TEK Ethyl acetate approach [CIELO]

[downwardsfromzero]

DWZ, if you want, you can read the TEK's "lab notes". I tired to summarize most of the thread results there for convenience. See if you find any issues with our logic and tentative conclusions. Also, feel free to update that section with your thoughts or observations.

The lab notes look good. I think the reactivity of mescaline base (or perhaps a proxy amine like DMPEA) with EtOAc could do with being quantified. The reaction of primary and secondary amines with esters is well established.

Thanks for your thoughts!

And thank you for your practical efforts, all contributors!

The difference between the 3 minute pulls and the 10 minute pulls is paramount. With the longer pulls there is over 3 times the contact time with the lime, which despite its poor solubility is still as we know a strong base. This will react with the ethyl acetate to form calcium acetate and ethanol - and further base will dissolve to maintain equilibrium.

For those of us who dropped out of organic chemistry... :lol: Does further base dissolving mean that more calcium acetate and ethanol is formed, causing more base to dissolve, ad infinitum?

More or less, yes. At some point one or other of the reagents will get used up.

I think the calcium acetate is likely to be behind the stickiness that develops - perhaps along with the ethanol which will increase the 'wetting' of the paste by the solvent.

What does the wetting mean? And how does this affect the system?

As I see it, ethanol kind of bridges between the aqueous phase and the organic phase, being soluble in both. This allows the ethyl acetate to stick to the lime paste more readily. Calcium acetate will form a gel with ethanol, too. This all says "sticky" to my intuitive chemical imagination :?

In a similar vein, given enough time freebase mescaline will react with ethyl acetate to produce ethanol and N-acetylmescaline.

Any idea how much time this reaction takes?

All I can say here is, it looked like 30% losses for one of you experimenters over 24hrs - and that was with refrigeration(?).

It seems you've intuited this already by going straight from pulls to salting, but I think it's important enough to state for anyone who might be interested in testing this method themselves. N-acetylmescaline would represent a technical loss of yield. There's every chance it would remain in solution after the salting and it would be interesting to see if it's a component of the oily evaporation residue.

It's a loss of yield because the N-acetylmescaline doesn't further react to form mescaline citrate, and thus this N-acetylmescaline remains in solution, correct?

That's pretty much my reasoning, yes. Additionally, IIRC there's some data showing N-AcMesc to be essentially inactive. Would have to check that though. The thought of attempting to recover mesc from this makes me shudder

Ethyl acetate is a reactive solvent (compared to naphtha or tolu/xylene). It's very fortunate that those quick pulls work so well, as does the quick salting. Time really is of the essence here.

 

[downwardsfromzero]

As far as my own tangential experiments go, I've established that (largely) anhydrous citric acid has some slight level of solubility in butyl acetate [practically dry, straight from the can]. This could be as low as 1mg/g although I was checking the solubility curve with respect to temperature using small volumes rather than evaporating a significant volume of solvent. I have 10mL of BuOAc equilibrating with an excess of citric overnight, to be ready for filtration and evaporation starting in the morning.

 

[shroombee]

I have a comparison here of 6 x 3 minute pulls (immediate salting) versus 6 x 10 minute pulls (salted after 48 hours):

6 x 3 minute pulls: average yield 1.6%
6 x 10 minute pulls: average yield ~1.35% (measured over 1.4% but I'm conservatively subtracting 0.05% because this product wasn't washed)

So the loss from 1.6% to ~1.35% is about 19% reduction (1.6 / 1.35). Could easily be more loss if I had washed the product properly. It is unclear whether the loss was from the longer pulls or from letting the pulls sit for 48 hours before salting. Something else to test.

Loveall saw a reduction from 1.0% to 0.7% when testing 24 hour pulls, which is a 43% reduction (1.0 / 0.7).

Ethyl acetate is a reactive solvent (compared to naphtha or tolu/xylene). It's very fortunate that those quick pulls work so well, as does the quick salting. Time really is of the essence here.

