• Members of the previous forum can retrieve their temporary password here, (login and check your PM).

TEK Ethyl acetate approach [CIELO]

This topic contain a TEK
Migrated topic.
Loveall said:
Another possible easy test would be to add fumaric to the solvent crashed with citric. Have you tried that yet?
Click to expand...

Done as of last night! Keeping an eye on it. So far no change.

Found something pretty interesting in one of my jars of used citric salted solvent today. Oily droplets that looked exactly like M. It solidified when washed with fresh EA, just like the M oil too. I assumed it was product that had escaped while decanting, but it has no reaction to Marquis reagent and tastes sour. No bitterness.
 
I haven't been recording yield % for most runs since I had been dividing the solvent for various trials. Those crystals were combined into one filter funnel. I did a full scale 100g run and got 700mg of fumarate, which corresponds to 863mg citrate, 452mg of freebase. That'd be 0.452% mescaline by dry weight, which seems reasonable according to this erowid article
 
Thanks.

I think 1% is considered ok, bragging rights start higher; though, unlike dosage, most people don’t say what salt basis they are using.
 
Yeah, not the most exciting result for sure, but right now I'm happy I got anything

It would for sure be most useful if everyone reported their yields in terms of the freebase, not whatever salt was formed so we could compare apples to apples. But now that I've got a baseline and procedure that is working for me, I can at least compare directly against myself and look for consistency in the yield. If there's a lot of variability, probably my fault, otherwise, probably unimpressive starting material.

Eventually I'll have my own harvestable columns and not have to rely on a third party for my material.
 
Has anybody directly compared their yields of fumarate vs citrate for the same material? There are some properties of fumaric acid that make me think the formation of a dimescaline salt may be more probable than with citric acid. (Fumaric acid is about 2x as strong as citric acid, and its symmetry may be favorable for crystallization)

If that's the case, 700mg fumarate would be equivalent to 1049mg of citrate, or 549mg of freebase.
 
_Trip_ said:
I believe Loveall has, there's a topic on here somewhere but if you check the CIELO tek wiki page he has written them in there towards the bottom of the page.

Ethyl acetate approach [CIELO] - Preparation - Welcome to the DMT-Nexus here's the results it's in this thread.
Click to expand...

Thank you! That seems pretty convincing that the fumarate is a 1:1 salt. I'm very surprised that the malate would be 2:1 while others are not, considering the 2nd pKa is quite a bit weaker than either citric or fumaric acid.

Glad to finally have a baseline yield for what I'm working with. Hopefully it can be pushed up. If not, at least my yield is in range of published values.

Found a more thorough compilation of data in Trout's notes
 
orchidist said:
_Trip_ said:
I believe Loveall has, there's a topic on here somewhere but if you check the CIELO tek wiki page he has written them in there towards the bottom of the page.

Ethyl acetate approach [CIELO] - Preparation - Welcome to the DMT-Nexus here's the results it's in this thread.
Click to expand...

Thank you! That seems pretty convincing that the fumarate is a 1:1 salt. I'm very surprised that the malate would be 2:1 while others are not, considering the 2nd pKa is quite a bit weaker than either citric or fumaric acid.

Glad to finally have a baseline yield for what I'm working with. Hopefully it can be pushed up. If not, at least my yield is in range of published values.

Found a more thorough compilation of data in Trout's notes
Click to expand...

It may have more to do with the solubility thank the pKa. If 1:1 malate is soluble in EA it may react further and crash at 2:1. Not sure, just speculating on the meaning behind the measurements I got, could be wrong.
 
Metta-Morpheus said:
Hi Cheelin,

I have gone thru and deleted your one word/emoji posts. These are useless and just take up space. Please refrain from further one word responses.

Metta-Morpheus
Click to expand...


Petty!


Thanks Loveall et al, great tek!
 
orchidist said:
Yeah, not the most exciting result for sure, but right now I'm happy I got anything

It would for sure be most useful if everyone reported their yields in terms of the freebase, not whatever salt was formed so we could compare apples to apples. But now that I've got a baseline and procedure that is working for me, I can at least compare directly against myself and look for consistency in the yield. If there's a lot of variability, probably my fault, otherwise, probably unimpressive starting material.

