TEK Ethyl acetate approach [CIELO]

[Loveall]

I don't understand the result with the reused solvent.

If ethyl acetate does not separate the 3.9% yield, maybe consider converting to Mescaline HCl like _Trip_ did, or doing a mini CIELO TEK with fresh Ethyl Acetate.

 

[shroombee]

I don't understand the result with the reused solvent.

If ethyl acetate does not separate the 3.9% yield, maybe consider converting to Mescaline HCl like _Trip_ did, or doing a mini CIELO TEK with fresh Ethyl Acetate.

What's also interesting is 15 mg/gram of citric didn't form clouds. Adding the extra 10 mg/gram formed the clouds but produced the suspiciously large yield.

 

[downwardsfromzero]

I would imagine calcium chloride would do the same job, before salting?

I also gather sodium carbonate and calcium chloride won't affect the free base mescaline in the EA?


Where I'm from pellets aren't available but pool shops do stock pure calcium chloride in powder form. For those who can't get de-icer.


If calcium chloride doesn't react with FB mescaline I would be happy to try 5% before salting with citric acid on my next run.

I don't think pool supplies will stock calcium chloride. I think they would have calcium hypochlorite - bleaching powder - which has a formula corresponding roughly to CaOCl2.

If the product available through pool supplies lists a "free chlorine content" or something similar on its label DO NOT use it! Adding pool bleach to your mescaline/EA solution would be a VERY BAD IDEA!

Where I live, calcium chloride (CaCl2 - that's CL two, not cack twelve ) is available in general domestic supplies for use in dehumidifiers. Three refill sachets in a box costs next to nothing.

(OK, pool suppliers might conceivably sell electrolytic chlorine units which could use CaCl2 as a feedstock but I've never heard of them and neither am I a pool products salesperson so always check the label.)

 

[CuriousSeeker]

Thanks for the thoughts!

3.9% yield on your second extraction definitely sounds like too much. Have you tried washing with fresh ethyl acetate? That should leave the mescaline citrate. After evaporating the ethyl acetate you can evaporate it to yield the unknown alkloids. Curious whether they would be active.

This evening I mixed the 4.2 g tan crystals with 50 ml of clean ethyl acetate and the remaining filtrate is 3.5 g, moving the now 3.2% yield in a better direction, but still not within expectation. I'm wondering if maybe the washed solvent still had sodium carbonate saturated water in it which precipitated (hah!) these weird crystals. They are the texture of very coarse sand, or maybe sea salt, and very hard.

 

[Loveall]

I don't know why you got such different results with the washed ethyl acetate. Sodium Carbonate should stay our of the ethyl acetate rich layer in practice as I understand. The only significant thing that could remain in it is citric acid if not washed all the way. You could do a dummy run where you repeat your steps without cactus to verify (that's a bunch of work though).

Can you give more details of how you washed the used solvent? Did you check that the pH paper became neutral after washing the ethyl acetate (maybe not since it is not required). Did you freeze the EA and filter the ice xtals (again, maybe not since freezing is not required).

Perhaps we should all dry the ethyl acetate with sodium carbonate or CaCl2 after washing for reuse. Also, as mentioned before, maybe we should also chemichally dry the ethyl acetate extract before salting during the main TEK. That could be a more robust approach overall and give more consistent results among all of us (?).

Edit: In this example of ethyl acetate reclaim they chemichally dry it at the end. Not sure why they do two different water washes (first 5% Na2CO3, them saturated CaCl2 or NaCl) instead of going straight to a saturated Na2CO3 water wash like we do.

 

[shroombee]

Also, as mentioned before, maybe we should also chemichally dry the ethyl acetate extract before salting during the main TEK. That could be a more robust approach overall and give more consistent results among all of us (?).

I thought we need a little water (but not too much) in the extract to facilitate the xtalization?

 

[_Trip_]

I thought we need a little water (but not too much) in the extract to facilitate the xtalization?

In few runs I have done I have had a decrease in yield if water is present. Learnt this the hard way first run through.

I don't think pool supplies will stock calcium chloride. I think they would have calcium hypochlorite - bleaching powder - which has a formula corresponding roughly to CaOCl2.

Pool shops certainly do, well where I live anyway.

It's called calcium increaser and it is 100% Calcium Chloride CaCl2. I think it is in dihydrate form I don't know if that would affect it though. Also it is not grannulated but in chunks similar to de-icer i would imagine. And it seemed to work fine on small test run.