We'll have to keep this in mind. Perhaps advise pre-weighing all the solvent for each pull to ensure the process runs quickly. And strongly recommend a french press which enables easy, fast decanting.

 

[grollum]

What a lovely technique. Unfortunately my fist try didn't yield anything so far.
I used supposedly not very potent terscheckii material for a first try which consisted of lots of skin and core. Will have another try with more potent material.

Sadly I lost lots of the first pull on the floor because I used a clunky glass jar which I couldn't handle right. I then switched to a french press which was great to handle. Parts of the french press are made from Polypropylene which seems to be more or less OK in combination with Ethylacetate in low temperatures.

When salting the Ethylacetate with citric acid, it got cloudy quite fast and stayed cloudy for some hours. I then put more citric acid into it step by step and it slowly cleared up. After adding more acid it looked like the Ethylacetate could not dissolve the citric acid anymore and some tiny bits citric acid collected on the floor of the jar. So i stopped adding more acid and waited the night. Today solution was almost clear but still a tiny bit cloudy. I poured into a coffee filter and now wait for the solution to run through. It seems that there is almost no xtals in the filter.

I realized that something is building up on the walls of the jar which doesn't look like xtals but more like round water drops. It stayed at the walls after removing the solvent from the glass. I also discovered something on the floor which looked a bit like liquid sugar coating. I think that might be citric acid.

Will have another try tomorrow with better material.

 

[metta-morpheus]

^^^ Those are the same droplets that I got. Their process sounds par for course for me except for the letting sit overnight. I got the droplets immediately, decanted, and disolved into water.

Grollum: Rinse your jar with a little warm water. All my droplets dissolved into the water, and when I evaporated it, it has left an oily resin tgat is almost to scraping capability. It was a little gooey at first, now reminding me of clear cactus resin. When scraped I will weigh to see if it’s still in the realm of theoretical yield, if this goo somehow contains the goodies.

I have a 50 gram batch basing since 1pm yesterday, will be around 25 hours by the time I get to pulling it. Updates later.

 

[grollum]

^^^ Those are the same droplets that I got. Their process sounds par for course for me except for the letting sit overnight. I got the droplets immediately, decanted, and disolved into water.

Grollum: Rinse your jar with a little warm water. All my droplets dissolved into the water, and when I evaporated it, it has left an oily resin tgat is almost to scraping capability. It was a little gooey at first, now reminding me of clear cactus resin. When scraped I will weigh to see if it’s still in the realm of theoretical yield, if this goo somehow contains the goodies.

I have a 50 gram batch basing since 1pm yesterday, will be around 25 hours by the time I get to pulling it. Updates later.

I will try that. But I added some more citric acid to the filtered Ethylacetate to try if there might crash something with more acid. This acid is now sticking to the wall as well.

But will try to dissolve in water and evaporate the leftovers from the jar. By the way. My filter also had a slightly oily residue which din't feel oily anymore so much after drying it in the oven. But still the filter looks slightly transparent.

 

[metta-morpheus]

Today’s run:

Started with 51.45 Grams powdered cactus, added 13 grams lime and 150 grams water. Left basing for around 26 hours. Pulls were as follows:
Pull 1) 151g ethyl added- 99g recovered
Pull 2) 109 added- 103 recovered
Pull 3) 104 added- 96 recovered
Pull 4) 104 added - 102 recovered

All finished in about 20 minutes. Went straight to salting. Salting went as follows:
4.5 g citric added, clouded immediately. Magnetic stirred in high for about 3 minutes. Everything dissolved, no precipitation.
5.5 g citric added, magnetic stirred for 5 minutes until everything dissolved. No precipitation.
Added 5 g citric. Stirred another 5 minutes, everything dissolved.
Added 7 g citric. Stirred 5 minutes. Minor salt looking precipitation(or undissolved citric?) accumulates in bottom of jar.
Added 8 grams, for a total of 30 grams :shock: stirred about 8 minutes. Lots of solids built up in glass. Solution is also finally clear green again as well.