Eventually I'll have my own harvestable columns and not have to rely on a third party for my material.
Click to expand...
If it's comparing apples with apples we want, the reference standard should, clearly, be the malate salt. 😁
[chemistry joke - check the etymology of malic acid if you don't get it :D ]

Malate is, to a large extent, the salt form we can expect in the cactus - but really I'd like to bump that link to the salt equivalent calculator spreadsheet: {which will be here when I can find it, unless someone beats me to it ↓↓↓}
[EDIT: Orchidist found it - thanks and well done - and I've put the link here as well. And a few posts further on you'll find my update including mescaline citrates. It would be simple to add malates to the list as well.]
 
downwardsfromzero said:
orchidist said:
Yeah, not the most exciting result for sure, but right now I'm happy I got anything

It would for sure be most useful if everyone reported their yields in terms of the freebase, not whatever salt was formed so we could compare apples to apples. But now that I've got a baseline and procedure that is working for me, I can at least compare directly against myself and look for consistency in the yield. If there's a lot of variability, probably my fault, otherwise, probably unimpressive starting material.

Eventually I'll have my own harvestable columns and not have to rely on a third party for my material.
Click to expand...
If it's comparing apples with apples we want, the reference standard should, clearly, be the malate salt. 😁
[chemistry joke - check the etymology of malic acid if you don't get it :D ]

Malate is, to a large extent, the salt form we can expect in the cactus - but really I'd like to bump that link to the salt equivalent calculator spreadsheet: {which will be here when I can find it, unless someone beats me to it ↓↓↓}
Click to expand...

Love it 😁 My other hobby gives me tons of exposure to etymology, especially of the botanical sort.

And a calculator would definitely be great, I made my own in the spreadsheet I've been using to proportion ingredients for this tek. At some point, I'd love to spend some time writing up some calcualtors in javascript.

Anyway, Loveall, I forgot to share that I made saturated solutions of my citric acid in EA and water, no residues to speak of.

I spent some time in the references on the CIELO wiki, particularly the mycotopia thread regarding transparent tacky product from bridgesii. The product described there seems a whole lot like what I got. That thread continued, and it looks like it might not just be bridgesii, but more generally powder made from whole cactus. I have no way to be completely certain, but I wouldn't be surprised at all if all the powders I got use the entire cactus. That would account for the lower yields too.
 
Orcjidist, I used whole cactus powder earlie on and got xtals. However, there could be difference s in drying, cactus, etc.

Have you always gotten goo using citric acid with the other whole cactus powders?

Anyone else get xtals with whole cactus powder? If yes, how did they dry it?

Anyone get goo with outer skin after feeling they got the process done right?
 
Some points for consideration, from a new member here.
Nemooo said:
This is for the Ethyl acetate approach thread by Loveall. I can't seem to post in there.

Great job on coming up with a greener and faster method that appears to give high purity product!

A few suggestions:
1) Dry the solvent before trying to precipitate the alkaloid salts:
- I saw some effort to dry the ethyl acetate, but CaCl2 is generally not compatible with amines or esters as they can form a complex with it, it can also be slow and finicky.
- K2CO3 is your best bet, compatible with both amines and ethyl acetate. Only use just enough and give it time to do its job. Molecular sieves are a possibility too.
- A dry solvent will make things more reproducible and will lead to faster crystallisation and also should avoid the formation of the biphasic "oil" some have seen. The "oil" appears to be a very saturated solution of alkaloid salt and acid, the addition of the acid in the presence of water in the solvent means the more polar compounds can form aggregates and eventually separate out due to the increase in polarity/ ionic nature. The fact they are in solution also means the stoichometry of the alkaloid salt could vary.

2) Dissolve the solid acid of choice (citric, fumaric etc) in ethyl acetate first, then add this to the ethyl acetate extract.
- This, providing the extraction solvent is dry enough, will mean the amount of acid can more accurately titrated (yes excess acid is soluble in ethyl acetate, but if a biphasic system develops it will also partition itself between the aqueous and organic layers complicating things).
- The ethyl acetate may need to be heated or sonicated to get more acid to dissolve but this is ok, just let it cool before adding to the extract.

3) Consider trying succinic acid:
- Fumaric acid is a Michael acceptor and there are cases in the literature recording amines reacting with it in this way. Probably fine most of the time, but should a solution need heat sterilisation that could be a problem.