 

[downwardsfromzero]

downwardsfromzero wrote:

I don't think pool supplies will stock calcium chloride. I think they would have calcium hypochlorite - bleaching powder - which has a formula corresponding roughly to CaOCl2.


Pool shops certainly do, well where I live anyway.

It's called calcium increaser and it is 100% Calcium Chloride CaCl2. I think it is in dihydrate form I don't know if that would affect it though. Also it is not grannulated but in chunks similar to de-icer i would imagine. And it seemed to work fine on small test run.

Thanks for clearing that up for me. Admittedly my knowledge is restricted to the pool supplies aisle of DIY stores in Germany and the UK. I still find it a bit odd though. "Calcium increaser" :lol: - it's surprising to hear of the various uses that get thought up for what is something of a waste product. And to think that some people go to considerable effort to remove calcium from their water while others are paying to put it back in!

The dihydrate is capable of absorbing just short of 50% of its own weight of water to form the hexahydrate.

 

[_Trip_]

Thanks for clearing that up for me. Admittedly my knowledge is restricted to the pool supplies aisle of DIY stores in Germany and the UK. I still find it a bit odd though. "Calcium increaser" :lol: - it's surprising to hear of the various uses that get thought up for what is something of a waste product. And to think that some people go to considerable effort to remove calcium from their water while others are paying to put it back in!

The dihydrate is capable of absorbing just short of 50% of its own weight of water to form the hexahydrate.

Haha yeah for "increasing pool calcium hardness" whatever that means.

Thanks downwardsfromzero for the information on absorbing 50% that'll help me factor in how much to add when reusing solvent.

 

[CuriousSeeker]

Can you give more details of how you washed the used solvent? Did you check that the pH paper became neutral after washing the ethyl acetate (maybe not since it is not required). Did you freeze the EA and filter the ice xtals (again, maybe not since freezing is not required).

I washed the solvent as per the tek, though I didn't take notes during the process. I started with about 750 ml of used ethyl acetate, calculated 20% by volume and weighed an equivalent amount of water (1 ml = 1 gm), then added 35% of that by weight of washing soda. I added the saturated water to the solvent and shook vigorously, stopping frequently to release gas bubbles. I did check with pH paper and found it to be neutral. The solvent was decanted from the water and I didn't notice any water droplets remaining when I used it for the next extraction.

 

[Loveall]

Also, as mentioned before, maybe we should also chemichally dry the ethyl acetate extract before salting during the main TEK. That could be a more robust approach overall and give more consistent results among all of us (?).

I thought we need a little water (but not too much) in the extract to facilitate the xtalization?

Great question. I remember that I thought I experimentally saw that at one point. So much stuff was going on, I need to repeat. Also, I was drying with MgSO4 which is slightly acidic and could cause other issues. I want to try again using an alkaline drying agent only.

For a while I had been dismissing systematic solvent drying, but as more people do the TEK, water content seems to be a source of variability. Maybe by controlling properly with an alkaline drying agent the TEK is more robust for everyone (?).

 

[Loveall]

Can you give more details of how you washed the used solvent? Did you check that the pH paper became neutral after washing the ethyl acetate (maybe not since it is not required). Did you freeze the EA and filter the ice xtals (again, maybe not since freezing is not required).

I washed the solvent as per the tek, though I didn't take notes during the process. I started with about 750 ml of used ethyl acetate, calculated 20% by volume and weighed an equivalent amount of water (1 ml = 1 gm), then added 35% of that by weight of washing soda. I added the saturated water to the solvent and shook vigorously, stopping frequently to release gas bubbles. I did check with pH paper and found it to be neutral. The solvent was decanted from the water and I didn't notice any water droplets remaining when I used it for the next extraction.

Well that checks out. I can't think of why this reused solvent gave such different results for you. The main difference after this wash is that it has a little water in it compared to fresh ethyl acetate.

Maybe we do need to control the water and do a chemical dry before reuse so we all get more consistent results. Did you freeze the ethyl acetate and filter the ice before reuse? If not, then you had more water in your solvent than _Trip_ and me I believe. However, the TEK does allow for that as written (it could be that you found a bug in TEK: solvent washes not compatible with room temp extraction?). However, I don't understand the that could have caused an issue or what was the extra stuff that was came through.

 

[Loveall]

Thanks for clearing that up for me. Admittedly my knowledge is restricted to the pool supplies aisle of DIY stores in Germany and the UK. I still find it a bit odd though. "Calcium increaser" :lol: - it's surprising to hear of the various uses that get thought up for what is something of a waste product. And to think that some people go to considerable effort to remove calcium from their water while others are paying to put it back in!