Filtered solution, most Crystal stayed stuck to jar. Scraped what I could and threw in filter, and washed 5 times with fresh ethyl. Dissolved what was in jar, which was most of the solids, with minimal hot water, and dumped into glass bread dish.

Conclusion: im hopeful, yet Hesitant to celebrate. I used 30 grams citric to 400 grams ethyl, which comes to a 7.5% concentration, or 75 mg/g. So I’m well above the 50mg/g, therefore, a lot of my end result must be an abundance of citric. The collection of crystals in the filter seemed to have shrunk significantly after washing, so...

Also... no droplets this time. Maybe something to the immediate salting, as the previous times there was far more farting around and time gone by before adding the citric.

 

[shroombee]

Started with 51.45 Grams powdered cactus, added 13 grams lime and 150 grams water. Left basing for around 26 hours. Pulls were as follows:
Pull 1) 151g ethyl added- 99g recovered
Pull 2) 109 added- 103 recovered
Pull 3) 104 added- 96 recovered
Pull 4) 104 added - 102 recovered

This is pretty much how I run it. Including the 150 grams added and ~100 grams recovered on the first pull. Then adding 100 and recovering 100 for subsequent pulls.

Added 7 g citric. Stirred 5 minutes. Minor salt looking precipitation(or undissolved citric?) accumulates in bottom of jar.

The total added citric at this point is close to 50 mg/gram so it might be undissolved citric.

Conclusion: im hopeful, yet Hesitant to celebrate. I used 30 grams citric to 400 grams ethyl, which comes to a 7.5% concentration, or 75 mg/g. So I’m well above the 50mg/g, therefore, a lot of my end result must be an abundance of citric.

The most citric I've added is 20 mg/g. I get an abundance of snowy xtals at 5 mg/g. Just checking here, but are you sure you're using a mescaline containing cactus?

Have you used other teks on this batch? If so, what's the yield?

Attempting to eliminate any other variables in our processes... what's your basing technique? I slowly add the lime to the water to make milky water. Then slowly add powdered cactus to the milky water, making sure to incorporate thoroughly each time I add more powdered cactus. Incorporating slowly in this way takes about 5 minutes. Then I mix another few minutes. If you have unbased cactus or clumps of lime, perhaps that's affecting xtalization?

You're using technical grade ethyl acetate and anhydrous citric acid. What lime are you using?

 

[shroombee]

When salting the Ethylacetate with citric acid, it got cloudy quite fast and stayed cloudy for some hours. I then put more citric acid into it step by step and it slowly cleared up. After adding more acid it looked like the Ethylacetate could not dissolve the citric acid anymore and some tiny bits citric acid collected on the floor of the jar. So i stopped adding more acid and waited the night. Today solution was almost clear but still a tiny bit cloudy. I poured into a coffee filter and now wait for the solution to run through. It seems that there is almost no xtals in the filter.

In my experience, the crashing needs to happen immediately, meaning keep adding citric until I get xtals. Waiting for clouds to clear and xtals to form over time means I didn't add enough citric, and yields have always been much less. Once I add enough citric, mix thoroughly, and xtals form, the entire crashing process happens in a few minutes (or less) and the solvent is then clear.

How much citric did you add, and to how much solvent?

 

[grollum]

In my experience, the crashing needs to happen immediately, meaning keep adding citric until I get xtals. Waiting for clouds to clear and xtals to form over time means I didn't add enough citric, and yields have always been much less. Once I add enough citric, mix thoroughly, and xtals form, the entire crashing process happens in a few minutes (or less) and the solvent is then clear.

How much citric did you add, and to how much solvent?

hey shroombee,

in the second attempt with supposedly better material I ended up with 770g of solvent to which I added 4.5g of citric acid. I checked the acid. It is anhydrous citric acid. I get the same result. A strange layer of slime is building at the bottom, solution is getting clearer but not totally clear. I have the feeling that adding more acid is not the right solution.
There might something wrong in the process.

The Ethylacetate I use is like 99.92% pure. I got it from a paintshop. My feeling says it might be not pure enough or something strange is in there.
The citric acid says its pure and anhydrous.
My calciumhydroxyd is from aquarium supplies and is 98% pure.
I use normal water.

