline molecules should react with one molecule of citric acid. This makes it 90% as strong as mescaline HCl and just as strong as mescaline sulfate dihydrate. Note that this is an assumption and we could be wrong, but the bioassay matches this for that it's worth
We are also assuming that mescaline citrate is anhydrous and that could be wrong (however, no significant weight change was noted in an oven dry test).

Edit: Actually, the citric acid may not fully react. If the dihydrate salt precipitates immediately then we could have a product that is 62% less potent by weight.

**

There where questions about other acids. Shroombee tested malic acid and it did not work. Sulfuric sort of worked, but a separate layer forms, so we have been avoiding acids that carry water. There were also questions/concerns about stronger non-organic acids (e.g. HCl) breaking down ehtyl acetate - it is relatively easy to hydrolyze into ethanol and acetic acid. Sticking to citric acid seems to work well.

There were also some comments about the motivation behind the TEK. It is harm reduction/health maximization. Accurate dosing is part of the setting and important for responsible use and a pure product provides that. Also, use of toxic/more "dangerous" chemicals is minimized. Reuse of ethyl acetate is emphasized to make the TEK green. Scientists and indigenous people agree that use of psychedelics can enhance feelings of connectedness to nature (scientists add that psychedelics may improve brain health through neuroplasticity). These effects in turn could help people make better choices for themselves and for the future of the planet. Developing another process to isolate clean mescaline is an attempt to add a small grain of sand in that general direction.

Cheers and happy to try to answer any other relevant questions.

 

[shroombee]

Keep in mind that the citrate salt is almost 2x heavier per molecule than the hydrochloride. A 2% yield of the citrate salt mathematically converts to an approximately 1.2% yield of the hydrochloride.

I disagree with this. Citric acid has 3 protons with pKa < mescaline's pKa, so three mescaline molecules should react with one molecule of citric acid. This makes it 90% as strong as mescaline HCl and just as strong as mescaline sulfate dihydrate. Note that this is an assumption and we could be wrong, but the bioassay matches this for that it's worth
We are also assuming that mescaline citrate is anhydrous and that could be wrong (however, no significant weight change was noted in an oven dry test)

Can we test this? What's a process for converting the mescaline citrate to something like mescaline HCl? And then we'd need to get rid of the excess citric acid.

Edit: How about dissolve the mescaline citrate in water, add HCl to convert mescaline citrate to mescaline HCl, evaporate to yield mescaline HCl with excess citric acid. Wash with ethyl acetate to remove citric acid. This process assumes mescaline HCl is not soluble in ethyl acetate.

 

[merkin]

Reading that mycotopia thread was amusing. I can imagine your frustration at not being able to respond Loveall. What amuses me is how quickly it was ‘cynically’ dismissed as to good to be true. In deep contrast to this thread most comments are opinions on each other’s posts and not your tek or the process, no one actually tried it yet but they happy to weigh in on the topic. I’m sure as soon as someone actually tries it the whole thread will take a turn. The issues and experiments are so well documented in this thread I didn’t think for a moment it was ‘too good to be true’ in fact my reaction was the opposite - Ive gotta get that powder and try this for myself!

Same thing for me with sign up email, never received.

Couldn’t resist doing more this weekend and got the same good results. Next going to try the microwave version. Dissolved half of last yield in water to evaporate. Damn that takes a while! Really keen for crystals now, the powder seems too easy lol.

Rinsed all the dry glassware and final filter with some dh2O and drank. Super nice morning with slight mdma back jaw feeling. Very nice vibe tho.

 

[Loveall]

Keep in mind that the citrate salt is almost 2x heavier per molecule than the hydrochloride. A 2% yield of the citrate salt mathematically converts to an approximately 1.2% yield of the hydrochloride.

I disagree with this. Citric acid has 3 protons with pKa < mescaline's pKa, so there mescaline molecules should react with one molecule of citric acid. This makes it 90% as strong as mescaline HCl and just as strong as mescaline sulfate dihydrate. Note that this is an assumption and we could be wrong, but the bioassay matches this for that it's worth
We are also assuming that mescaline citrate is anhydrous and that could be wrong (however, no significant weight change was noted in an oven dry test)

Can we test this? What's a process for converting the mescaline citrate to something like mescaline HCl? And then we'd need to get rid of the excess citric acid.

* I have a typo up there, should be "three molecules" (not "there molecules" ).

I guess you can dissolve mescaline citrate in water, base, and do an A/B extraction using HCl and evaporate. Want HCl to be dilute (a few drops of 35% HCl in water) and titrate the salting down to pH7-6.

