TEK Ethyl acetate approach [CIELO]

[downwardsfromzero]

Hmm that sort of reminds me of how sodium diacetate is a thing, where two acetate ions share one proton. So, even a singly deprotonated citric molecule could, by analogy, attract another neutral citric molecule. The hydroxy group could be another point of stickiness too. Just some molecular-level ramblings...

 

[Loveall]

Well, TLC I do not have here now, I am about to buy to also throw that doubt, the % of yield was 2% (200g cactus powder: 4g oil)

Regarding the yield in terms of oil and calculating back on the original material I just want to shortly chip in and throw in something prior to a detailed post, I made some analysis on various possible results of the CIELO tek and also included the goo, sadly cannot finish all samples due to some technical problems :twisted: :twisted: :roll:

So while the full post will come hopefully as soon as possible I have some info about a possible goo formation, which will of course not be similar in everybody's case as this might differ from situation / person / cacti / extraction conditions.

But it seems like the typical goo is not just mescaline citrate, even though it might solidify over time. This indeed happens due to the slow removal of water due to evaporation. But the goo most certainly consists also of excess citric acid and also water. Even if you completely solidify your goo, it will still contain a lot of water. Data coming soon, but just to throw in here, you will probably only expect your goo to be 20-50 % mescaline citrate.

Quickly speaking I think getting goo is a result of excess water, which might still be present (in too large quantities) in some cases after fridge decant and not by too low amounts of CA. This will make all the Mescaline crystals move out into that excess water at a bottom layer and as citric acid just loves water more than anything, citric acid from the EA will also partially migrate inside. This salt-water-mix still contains too much water to solidify, as both Mescaline Citrate and CA are easily dissolved by minimal water amounts, so the stuff keeps free-flowing, yet at high viscosity. As you will not be able to tell the ratio, even a water-free goo would be difficoult to assume in terms of potency. But even a 100 % evaporated goo (which will turn 100 % solid) will contain quite a lot of water (probably because of the citric acid). So without doing any recrystallization this goo is probably impossible to judge in terms of potency. Waiting since quite some time to finish this and give some more visual data, but hope to have it soon and then it might be more clear.

Would isolating the goo, adding freh (dry) EA to it and waiting move the water and citric citric acid out of the salt?

 

[_Trip_]

Ethanol had been reported to work very well by several members now.

 

[antichode]

On a recent extraction I thought I would try Endlessness approach of using CASEA. My acid must be anhydrous as it would not dissolve even 10g into 250ml of fresh EA (even after four days) So I added a small amount of water over a few days to dissolve it all. I ended up using 4ml of water.

When I used this to salt a fresh extraction it clouded up vigorously but within a few hours I could tell that the crystallisation was different, strands of crystals stuck to the bottom of the jar and formed with gooey streaks up the sides. After 72 hours there were the usual well
Formed crystals so I filtered everything but there was a layer of sticky crystals in the bottom of the flask and they were impossible to pickup with fresh EA. I had to pick them all up with water and evaporate that. This left behind almost the same thing. A sticky layer with crystals through it. In the end I used a small amount of water to pick it all up and bombed it with IPA which precipitated everything straight away. Adding water to the mix early on certainly made a mess of things.

It amazes me that some seemingly very finicky variables are so wonderfully taken care of with a fridge rest and even the amount of citric doesn’t matter as it dissolves in solvent with naturally the right amount of water and freebase molecules that the extraction creates. The great magnet was spinning in your direction when you put this together Loveall.

 

[Loveall]

On a recent extraction I thought I would try Endlessness approach of using CASEA. My acid must be anhydrous as it would not dissolve even 10g into 250ml of fresh EA (even after four days) So I added a small amount of water over a few days to dissolve it all. I ended up using 4ml of water.

When I used this to salt a fresh extraction it clouded up vigorously but within a few hours I could tell that the crystallisation was different, strands of crystals stuck to the bottom of the jar and formed with gooey streaks up the sides. After 72 hours there were the usual well
Formed crystals so I filtered everything but there was a layer of sticky crystals in the bottom of the flask and they were impossible to pickup with fresh EA. I had to pick them all up with water and evaporate that. This left behind almost the same thing. A sticky layer with crystals through it. In the end I used a small amount of water to pick it all up and bombed it with IPA which precipitated everything straight away. Adding water to the mix early on certainly made a mess of things.

