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What are these crystals in my crude Syrian Rue extracts?

awalmartbag

awalmartbag

Rising Star
Hey,

I finally got my first Syrian Rue extraction in progress. Cooked in slightly acidic solution, basified with NaOH yesterday, but could not get all the liquid through the coffee filter, so I've been letting the wet solids air-dry.

I noticed some small, pure white crystals growing on top of the organic sludge. Anyone know what these are? Sodium acetate? Sodium hydroxide? Alkaloids (too good to be true, probably)?

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The Sofa Traveler said:
Did you clean/filter the acidic decoction before basifying ? I feel like there is a lot of gunk in your coffee filter which should not be there.
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I admit, I felt the same looking at it, though I did filter them through a cheese cloth, then a cotton plug, then a coffee filter. Maybe a different brand of filter? Or maybe I ground the seeds too finely?

When I had the seeds boiling, the solution also never turned a nice red color as seen in the guide, more a dark orange/brown. I added some vinegar after boiling off ~3/4 of the liquid to see if it would change. It did not.
 
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Transform said:
Sodium acetate and maybe sodium carbonate (from lye + atmospheric CO₂).

Best to let the freebase alkaloids settle out, before decanting off the liquid and washing the precipitate with distilled water. Settle again, decant and repeat.

Filtering crude harmala anything is a total pain and best avoided.
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Thank you. Could I avoid all that by doing a liquid-liquid extraction instead to separate the freebase? Maybe with limonene or toluene?
 
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To my knowledge harmine/harmaline are insoluble to only mildly soluble in most non polar solvents. I believe may be more soluble in DCM and chloroform however there are no reports I can find using these as extraction solvents.

I will do an extraction on some Syrian rue soon using DCM and see whether it works.
 
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To clarify, I should have said ‘most common NP solvents’.. as I’m sure there’s some out there that work. If you could get harmine freebase to dissolve in DCM or some other NP solvent, I imagine a mini A/B could clean it up a bunch. It would be very satisfying to get a nice harmine crystal.. I’ve always gotten a tan coloured powder that looks like dried crumbled clay.
 
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Hmm... I think I'll have to upgrade my equipment and try this myself. The guide I was looking at also yields a tan powder, even after repeated cleanup cycles.

For the final crystallization step, would you precipitate the base in NP solvent or the salt in water?
 
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awalmartbag said:
Thank you. Could I avoid all that by doing a liquid-liquid extraction instead to separate the freebase? Maybe with limonene or toluene?
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On a test tube scale as a pilot experiment, I've cleaned up harmala alkaloids by dissolving the first (ammonia-precipitated) freebase in butyl acetate and crashing with a solution of citric acid in either acetone ('CASA') or pre-wetted butyl acetate ('CASBA'). To dissolve the harmalas, I set up a small "column" (glass straw or Pasteur pipette) packed with the freebase and allowed the BA to percolate through until all of the material had dissolved except for a dark blob of "harmala crud". A similar method was used to prepare the CASBA, but CASA was simply made up in an Erlenmeyer flask, decanting away from any remaining undissolved CA excess.

Dropwise addition of either of these solutions using a pipette produced a dense precipitate of fine harmala citrate powder. I was planning to do some more tests on the precipitated salt but I ate it. I'd like to have tested for insolubility in acetone, since the BA leaves a BAnana flavour to the material which can be unappealing for some. It would be handy to be able to rinse this off with acetone.

The entire experiment requires repeating but with some actual figures for the harmala solubility. I did find a figure for CA solubility in BA, which should be on the record somewhere under @downwardsfromzero's posts. @_Trip_ experimented a little with using warm BA to pull from rue seed-lime paste but the solubility was too poor for that to be practicable. Possibly, the freebase harmala alkaloids precipitate from water in a more BA-soluble form.

Acetone was chosen for the mixed solvent citrate (CASA) precipitation because it has a much lower boiling point than BA, thus facilitating subsequent separation via distillation.
 
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Ethyl Acetate Approach for Harmala

Love ya work DFZ, For memory the EA stayed red after freezing precipitating the harmala. This wasn't crude harmala extracted EA. It was with already purified harmala that was then dissolved in EA to test freeze precipitation. Thanks 😊 I'll earmark a sample of freebase solution...
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downwardsfromzero said:
Here we have the long awaited pic of rue harmala citrates crashed from butyl acetate! (Summer happened and the test ideas got greatly simplified.)