 

[Loveall]

Reading that mycotopia thread was amusing. I can imagine your frustration at not being able to respond Loveall. What amuses me is how quickly it was ‘cynically’ dismissed as to good to be true. In deep contrast to this thread most comments are opinions on each other’s posts and not your tek or the process, no one actually tried it yet but they happy to weigh in on the topic. I’m sure as soon as someone actually tries it the whole thread will take a turn. The issues and experiments are so well documented in this thread I didn’t think for a moment it was ‘too good to be true’ in fact my reaction was the opposite - Ive gotta get that powder and try this for myself!

Same thing for me with sign up email, never received.

Couldn’t resist doing more this weekend and got the same good results. Next going to try the microwave version. Dissolved half of last yield in water to evaporate. Damn that takes a while! Really keen for crystals now, the powder seems too easy lol.

Rinsed all the dry glassware and final filter with some dh2O and drank. Super nice morning with slight mdma back jaw feeling. Very nice vibe tho.

Good luck. I think the cold extraction can also help the xtals grow. Also, letting citric acid diffuse slowly (not actively dissolving it). Use fresh ethyl acetate (you may already be planning this). We don't have the cold extraction documented in the TEK, but it can help grow bigger xtals. Essentially you put the ethyl acetate in the freezer and the paste in the fridge for a day before extracting and pulls are shorter to avoid room temp warming with 60s of stirring (rest of the steps can stay the same). The extract color will be very light. You can still try to grow xtals without the cold extraction, it should work, they will just be smaller.

 

[Loveall]

Edit: How about dissolve the mescaline citrate in water, add HCl to convert mescaline citrate to mescaline HCl, evaporate to yield mescaline HCl with excess citric acid. Wash with ethyl acetate to remove citric acid. This process assumes mescaline HCl is not soluble in ethyl acetate.

I think this could result in a mix of Mescaline HCl and different citrate salts (dihydrogen citrate, hydrogen citrate, and citrate), but not sure.

 

[Loveall]

Keep in mind that the citrate salt is almost 2x heavier per molecule than the hydrochloride. A 2% yield of the citrate salt mathematically converts to an approximately 1.2% yield of the hydrochloride.

I disagree with this. Citric acid has 3 protons with pKa < mescaline's pKa, so there mescaline molecules should react with one molecule of citric acid. This makes it 90% as strong as mescaline HCl and just as strong as mescaline sulfate dihydrate. Note that this is an assumption and we could be wrong, but the bioassay matches this for that it's worth
We are also assuming that mescaline citrate is anhydrous and that could be wrong (however, no significant weight change was noted in an oven dry test)

Can we test this? What's a process for converting the mescaline citrate to something like mescaline HCl? And then we'd need to get rid of the excess citric acid.

Edit: How about dissolve the mescaline citrate in water, add HCl to convert mescaline citrate to mescaline HCl, evaporate to yield mescaline HCl with excess citric acid. Wash with ethyl acetate to remove citric acid. This process assumes mescaline HCl is not soluble in ethyl acetate.

Maybe we could test this with a pH check of the product on water (e.g. 1g in 20ml). Mescaline citrate, (MesH)3Cit, should be closest to neutral, mescaline Hydrogen Citrate, (MesH)2HCit, would be more acidic, and finally mescaline dihydrogen citrate, (MesH)H2Cit, would be the most acidic. The product would have need to be washed well to remove any residual citric acid, H3Cit, for this test to be valid. Also, a freshly calibrated pH meter should be used.

For reference the pKa values of citric acid are 3.1, 4.7, and 6.4. I think Mes3Cit should have a pH ~ 7.

Edit: The situation is similar to the sodium citrate salts. Na3Cit is slightly basic (pH 7.5-9), Na2HCit is slightly acidic (pH ~ 4.5-5.5), and NaH2Cit is the most acidic (pH ~ 3.5-3.8 ). Since Mescaline is not a strong base, mescaline salts will have different pH values (slightly lower I believe), but should be of this order. Bottom line: if our product is not very acidic and near neutral (pH > 6), it is likely Mes3Cit.

Edit2: I've been assuming that mescaline and citric acid react completely im ethyl acetate to form Mes3Cit. One could ask, how do me know Mes2HCit and MesH2Cit don't also form in the crystallization chaos? I simply think the reaction goes to completeness in ethyl acetate and all the protonic sites of citric acid become occupied by mescaline. But I'm not sure that is really now it works. If Mes2HCit and MesH2Cit crash on their own, and there is a lot of citric acid and not a lot of mescaline, it could be possible that these other salts form (?)