It amazes me that some seemingly very finicky variables are so wonderfully taken care of with a fridge rest and even the amount of citric doesn’t matter as it dissolves in solvent with naturally the right amount of water and freebase molecules that the extraction creates. The great magnet was spinning in your direction when you put this together Loveall.

Thank you. There was A LOT of trial and error and collaboration from the community. Many ideas failed before we found this specialized system for mescaline, which was built upon previous work by Someblack guy with ethyl acetate and the the lime paste tek folks.

 

[Loveall]

Ethanol had been reported to work very well by several members now.

Thanks. I added some info using IPA to recover goo a while back. I have never done it, so it would be nice if it could be edited or reviewed by someone who had gotten it to work. We can add ethanol info too, but again I have never done that recovery.

 

[_Trip_]

Neither have i, i have never gotten goo but twilight_person first reported ethanol working and fruit is life and Mr_teknique among others reported it worked flawlessly and instantly converts it to crystal.

 

[Brennendes Wasser]

Would isolating the goo, adding freh (dry) EA to it and waiting move the water and citric citric acid out of the salt?

Quite sure it would not do much, as M-Cit + CA + water would be totally mixed up together, so the
only way would be to one-time dissolve all of them at once and then only precipitate the M-Cit again. So therefore I think this re-x in OTC alcohols is the way to go.

I put some solubility data in the chemical guide thread, but as it is a goo it is not easy to be measured. So simply just use low amounts of IPA or Ethanol (IPA preferred, as it is easier to come by as 99+ %). The issue would be that the goo is very sticky of course. Therefore it cannot easily be transported into another vessel, which can be heated, without leaving behind a bigger load. Therefore if people encounter goo more often, then I would already start crystallizing in a vessel that you can also heat up. With many glassware it might not work. But going low on the alcohol and therefore heat it as much as possible is the key to not loose too much during this re-x.

Formed crystals so I filtered everything but there was a layer of sticky crystals in the bottom of the flask and they were impossible to pickup with fresh EA. I had to pick them all up with water and evaporate that. This left behind almost the same thing. A sticky layer with crystals through it. In the end I used a small amount of water to pick it all up and bombed it with IPA which precipitated everything straight away. Adding water to the mix early on certainly made a mess of things.

Great that it gave you nice crystals, but here I would say 2 things:

1. dont already pre-dissolve it in water. It is just enough to simply use hot IPA and start stirring. It will also dissolve. Pre-dissolving it in water will add more water to the whole system and then make less of your crystals precipitate when adding the IPA. Secondly also as always put it into the freezer to get the max of your crystals back :thumb_up:

2. Now regarding simply dissolving in something (being it water or ethanol) and letting it evaporate again:
This will not help anything sadly. As I said the goo seems to also carry a huge load of plain citric acid. It will also remain like this obviously. Some time ago Twilight Person told to use Ethanol and then simply evaporate it off again. Maybe that can get you something which is solid, because the evaporating ethanol will continuously carry away the excess water. The remaining stuff will be very low or free of water, but still contain a mix of M-Cit + CA. And with water isntead of Ethanol you dont even have the side effect of dragging away the water continuously, so excess water even end again inside of your remaining stuff, making it a goo again.

But in any way this shows that you need to precipitate it from an alcohol if you ever want to separate it from excess citric acid and water. IPA is probably better, it will be easier to get it as waterless as possible. Manual drying not needed (the goo anyways brings water), but definetly use 97+ % IPA instead of 90 %!



So now sadly as I told I have the nice CIELO product and the re-x product sitting and waiting for the instrument, but I cannot do currently So instead of posting all the data for the goo experiments prematurely, I instead will just give some numbers so you can see what is going on.

The final CIELO product will probably be quite the same all across the world, if you get those nice long needles So for goo it might be different as I said, which might depend on various factors like actual excess of water or citric acid etc. ... but still I guess the overall composition will be quite the same, like there will be nobody who has a goo and 0 % water inside.