4) Do an A/B extract on the residue to prove all alkaloids have been extracted.
- I think you should do this to confirm it gets all the alkaloids.

5) Melting point
- Do a melting point.This will tell you how pure it is.
- Popping or change in crystal structure prior to melting would indicate solvent or water or crystallisation/ hydrate.
- Otherwise more spectroscopic data to show it is clean and doesn't need recrystallisation. That Mass Spec you showed doesn't say how it was obtained, and doesn't tell the whole story. Im guessing it was run in positive mode only so no acids present?

6) Recrystallisation.
- Would be great to see some solubility information on the citrate/ fumarate/ succinate and also recrystallisation.
Click to expand...
 
Loveall said:
Orcjidist, I used whole cactus powder earlie on and got xtals. However, there could be difference s in drying, cactus, etc.

Have you always gotten goo using citric acid with the other whole cactus powders?

Anyone else get xtals with whole cactus powder? If yes, how did they dry it?

Anyone get goo with outer skin after feeling they got the process done right?
Click to expand...

Unfortunately, I have no way to be sure of how these powders were prepared. Wish I did.

I still have one more powder to try, just looking at the paste, it's definitely a different cactus than the others--using the same ingredient proportions as prior runs, this one mixed up to a tough, rubbery consistency, and stuck to the spatula aggressively as I mixed. Really made my arm hurt. Not sure if more water will fix it, but at the risk of introducing more variables than I can deal with, I'm going to carry on with the next steps, hoping it'll loosen up when the EA is introduced.

For comparison to any others who may report back on results with whole cactus powder and drying, I've been using Na2CO3. I may not have allowed it enough time to completely dry the solvent, so I can try leaving it for longer, or switching to K2CO3 if Na2CO3 isn't a good substitute for it. I also have molecular sieves now, so I could try that out as well.

I do see the benefit of drying, even if my procedure resulted in incomplete drying. With fumaric acid, the extra step gave bigger crystals than when I left it out.

It does seem that what I'm observing with citric acid is consistent with the formation of a biphasic system and ultimately a mixture of acid and salt like Nemoo described. With the addition of CA, my solvent partitions into layers, and the oil forms in the lower layer, almost exclusively near to where crystals of solid CA were present. Adding a quantity of CA calculated to be slightly in excess of the yields I got from my successful run with fumaric acid also produced oil, in that case, the oil formed exclusively around where the pile of citric acid had been before it dissolved.

I'll put extra effort into improving my drying process and give dissolved citric acid a try as well. Thanks Nemoo for the suggestions :)
 
I updated the goo FAQ section of the TEK. Let me know if I got anything wrong or someone disagrees. Thanks.

CIELO TEK said:
Q: After adding citric acid, goo precipitated instead of crystals, what gives?

This is the most common issue people encouncer. Cause/Causes are unkown, but there are some theories:
-Poor TEK execution: This is believed to be the most common issue. Make sure the TEK instructions were followed, in particular: well mixed paste, short pull times, clean extract free of debris (including water droplets), citric acid is in range, etc. In particular, before adding citric acid, allow the extract to rest and ensure water is not an issue.
-Cactus powder: Some cacti or parts of some cacti may cause goo. orchidist[22] shower that in one case, use of fumaric acid resulted in crystals, while citric acid resulted in goo.
-Xtalization dynamics: A separate water phase with salt/acid could separate before xtals form. Try dissolving citric acid in fresh ethyl acetate and slowly adding that drop wise to the extract.

If you see or overcome goo, please report it on the forum. You could help solve this issue that some workers come across.
Click to expand...
 
I think I have some strong support for the citric acid/citrate mixture hypothesis here:

I had a jar of citrate oil from a week or two ago, I discarded the extraction solvent into my waste jar and added a small amount of clean solvent, capped it and forgot about it.

I just rediscovered it, and found crystals beginning to form out of the oil! Even more convincing, the solvent is acidic. Seems that once the oil is formed, it takes quite a while to diffuse back out into solution, so a quick wash won't cut it, but it eventually does move out of the precipitate and crystals can form.

Just a note: the table I'm working on is very beat up, what looks like particles in the solvent are just chips in the laminate below.
 

Attachments

  • washed_oil_crystallizing.png
    washed_oil_crystallizing.png
    2.2 MB · Views: 3
Back
Top Bottom