The dihydrate is capable of absorbing just short of 50% of its own weight of water to form the hexahydrate.

Haha yeah for "increasing pool calcium hardness" whatever that means.

Thanks downwardsfromzero for the information on absorbing 50% that'll help me factor in how much to add when reusing solvent.

It is possible to dry CaCl2 in the oven also. However, dry pellets are so cheap that it is better to buy anhydrous if easily available. Check the brewery supply store, they may have some there (used to harden water for certain beer styles).

If drying CaCl2 in the oven, heat up slowly in incremental steps and stir frequently. Otherwise, if heated too quickly, CaCl2 dissolves in the heat as water is released and turns into an extremely hard block.

Also, I'm pretty sure Sodium Carbonate can dry ehtyl acetate. If making it from sodium bicarbonate in an oven it should be anhydrous to begin with

 

[CuriousSeeker]

Did you freeze the ethyl acetate and filter the ice before reuse? If not, then you had more water in your solvent than _Trip_ and me I believe. However, the TEK does allow for that as written (it could be that you found a bug in TEK: solvent washes not compatible with room temp extraction?). However, I don't understand the that could have caused an issue or what was the extra stuff that was came through.

I did not freeze the ethyl acetate, though before the second extraction I let it sit overnight and the next day observed a little water (25 mils.?) on the bottom of the jar, which I removed. My 'room temperature' in the garage was about 90 F, so maybe that made a difference?

If my odd crystals have anything to do with too much citrate, would the "dropping acid" approach using less (5 grams?) work better?

 

[Loveall]

Did you freeze the ethyl acetate and filter the ice before reuse? If not, then you had more water in your solvent than _Trip_ and me I believe. However, the TEK does allow for that as written (it could be that you found a bug in TEK: solvent washes not compatible with room temp extraction?). However, I don't understand the that could have caused an issue or what was the extra stuff that was came through.

I did not freeze the ethyl acetate, though before the second extraction I let it sit overnight and the next day observed a little water (25 mils.?) on the bottom of the jar, which I removed. My 'room temperature' in the garage was about 90 F, so maybe that made a difference?

If my odd crystals have anything to do with too much citrate, would the "dropping acid" approach using less (5 grams?) work better?

Yeah, when warmer, ethyl acetate should hold more water.

Drop acid or stir should both work as far as I know, but my solvent reclaim condition was different than yours because I chilled the solvent and filtered the ice.

I do think we may need better water control in the TEK. I'm going to test chemical drying to again (extract and reclaim). If I see no issues, I suggest we add these steps to the TEK. Even if there are no improvements in my particular case, it could make results a lot more uniform for everyone. Can't hurt to control one of the variables better anyway.

I think I'll test using Na2CO3 as the drying agent. Very available to everyone, can even be made starting with baking soda in an oven. Would also be multipurpose during cleanup. I don't like MgSO4, it becomes wispy I'm ethyl acetate and I've had issues with it and this particular solvent. CaCl2 could be a good option, but it can be confusing to source anhydrous pellets, and it can be difficult to dry the hydrated since they can form a "cement" block in the oven.

If would be nice if controlling water makes the TEK more robust and xtalization goes a lot more similarly for everyone.

As I said before, in the professional lab, chemichally drying the solvent water contact is standard, so we would just be making the procedure more standard.

 

[shroombee]

I do think we may need better water control in the TEK. I'm going to test chemical drying to again (extract and reclaim). If I see no issues, I suggest we add these steps to the TEK. Even if there are no improvements in my particular case, it could make results a lot more uniform for everyone. Can't hurt to control one of the variables better anyway.

The inconsistent results people are seeing may be due to water, other alkaloids, plant matter, or a combination of all three. Maybe there's others?

Before recommending a chemical drying process, can we investigate the degree in which water impacts xtalization. For example, take an extract and split it into four jars. Use one as a control and add a different amount of water to each of the other three. Then salt with citric acid. Note the ease/difficulty of xtalization and resulting yield.

 

[_Trip_]

Before recommending a chemical drying process, can we investigate the degree in which water impacts xtalization. For example, take an extract and split it into four jars. Use one as a control and add a different amount of water to each of the other three. Then salt with citric acid. Note the ease/difficulty of xtalization and resulting yield.

Not a bad idea but my money is on the jar with less water.

Just thought I would share, I've mentioned this before. On my first run through I froze my ethyl acetate as the mescaline citrate precipitation was horrible. Although there was no visible water layer in my EA, when frozen, floating ice crystals formed in the ethyl acetate. I filtered the floating ice crystals out and put it back in the freezer. When I checked in the next day I again had more ice crystals but this time had a white frozen layer at the bottom. The white layer was recovered and indeed turned out to be mescaline citrate. Leading me to believe water was bad for mescaline citrate formation.