I made a water pull from the leftover Ethylacetate from the first try yesterday. I also washed out the droplets which where sticking to the jar walls and evaporated everything in the oven. I got something like a slightly brown clear spray paint layer in my dish. Which is sticky. Might need more time to fully dry. No xtals.

 

[shroombee]

I've been using Peruvian Torch for my experiments. I'm going to try San Pedro and see whether I get the same xtals. Perhaps the cactus makes a difference. I believe Loveall has been using San Pedro though.

Here is my full process in case anything pops out as different:

- 50 grams finely powdered cactus, 12.5 grams Mrs. Wages pickling lime, 150 grams purified water, ethyl acetate, anhydrous citric acid. My ethyl acetate is HPLC-UV, very high purity. Loveall has been using hardware store "M.E.K. substitute" ethyl acetate. Loveall and I both use the same Milliard brand citric acid;

1) Add lime to water to make milky water;

2) Slowly add cactus to milky water, ensuring each addition of the cactus is well-incorporated before adding more cactus. This process takes about 5 minutes. Stir an additional 3 minutes;

3) Transfer clumpy cactus to a sealed jar and let it react for 24 hours;

4) Transfer cactus to a french press;

5) 1st pull: Add 150 grams ethyl acetate. Stir very gently for 30 seconds. Wait 2.5-3 minutes. Decant ethyl acetate. Should recover about 100 grams ethyl acetate. pH paper dipped into pull should be dark green;

6) 2nd through 6th pulls: Add 100 grams ethyl acetate. Stir very gently for 30 seconds. Wait 2.5-3 minutes. Decant. Should recover about 100 grams ethyl acetate for these pulls. 2nd pull pH paper dark green. 3rd pull slightly lighter green. 4th pull faint green. 5th and 6th pulls almost no color change. 5th and 6th pulls seem unnecessary. However, I have not salted a stronger 4-pull extract. Shouldn't change the result, but stating this here for completeness;

Edit: Wild guess here - perhaps the first pulls draw water from the cactus, but the last pulls do not. Thus my combined 6-pull extract ends up with a lower percentage of water than a 4-pull extract. Will have to test this.

7) Combine all pulls. I've been splitting these combined pulls into 2-4 separate jars so I can experiment with different salting techniques, so I have never salted more than 25 grams equivalent cactus at a time;

8. Add 5 mg citric per gram of solvent. I've also done 15 mg/g and 20 mg/g. I add the citric all at once;

9) Fast stir on magnetic stirrer for 5-10 minutes (5 minutes should be enough but I've done 10 minutes). Within 1 minute I see xtals. Within 2-3 minutes the solvent is clear enough to see the vortex at the center of the solvent;

10) Let solvent sit maybe 10 minutes until xtals fall to the bottom. I assume no more xtals will be created after this;

11) Pour solvent through coffee filter. Use fresh ethyl acetate or transfer solvent back to jar a few times to get most of the xtals out of the jar;

12) Wash xtals in coffee filter a few times with fresh ethyl acetate;

13) Let ethyl acetate evaporate in coffee filter. Happens quickly, within 30-60 minutes. I wait a lot longer to be sure all the ethyl acetate has evaporated before scraping out the product;

14) Dissolve xtals that were stuck in the jar with warm water, pour water onto an evaporation dish, and let the water evaporate. I use a dehydrator at 95 degrees;

 

[grollum]

Thanks Shroombee!!

your explanation makes some of the steps clearer for me.
For example how you mix the base step by step.
I will do the next tests with 50g powder. Should be enough to see if the xtals form.
I will also split in several glasses before salting.

What vessel do you use for putting the water in the dehydrator? Mine is quite small? Petri dishes or something similar?

Will the Ethylacetate loose the green color when the xtals form? On one of Loveall's photos from the thread it looks like.

Labgrade Ethylacetate can be quite expensive but i think I found a good source for a good price which seems to be 100% clean. Will try that one as an alternative. Also will get some cleaner lime and try again. Maybe also a different citric acid.