Edit3: Grams of product with 1 milimole of mescaline
- Mescaline HCl: 247
- Mescaline Sulfate Dihydrate: 278mg (90% strength vs Mescaline HCl).
- Mescaline Citrate (MesH)3Cit: 275mg (90% strength vs Mescaline HCl).
- Mescaline Hydrogen Citrate (MesH)2HCit: 307mg (80% strength vs Mescaline HCl).
- Mescaline Dihydrogen Citrate (MesH)H2Cit: 403mg (60% strength vs Mescaline HCl).

 

[Loveall]

Product pH check is coming in at 3.55 (750mg dissolved in 15ml of warm water). This could mean (1) I did not wash out all the citric acid or some other contaminant that can affect pH (but I think I did need to double check), or (2) that the dihydrogen salt is forming: (MesH)H2Cit, or (3), I'm missing something in the logic for the the pH expectations for the different mescaline citrate salt forms, or (4) something else is going on that I'm not aware of.


If it is indeed we are forming the dihydrogen salt, it would be 68% as potent by weight as 3(MesH)Cit which I had been assuming (because of the large pKa differences).


I think this remains an open question at the time. All I can say is that the pH test was not consistent with (MesH)3Cit. Can't draw a strong conclusion though because there are other possible explanations beyond the salt form. Perhaps converting to HCl and back to citrate would be a more robust check (but more work).


This salt was made with with both the "drop acid" and the mechanical shaking methods (I mixed both products together for storage). It may be worth checking salts from the magnetic stirring method and acid drop method separately. I think it should be the same result, buy may be worth checking to make sure.

In other news, there have been some revisions to the TEK from shroombee and me (thanks shroombee):

- FAQ section added
- Cold extraction option added
- Material section expanded
- More references added (including a mycotopia result for whole bridgessi which gave a tacky active potent product).

 

[downwardsfromzero]

For me, Occam's razor says here that if mesc.H2citrate is insoluble in EA it will simply crash out. There's a simplicity in the bimolecular reaction. It would be sensible to try washing the product in warm, dry EA on the vacuum pump a couple of times and then test the pH again.

(3), I'm missing something in the logic for the the pH expectations for the different mescaline citrate salt forms

Mescaline is a weaker base than sodium hydroxide so the dimesc.Hcitrate could be more acidic than your estimate. Titrating weak acids with weak bases can get pretty fuzzy (indistinct).

One way to be absolutely sure about this is to prepare a standard solution of mescaline freebase in EA and allow it to react, in three separate aliquots, with measured equivalents of citric acid corresponding to the three possible stoichiometries. Evaporation of the solvent is then followed by washing of the (weighed) solids with fresh solvent as mentioned above.

It could be that the dissociation equilibrium of the higher mescaline citrates will lead to freebase mescaline redissolving in the solvent wash, which can be then be crashed with further (excess) citric acid and all the weights compared. This is a fair bit of work, so if anyone thinks of a simpler approach to the question of mescaline citrate stoichiometry - well, hats off to them, I say!

One more thing - we might also find a more complicated stoichiometry like 2:3 ("sesquicitrate"), etc.

 

[Loveall]

Yep, I agree that mescaline salts would be more acidic than the sodium salts because of they are the conjugate acid of a weaker base, so the hydrogen salt could be giving a pH of 3.55 instead of the dihydrogen.

I'll wash the product again in ethyl acetate. Will make sure the ethyl acetate wash is neutral on pH paper and then check the pH of the dried product again.

Could it be possible for the following to happen during the washes with fresh ethyl acetate (?):

2(MesH)H2Cit -> (MesH)2HCit + H3Cit
3(MesH)2HCit -> 2(MesH)3Cit + H3Cit

Or combined into, 6(MesH)H2Cit -> 2(MesH)3Cit + 4H3Cit

Also, if there is a lot of excess citric acid (as is done when plant matter is present) would that push these reactions to the left towards an equilibrium? I don't know much about polyvalent salt formation in solvents that have a few % of water

 

[shroombee]

In other news, there have been some revisions to the TEK from shroombee and me (thanks shroombee)

You're welcome. Glad I could finally find some time to contribute to the writeup.

Question on the solvent reuse section: After washing solvent and removing the water layer, should we add a 24 hour freezer step followed by removal of ice crystals? Seems that would be a best practice, especially since ice crystal removal is recommended if reusing solvent with cold extraction.

 

[Loveall]

In other news, there have been some revisions to the TEK from shroombee and me (thanks shroombee)

You're welcome. Glad I could finally find some time to contribute to the writeup.

Question on the solvent reuse section: After washing solvent and removing the water layer, should we add a 24 hour freezer step followed by removal of ice crystals? Seems that would be a best practice, especially since ice crystal removal is recommended if reusing solvent with cold extraction.