Long story short after rescuing the mescaline citrate I put the same jar of EA back in the freezer. Yet again ice crystals formed (so there was still a small amount of water hidden in the EA) but no mescaline citrate formed as I seemed to have already recovered it.

Now, after each experiment I used this same jar of EA (the one that still had some ice crystals in it) as a collection jar for all my used EA from following experiments and left it in the freezer. So the jar now had about 3 experiments worth of used EA. No mescaline citrate crashed out but there were a few floating water ice crystals in there.

However, the other night I put some CaCl2 pellets in the jar, put it back in the freezer and forgot about it. When I checked it the next day. There was no floating 'water' ice crystals but I had what appeared to be a white frozen layer of mescaline citrate (just like the first run through I tried), stuck to the bottom of the jar and next to it was a separated green layer of sludgy water (which I believe to be the CaCl2, water and possibly some other impurities?).

Which reinforces my believe that when water content is low more mescaline citrate can crash out. However, this time I couldn't rescue the mescaline citrate layer to confirm it was indeed mescaline citrate due to the fact the green sludgy layer wouldn't separate cleanly from one another. The green sludge just stuck to everything and couldn't be decanted properly.

I'm still experimenting to separate the two.

I'm having trouble embedding the image here's a link.

20210731 210103[1] — Postimages

postimg.cc

 

[downwardsfromzero]

Quick question about troubleshooting cloudy solvent: what do any of you think causes solvent pulls to become cloudy? It very much appears to be from the calcium hydroxide. Perhaps a more thorough mixing is necessary at the very first stage, making the milk of lime? I was going to read through the whole thread again having some recollection of this having been discussed previously but it's got a bit late in the day for that.

Another possibility is that way too much lime was used, 80g instead of 30g (well, even 24g would have sufficed for the amount of plant material).

 

[_Trip_]

Quick question about troubleshooting cloudy solvent: what do any of you think causes solvent pulls to become cloudy? It very much appears to be from the calcium hydroxide. Perhaps a more thorough mixing is necessary at the very first stage, making the milk of lime? I was going to read through the whole thread again having some recollection of this having been discussed previously but it's got a bit late in the day for that.

Another possibility is that way too much lime was used, 80g instead of 30g (well, even 24g would have sufficed for the amount of plant material).

Speaking for myself, I've found sticking with the ratios in the Tek, using the microwave and cold pull option as well as filtering with a lab filter before adding citrate, gives a clear clean solvent (still an off yellowy green but clear). I still have a belief water is the issue. I've notice that if water is present and you freeze and then filter out the "floating ice water", the water has a lot of gunk in it when evaporated. Even though you may not see a water layer; what little is in the EA may be collecting other alkaloids and causing a cloudy solvent. Just a theory from what I've observed with. Could very well be a lime issue or something else.

 

[downwardsfromzero]

Yes, following all the guidelines of an optimised method is obviously best. The 80g lime was purely the result of an outburst of cognitive flatulence, alongside the whole attempt being an experiment outside the parameters of the CIELO tek: butyl acetate was used - as ethyl acetate was not readily available - and the cactus powder was from rotten cactus which may as well have ended up in the compost if it wasn't for this. Not only that, but owing to the poor solubility of citric acid in butyl acetate, CASA was used prior to adding a further amount of solid citric acid.

Perhaps unsurprisingly, the turbidity passed clean through a coffee filter, btw. And microwaving wasn't possible due to the use of a stainless steel bowl :6

A couple of useful data points have been derived here: citric acid does not precipitate when CASA is added to butyl acetate up to about 10%, and butyl acetate absorbs sufficient water that about a tablespoon of floating ice crystals forms at -22°C from 300mL.

Clouding occurs when CASA is added to the BuOAc plant extract (at least with a late, clear fraction that was recovered from the lime paste after about 18 hrs) but further crystallisation has yet to be observed after refrigeration.

The use of chilled solvents was problematic due to condensation forming because of high humidity. With solvents from the freezer this was even worse. Anhydrous sodium carbonate went some way towards drying the solutions; after placing the citric acid treated extracts in the freezer overnight further observations will indicate whether additional drying might prove necessary.

With any luck, some aspects of this mess will clear up over the coming days and there'll be something more worthwhile to report in due course. If it gets properly knocked into shape it'll get its own thread.