The cactus I used for my second try was a fat bridgesi which was stressed for a few weeks in darkness before converting it into flakes / powder. Should be better then the terscheckii from first try.

 

[downwardsfromzero]

A small report on the butyl acetate tangent:

The citric acid solubility test is still running - but butyl acetate evaporates very slowly at room temperature (of course!) There is some evidence of solid material being deposited in the evaporation container, and the observed behavior of the solid citric acid when mixed with the butyl acetate indicated that some of it was dissolving. Fine particulates disappeared and loose crystals remained. This allowed some reasonable confidence that at least a saturated solution of citric acid in butyl acetate had been prepared.

The solution will be transferred to a forced-ventilation environment in the morning. Cactus extraction testing will ensue at a suitable point in time. It will be useful if this turns out to be an otc alternative to EtOAc for those struggling to find it and not wanting to purchase online.

 

[shroombee]

What vessel do you use for putting the water in the dehydrator? Mine is quite small? Petri dishes or something similar?

My dehydrator has multiple racks in which I can fit 10" square glass serving dishes. For a smaller dehydrator, you can use a small baking dish or multiple petri dishes, or pour the water into a larger baking dish and let it dry in front of a fan. The yield from the evaporation won't be much unless a lot of xtals stuck to the jar and wouldn't come out with the solvent.

Will the Ethylacetate loose the green color when the xtals form? On one of Loveall's photos from the thread it looks like.

The solvent will still have a greenish/yellow tint. I am not sure if it loses any color versus unsalted solvent. I will check that on my next runs.

Labgrade Ethylacetate can be quite expensive but i think I found a good source for a good price which seems to be 100% clean. Will try that one as an alternative. Also will get some cleaner lime and try again. Maybe also a different citric acid.

I am not sure any of this makes a difference, but it wouldn't hurt to try. Especially as my ethyl acetate is high purity and Loveall is using hardware store ethyl acetate.

My ethyl acetate is HPLC-UV and food grade. It costs $37 per gallon plus about $15 per gallon for shipping.

The cactus I used for my second try was a fat bridgesi which was stressed for a few weeks in darkness before converting it into flakes / powder. Should be better then the terscheckii from first try.

I have some bridgesii powder in which I've been debating whether I want to use this tek because the bridgesii is rumored to have less mescaline but with MAOI's which make it seem stronger. Thus I was thinking to use more of a full spectrum tek like ethanol extraction. In addition, if it has less mescaline then perhaps this tek won't work? Maybe I can offer up a small amount to test with this tek.

 

[shroombee]

Bioassay report on 300 mg of citrate product from batch #4:

I used 600 mg of mescaline acetate a couple months ago and that was a strong, enjoyable dose. Being unsure of the acetate purity versus the citrate, and noticing extra sensitivity to psychedelics lately, I decided to go with 300 mg citrate.

Assuming 85% purity of the citrate, I'm roughly at 255 mg mescaline and that's pretty much what the trip felt like. A pleasant, moderate trip. I had some mild jitters the second hour (not as much as the 600 mg acetate) and then some sedative effects for about an hour. Maybe those are the impurities?

The citrate was very easy on the stomach. No bloating which I sometimes get with acetate or HCl.

I'll try 500-600 mg in 2-4 weeks.

 

[Loveall]

Today’s run:

Started with 51.45 Grams powdered cactus, added 13 grams lime and 150 grams water. Left basing for around 26 hours. Pulls were as follows:
Pull 1) 151g ethyl added- 99g recovered
Pull 2) 109 added- 103 recovered
Pull 3) 104 added- 96 recovered
Pull 4) 104 added - 102 recovered

All finished in about 20 minutes. Went straight to salting. Salting went as follows:
4.5 g citric added, clouded immediately. Magnetic stirred in high for about 3 minutes. Everything dissolved, no precipitation.
5.5 g citric added, magnetic stirred for 5 minutes until everything dissolved. No precipitation.
Added 5 g citric. Stirred another 5 minutes, everything dissolved.
Added 7 g citric. Stirred 5 minutes. Minor salt looking precipitation(or undissolved citric?) accumulates in bottom of jar.
Added 8 grams, for a total of 30 grams :shock: stirred about 8 minutes. Lots of solids built up in glass. Solution is also finally clear green again as well.