Beaker on the left has relatively light fluffy stuff, yellow in suspension and orange-brown in bulk when still moist with solvent. On the right, a denser, olive-brown, clumpy material. Both display a similar fluorescence as seen in Loveall's photo.

This material was prepared by drip-leaching rue bases (precipitated from rue tea using ammonia) with butyl acetate through a cotton wool filter plug in a glass pipette. Black, insoluble material remained trapped in the filter. A differential solubility was observed (although whether this was noted down is another matter entirely... [EDIT: here they are!]) and this is what gave rise to the two fractions as seen in the photograph. One of them dissolved first, it doesn't entirely matter which, but it could at least be observed by the relative colour of the material in the extraction tube.

To the two resulting batches of orange-yellow solution was added a saturated solution of citric acid in moistened butyl acetate ('CASBA').

Moist butyl acetate was prepared by repeatedly shaking 100mL butyl acetate, fresh from the tin, in a stoppered measuring cylinder with ca. 2mL of distilled water several times for about ten seconds each time, followed by a short pause to allow droplets to settle. After this became too boring and it looked like no more water was being absorbed, a saturated citric acid solution was prepared by dripping the moist butyl acetate through another glass filter column with a cotton wool filter plug, this time filled with citric acid. The packet claimed this was anhydrous citric acid but that seems a tad spurious; it may well have been the monohydrate. Its hydration level was not assessed.

It is possible to be reasonably confident about the solution being saturated because the unused CASBA deposited crystals of citric acid quite readily owing to some evaporation of the solvent during storage, as well as the preparation method being a reasonable guarantee of producing a saturated solution.

The material in the photo is what remains after allowing the precipitates to settle and removing the supernatant.

Rinsing with fresh butyl acetate should remove any excess citric acid from solvent residues and evaporation thereof. If the solubility of citric acid is insufficient for this cleanup, a rinse with anhydrous acetone will be attempted, where there is a better solubility, but the solubility of harmala citrates in acetone is yet to be determined (as far as I'm aware).

More data to follow. Time for a pull from the seeds with BA, and I ought to get that chroma sorted too. Little (tiny) column is ready and waiting to be packed.
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Ethyl acetate may hold promise for freeze precipitation of harmala alkaloids:

Ethyl Acetate Approach for Harmala

Hey DFZ, how did your experiments go? Although the Tek has delivered good results it is still in developmental stage. I believe the lab results speak for themselves so I have (struggled to) add a wiki page. Feel free to add to it. I have also fixed some photos and hope to add more...
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Loveall said:
Hi _Trip_, this is great work, thank you 🙏

I'm finding a potential application where the EA extract is done later. Start as usual with the water/vinegar extracts and base precipitation Sakkadelic style.

Then, dry and extract the crude harmalas with boiling EA. It leaves a bunch of gunk behind and seems very selective. Indeed, upon cooling white free base harmala candidate begins to precipitate. It is sparkly and white I don't even need to salt. I think freezer temp will Xtalize a lot of the FB. The used EA should be usable for the next batch too.

So instead of:

- Acidic water extraction, base, decant, multiple water washes, manske, dissolve and base again, rinse, etc, etc, dry.

Another possible apporach could be simply:

- Acidic water extraction, base, decant, dry, EA re-X

Also, as FYI, I re-Xed the precipitated water pulls separately. The first pull had a lot more junk. For what it's worth, the ratio of junk/product is highest in the first pull. I think Sakkadelic mentioned doing a quick water wash before extracting to eliminate the junk up front without affecting product. That could make sense, junk solubility in water must be super high based on the re-x gunk I get from the 1st pull.
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Harmalas extraction-syrian rue (by SAKKADELIC)

After reading some harmalas extraction teks on this site and understanding the basic ideas in them i tried to follow a similar method but with some modifications that i made and after repeating few times it turned out to be good. i hope for this method to be helpful for all and a good...
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I've gone back to doing the EA harmala tek despite BWs no manske evidence. I still found it needed too much filtering and filtering time despite his methods. The EA harmala tek negates the slow filter times. The whole tek takea only a couple hours. For best yields you may need 2 runs. It can be a tricky tek at first, however if you familiar with cielo it's not much different. And the EA is recyclable. The other issue with the EA harmala tek is yeilds aren't consistently higher, they're always decent yields never low but still needs fine tuning to get one run high yeilds. Still 2 runs can be done in just over 3 hours. Microwave step is the biggest hassle at times (especially if using more starting material than less).