Goo from CIELO, no modification:

19 % Mescaline Freebase
43 % Citric Acid (so roughly ~ 1:1 Mescaline Citrate : excess Citric Acid)
38 % Water

Goo from CIELO, after full evaporation to dryness (50 °C at 40 mbar):

22 % Mescaline Freebase
51 % Citric Acid
27 % Water

This shows even if you leave your goo for ages until it fully dries, it will still contain a LOT of water. So you should always go for the IPA re-x.

Attached pictures:

Up-Left = "wet" Goo
Up-Right = "dry" Goo. While drying it formed big bubbles, which then solidified as popped bubbles upon solidification

Down-Left = Product after IPA-re-x. Not analyzed but water-free and probably CA-free.
Down-Right = just some regular CIELO needles

These bottom last 2 still missing and then can make a post about full process ...

 

[modern]

I did a dry run of the cielo and tried using selenicereus as the dry material.

Seeing as it should have hordenine and tyramine I was expecting it to possibly salt out following cielo but there was none. I attempted adding more citric acid to lower ph more and will see if it works.

I was wondering if anyone could explain why nothing salted... It may also just be too low content but is it due to the higher logP values? Mescaline and ethyl acetate are at .7 logP so works great the other two are higher so not pulled? If nothing forms I'll add some water and then evaporate the water to see if any salts form.


Side question has anyone tried adding a drying agent to the ethyl acetate after the pulls rather than fridge rest? I believe there needs to be some water but more as a way to accelerate the process?

 

[Loveall]

I did a dry run of the cielo and tried using selenicereus as the dry material.

Seeing as it should have hordenine and tyramine I was expecting it to possibly salt out following cielo but there was none. I attempted adding more citric acid to lower ph more and will see if it works.

I was wondering if anyone could explain why nothing salted... It may also just be too low content but is it due to the higher logP values? Mescaline and ethyl acetate are at .7 logP so works great the other two are higher so not pulled? If nothing forms I'll add some water and then evaporate the water to see if any salts form.


Side question has anyone tried adding a drying agent to the ethyl acetate after the pulls rather than fridge rest? I believe there needs to be some water but more as a way to accelerate the process?

Thanks for your report! Those alkaloids contain -OH groups which can keep them insoluble in EA.

Yes, an alternative to the fridge rest is to add 0.3% solid sodium carbonate drying agent. This partially separates water at room temp, similar to the fridge rest (and is faster). Fully drying the extract before salting does not work well.

I prefer the fridge rest. The extra time and cold allows other stuff to become sediment and it is one less ingredient to use for lazy people like me.

 

[Loveall]

Thanks BW!

So we can say:

- Goo forms under certain situations when the TEK is not followed properly and there excess water or insufficient citric acid. Note: perhaps the citric acid partially dehydrates the EA (especially anhydrous citric acid), so there is an interaction with the citric acid amount and xtalization dynamics.
- Goo is roughly equal parts water, citric acid, and product. It does not dry much: water is mostly trapped.
- Sometimes novices get goo. However, once they do the TEK properly results are very consistent with white needles.
- A simple re-X in 99% IPA will convert the goo to pure product; Use heat and small/minimal ammount of IPA to dissolve goo, then cool in freezer to recover pure product.

Question: if you evap the IPA after re-X, do you simply get solid citric acid?

 

[navegandouniversos]

Thank you all guys, for your time invested in this, dedication and kindness to share it, I really appreciate it.

So here we go straight to the plate to dry that goo and then proceed with ipa and cold ,,, I have the same question as you Loveall about the ipa filtered once the re-x is done ,,, will the excess CA be there when evaporating that ipa ? and about the amount of ipa to use, could I calculate double the amount of the goo ? or a little less, or a little more ?.....

Now I am understanding something, clearly those two things that I saw precipitate from the ipa, one was the alkaloids and the other frozen water, I estimate that yes, since when I removed the excess IPA, it returned to that oily sticky state completely difficult ....

 

[downwardsfromzero]

modern - the OH groups may also keep them bound to the lime as calcium phenolates.