Good question. For cold extraction yeah it makes sense to go through the freeze and ice removal. If pulling at room temp it doesn't seem to matter (the wet paste will give warm acetate a little bit of water anyway).

I made a small edit to the reuse section.

 

[Loveall]

I mixed the product in fresh ethyl acetate, the pH paper is neutral. I'm going to leave it stirring over night to see if that slowly changes but I don't think it will.

The two pH measurements together, neutral in ethyl acetate but acidic in water, could mean that we have the less potent hydrogen salt(s) precipitating. That could drop the strength by weight relative to Mescaline HCl down to 81% (for mescaline hydrogen citrate) or even 62% (for mescaline dihydrogen citrate). Based on naive pKa's I had been assuming that the mescaline citrate salt was forming (which would have been 90% as strong as mescaline HCl). All these numbers assume no hydrates form.

Will keep on doing tests and will ask around see what Mindlusion or Benz think. The conversion to HCl and back to mescaline citrate could confirm that we do have a (di)hydrogen salt.

I've updated the TEK to let people know that there is a potency range and that we are not sure of the actual salt mescaline/citrate ratio.

Bioassays were pretty strong. Was comparing to mescaline sulfate and they seemed similar. However this is subjective and mescaline seems kind/gentle for a pretty big range of doses.

 

[downwardsfromzero]

Could it be possible for the following to happen during the washes with fresh ethyl acetate (?):

2(MesH)H2Cit -> (MesH)2HCit + H3Cit
3(MesH)2HCit -> 2(MesH)3Cit + H3Cit

I would say the equilibrium is likely to lie to the left, or we could consider the other equation:
(MesH)3Cit → (MesH)H2Cit + 2Mes where freebase mescaline would go into the EA.

Or combined into, 6(MesH)H2Cit -> 2(MesH)3Cit + 4H3Cit

This factors out to 3(MesH)2HCit -> (MesH)3Cit + 2H3Cit

 

[Loveall]

Could it be possible for the following to happen during the washes with fresh ethyl acetate (?):

2(MesH)H2Cit -> (MesH)2HCit + H3Cit
3(MesH)2HCit -> 2(MesH)3Cit + H3Cit

I would say the equilibrium is likely to lie to the left, or we could consider the other equation:
(MesH)3Cit → (MesH)H2Cit + 2Mes where freebase mescaline would go into the EA.

Or combined into, 6(MesH)H2Cit -> 2(MesH)3Cit + 4H3Cit

This factors out to 3(MesH)2HCit -> (MesH)3Cit + 2H3Cit

Then we would see the pH paper turning green I guess.

Update: There was no pH change in fresh EA after 12 hours of magnetic stirring. Whatever salt is forming doesn't change and is inert in EA once it crashes, which makes sense.

The water pH in water as mentioned before is 3.55, so it is likely the product is a hydrogen salt, 62% to 81% less potent than MescalineHCl depending on if it is the dihydrogen or hydrogen form respectively (the old naive assumption was that we had mescaline citrate fully reacted which would have been 90% as strong as MescalineHCl).

A salt conversion to HCl with an A/B workup should give an answer. However that seems like a lot work now

I'll try to find a salt that only has one option (monomescaline). Lactate, Ascorbate and Benzoic should all carry one mescaline molecule (since only one proton is available or only one proton has pKa < mescaline's pKa). Gonna try to see if any of these salts xtalize well from ethyl acetate. If any work, split am extract and salt one side with citric and the other side with the monomescaline salt. Assuming yields are the same, the mass ratio would tell us the form of the mescaline (X-hydrogen) salt (with X between 0 and 3).

One thing we have not tried is to dry the extract chemichally and salt with 35% HCl. The water should be absorbed by the dry ethyl acetate and HCl xtals may crash. Concern is any free HCl breaking down the solvent.

 

[Loveall]

Edit: How about dissolve the mescaline citrate in water, add HCl to convert mescaline citrate to mescaline HCl, evaporate to yield mescaline HCl with excess citric acid. Wash with ethyl acetate to remove citric acid. This process assumes mescaline HCl is not soluble in ethyl acetate.

I think this could result in a mix of Mescaline HCl and different citrate salts (dihydrogen citrate, hydrogen citrate, and citrate), but not sure.

Thinking about it more, this may work. Concentrated HCl should be strong enough to pronate all the citric acid (once pH is 1.1, citric acid would be 99% fully pronated). That could dry to MescalineHCl + CitricAcid. However, if HCl evaporates too early and the pH rises then the citrate salts could start forming.

I just don't know so it may be worth trying out.