Filtered solution, most Crystal stayed stuck to jar. Scraped what I could and threw in filter, and washed 5 times with fresh ethyl. Dissolved what was in jar, which was most of the solids, with minimal hot water, and dumped into glass bread dish.

Conclusion: im hopeful, yet Hesitant to celebrate. I used 30 grams citric to 400 grams ethyl, which comes to a 7.5% concentration, or 75 mg/g. So I’m well above the 50mg/g, therefore, a lot of my end result must be an abundance of citric. The collection of crystals in the filter seemed to have shrunk significantly after washing, so...

Also... no droplets this time. Maybe something to the immediate salting, as the previous times there was far more farting around and time gone by before adding the citric.

I think it is a very good sign that the cloudiness dissapears after adding enough citric. It is likely that the goodies crashed.

I also think some of the variability we are seeing could be because of water in the ethyl acetate pulls and whatever cactus stuff comes with it (which could vary by cactus). This water could have increased the citric acid solubility above 50mg/g.

Possible ways of lowering water content to make the process more robust:

1) Add 100g of NaCl (or 33% vs water) to the paste before pulling, the water content should drop from 3.4% to 1.9%.
2) Adding 150g of CaCl2 to the paste (or 50% vs water). Water content should drop even more.
3) After the pull, chemically dry the extract with excess CaCl2 pellets. That should remove almost all the water (and water soluble stuff that could stop crystalization). The pellet dry can be done quickly (15 minutes or so).

I plan on testing 3) again soon. I did it earlier (and shroombee too), but that was before understand quick pulls help. 1) and 2) change the paste and I'm reluctant to re-visit that because I really like how well the paste is pulled as-is. Also, 3) is a "standard" general lab step where solvents are dried after pulling and before salting - perhaps it was a mistake to remove it despite early good results in some examples.

Other drying agents could be used. Just FYI that in my case MgSO4 was difficult to filter/decant from ethyl acetate so I prefer CaCl2 pellets (anhydrous).

 

[Loveall]

Will the Ethylacetate loose the green color when the xtals form? On one of Loveall's photos from the thread it looks like.

The solvent will still have a greenish/yellow tint after xtalization. I am not sure if it loses any color versus unsalted solvent. I will check that on my next runs.

From what I have seen there is no color change with salting. I think the picture with no green was from early experiments using a microwave on the paste. We stopped doing that once we found it was not necessary.

At the very begining microwaving seemed to break plant material and make xtalization easier, but once we found out that citric acid excess could force xtalization (at least I'm our case) we removed that step.

 

[downwardsfromzero]

With drying agents, if yield appears to go down when using Ca/Mg salts I'd suggest (as previously mentioned) maybe to try something less Lewis acidic than that such as sodium carbonate. It's possible there might be less yield loss to complex formation that way, although my mescaline-alkaline earth metal complex formation hypothesis is untested afaik so make of that what you will.

 

[downwardsfromzero]

The citric acid saturated butyl acetate has been evaporated. Gentle heat and forced airflow was necessary to speed this up.

10 grams of solution contained about 40 mg (35-45 mg, the scale sucks) of citric acid, so the solubility of citric acid in butyl acetate is about 4mg/g. It might just be worth it to give the rest of this experiment a shot.

Does anyone have solubility data for mescaline citrate in ethanol?

 

[Loveall]

With drying agents, if yield appears to go down when using Ca/Mg salts I'd suggest (as previously mentioned) maybe to try something less Lewis acidic than that such as sodium carbonate. It's possible there might be less yield loss to complex formation that way, although my mescaline-alkaline earth metal complex formation hypothesis is untested afaik so make of that what you will.

Thanks, yes I remember you mentioning that. Was planning to keep an eye on the yield.