Brennendes Wasser - thanks for your ongoing investigations; I'm not remotely surprised to see that you've found what appears to be a 1:1 M citrate:citric acid stoichiometry. This does rather suggest that citrates can form dicitrate monoanions, which would be analogous to the known diacetate monoanion.

A slightly shoddy diagram is attached. Really there will be a couple of water molecules in there too, helping it all to stick together in a gooey mess...

 

[Loveall]

BW, how did you get goo?

 

[Loveall]

TEK has been updated to reccommend simple 99% IPA re-X for goo to xtal conversion.

 

[Brennendes Wasser]

- Goo forms under certain situations when the TEK is not followed properly and there excess water or insufficient citric acid. Note: perhaps the citric acid partially dehydrates the EA (especially anhydrous citric acid), so there is an interaction with the citric acid amount and xtalization dynamics.
- Goo is roughly equal parts water, citric acid, and product. It does not dry much: water is mostly trapped.
- Sometimes novices get goo. However, once they do the TEK properly results are very consistent with white needles.
- A simple re-X in 99% IPA will convert the goo to pure product; Use heat and small/minimal ammount of IPA to dissolve goo, then cool in freezer to recover pure product.

Sounds like what I have seen from that samples. I bought a cactus for extraction and made a test which was crystallization vs. water content and it seems some did not give crystals, instead it looked like nothing formed. But based on weight there was an increase, so that must be super tiny amounts of goo. Now soon repeating that, because I used too low amounts :roll: But that looked to me like some certain water amounts were giving crystals and some just gave the goo ...

BW, how did you get goo?

That was a sample I got to analyze some weeks ago from unlucky Twilight Person :surprised From that stuff I made the post about the properties. Now I wanted to see if the true crystals have the same water amount and if the IPA rex is truly giving a pure product. So now bought me a small cactus and did CIELO last week, but now cannot go to the analytics :thumb_dow But I bought a huge cactus now, will just leave in darkness for like 1 week (hope that is at least something) and then maybe do that crystallization vs. water content again.

Another option to verify if IPA re-x is successfull could be simply dissolve goo and re-x product in water and compare pH. Even Meskalin-Citrate still has 2x acidic protons, but their pKa is way reduced, so pH should not drop much, while with goo it should be 2-5 I guess.




As a sidenote the precipitation from IPA rex will partly be pretty solid, party super fine powder, which will float inside of the IPA (that is the stuff in the filter paper I posted above). Therefore you cant just decant like with DMT re-x ... you would need to also use a filter paper and then just let it drip over it, wash with a little fresh IPA. If people would be lazy and try to decant they would either loose some goodies or keep some of the IPA, which results in getting some CA back into their product. That can be visibly seen by having a slightly yellow crystal at the end instead of pure white.

 

[Twilight Person]

It's the stuff which i also posted from my last CIELO in the alu pan. Strong clouding at the start but then no xtals next days.

 

[modern]

I skipped the fridge cold rest thinking there was no water since it was clear and ended up with goo I think. It clouded at first then goo. So tomorrow I'll separate the goo and try recrystallizing in IPA. I only have 70% so I'll salt out and dry with sodium sulfate.

EDIT I actually skipped the fridges step because I thought adding 10% ethyl acetate would prevent gooing since it would dilute the water? Maybe I needed to add more?

 

[Loveall]

I skipped the fridge cold rest thinking there was no water since it was clear and ended up with goo I think. It clouded at first then goo. So tomorrow I'll separate the goo and try recrystallizing in IPA. I only have 70% so I'll salt out and dry with sodium sulfate.

EDIT I actually skipped the fridges step because I thought adding 10% ethyl acetate would prevent gooing since it would dilute the water? Maybe I needed to add more?

10% ethyl acetate could work, but only if it is dry to begin with. This was a theory to help improve the tek robustness, but not sure if it was ever done alone and tested before. Perhaps it should be removed from the TEK because of what happened to you.

 

[modern]

I'll redo it with 20-25% EtAc next time to see if it works. Anything over that amount might be too much to make it worth while. And the fridge step might be best option.

I wanted to try drying with sodium sulfate but at the moment I forgot I had it and didn't use it.