From lowest solubility to highest i found BA, the least soluble followed by acetone and EA for memory. On paper DCM should be the best solvent for harmala but I struggled to get a salt combo to precipitate harmala in DCM like citrate does with harmala and EA. I tried a number of salts but there's still more to test. DCM would likely increase yield but it's toxic stuff to work with.
 
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I've just noticed a comment in the wiki entry for Ethyl Acetate Approach for Harmala: on the use of butyl acetate

Ethyl Acetate Approach Harmala - DMT-Nexus Wiki

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where it is stated that harmala citrate does not crash from BA. This may be the case for BA pulls from a rue/lime paste on treatment with CA powder but, as reported above, I have successfully crashed harmala citrate from BA using solutions of CA in acetone or wet BA, when harmala base precipitated from water cooks had been redissolved in BA. This contrast may be due to impurities in the crude BA pulls direct from lime paste, or the use of solid CA, or both.

BA can be used as a purification step as per the question in this very thread, and it's more than likely that EA would fulfill this role equally well if not better.
 
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Might need retesting with BA then. I tested it with pure FB harmala and citric acid. So I'd wager you're right Transform, that it works as a 'wet' solvent with the lime paste as you've reported.

I need to update a few things in those notes it does, as one would have hypothesised, work for caapi too.
 
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_Trip_ said:
Might need retesting with BA then. I tested it with pure FB harmala and citric acid. So I'd wager you're right Transform, that it works as a 'wet' solvent with the lime paste as you've reported.

I need to update a few things in those notes it does, as one would have hypothesised, work for caapi too.
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Adding the caapi results would be awesome - that's great news!

I'm planning (still) to make my own attempt with BA and the lime paste, plus some further fiddling around with the dissolution and precipitation of already-isolated harmala freebase. Mostly because I already have the BA. I'm not sure of the exact details of what may have not worked [for you] with BA pulls on harmala/lime paste, so it's difficult to see what may have effected this divergence in results. As previously stated, my experiments were only performed on freebase precipitated from water using aqueous ammonia.
 
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@Brennendes Wasser recrystallised harmalas from DMSO:

Tracking Harmala-Separation & THH purification with NMR

I wanted to make some more THH and needed a new load of Harmalas. I was using different sources on about at which pH I need to stop freebasing ... my old protocol (retrieved from somewhere here) told to stop at pH 7. That is just neutral and therefore I was wondering if indeed you can already...
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DMSO takes forever to evaporate, though, so crystals from that method would require an additional cleanup before use in changa.
 
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Interesting. I was planning to take it orally with DMT, so I wouldn't be too concerned about some leftover ACS/pharma grade DMSO. Although I don't know how much that would throw off dosage measurements.

Seems like pure ethanol might be a viable re-x solvent too - 8g/L @ 78C, about the same as EA.

The high solubility in DMSO seems very appealing. I am tempted...
 
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awalmartbag said:
Interesting. I was planning to take it orally with DMT, so I wouldn't be too concerned about some leftover ACS/pharma grade DMSO. Although I don't know how much that would throw off dosage measurements.

Seems like pure ethanol might be a viable re-x solvent too - 8g/L @ 78C, about the same as EA.

The high solubility in DMSO seems very appealing. I am tempted...
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The success of recrystallisation seems to be predicated rather more on poor to mediocre solubility along with a favorable temperature/solubility slope. It seems BW was using deuterated DMSO-d₆ for the NMR experiment, I suspect on account of chloroform-d being too reactive to use with harmala freebase.

Speaking of reactivity, I'd draw your attention to @downwardsfromzero's observation that DMSO + HCl can oxidise indoles at the 2-position to form indolinones, which may be relevant in the context of DMT.
 
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