Harmine, harmaline and THH from Syrian Rue. Verification and finetuning of the VDS-protocols

[ijahdan]

I started separating another batch of mixed rue alks to get more harmaline to play with but having a few issues.

Firstly, I did 5 manskes, as in the VDS paper. This seemed to clean things up a lot. I dissolved the last batch of hydrochlorides in warm water, giving a clear reddy brown solution. This was divided into two parts so I could try different techniques on each batch without losing everything if things went wrong.

Anyway, I left both jars (each containing approx 5g mixed harmala hcl) in the shed for a few days. Had a few cold nights, not below freezing though, and when I had a look at them, there were loads of crystals formed on the bottom of the jars. Couldnt get them to redissolve, even after adding vinegar and heating so I filtered them out. Weighed only about 0.5g.

I dissolved sodium bicarbonate in cold water till saturated and then added this to the harmala solution (once it had cooled). Tan precipitate formed, presumed harmine. This was filtered off. Looked like a few grams, but havent dried and weighed yet.

Saturated sodium carbonate solution was then added to the solution to precipitate harmaline. Unfortunately on a tiny amount of very fine white powder precipitated. Again, havent dried and weighed but looks much less than the first lot.

I was thinking maybe the presumed harmine fraction actually contains harmaline too, so Ill probably redissolve it in vinegar water and try the sodium bicarbonate separation again. Dont have a pH meter, so not able to do more accurate pka based separation.

One more thing that might be affecting things is how dilute my solutions are. In trying to redissolve the crystals formed in the cold room, I added more water, ending up with 500ml per (approx) 5g harmala hydrochlorides. Plus some NaCl contamination from the manskes.

 

[An1cca]

Anyway, I left both jars (each containing approx 5g mixed harmala hcl) in the shed for a few days. Had a few cold nights, not below freezing though, and when I had a look at them, there were loads of crystals formed on the bottom of the jars. Couldnt get them to redissolve, even after adding vinegar and heating so I filtered them out. Weighed only about 0.5g.

What did the crystals look like? Surely not like harmala-HCl needles I suppose? By the way, the weight of post-Manske HCl-alkaloids is difficult to interpret. Freebases don't carry this salt-contamination and give a more exact picture...

I dissolved sodium bicarbonate in cold water till saturated and then added this to the harmala solution (once it had cooled). Tan precipitate formed, presumed harmine. This was filtered off. Looked like a few grams, but havent dried and weighed yet.

Saturated sodium carbonate solution was then added to the solution to precipitate harmaline. Unfortunately on a tiny amount of very fine white powder precipitated. Again, havent dried and weighed but looks much less than the first lot.

I was thinking maybe the presumed harmine fraction actually contains harmaline too, so Ill probably redissolve it in vinegar water and try the sodium bicarbonate separation again. Dont have a pH meter, so not able to do more accurate pka based separation.

This is indeed the way to do it. It takes about five cycles of bicarbonate-carbonate to get the two alkaloids separated. VDS did the same thing in experiment 2.4 and showed in his results that after 5 cycles, the two alkaloids were indeed separated.

However, if you're only interested in (a bit of) DHH, you should know that the alkaloid you precipitate with the carbonate is pure DHH. Only the bicarbonate fraction is mixed. So you could stop at anytime, using only the second precipitates of each cycle.

When using bicarbonate, do make sure all carbonic acid has reacted away before filtering (or filter multiple times until the filtrate doesn't get cloudy any longer).

One more thing that might be affecting things is how dilute my solutions are. In trying to redissolve the crystals formed in the cold room, I added more water, ending up with 500ml per (approx) 5g harmala hydrochlorides. Plus some NaCl contamination from the manskes.

In my experience, dilution did not affect yield a lot. Time and stirring however, did seem to matter. It has become clear from the experiments in this thread, that adhering to VDS's experimental conditions is a good idea. When in doubt, check there...

Thanks for joining the research Ijahdan, looking forward to hearing from you!:thumb_up:

 

[ijahdan]

Quote:
"What did the crystals look like? Surely not like harmala-HCl needles I suppose?"



No, they looked more like rock salt, big clear rectangular things. Tasted slightly salty and very bitter.

Good to know Im on the right track with the separation. Ill keep going with the bicarb/carb till Ive got a decent bit of harmaline to reduce, then hit it with the ammonia.

Cheers.

 

[ijahdan]

Update; I washed my harmine in water, let it settle and syphoned off most of the water (to remove any bicarb). Just out of curiosity, I added some ammonia to this water and was surprised when a lot of fine white powder precipitated. Thinking this might be bicarb, I added some ammonia to a saturated bicarb solution and nothing precipitated, so I assume it must be harmaline.

I then redissolved the harmine with a bit of vinegar water and tried reprecipitating with bicarb. Nothing came out, even after much stirring and waiting for it to stop bubbling, and even after adding more dry bicarb. So I added ammonia, which caused the solution to turn milky white. As it settled, I could see some brown precipitate (harmine?) gathering at the bottom of the jar, and lots of much finer white powder (harmaline?) settling on top of it.

Im thinking Ill redissolve this and try to precipitate again using ammonia, but just add drop by drop, hopefully being able to drop out just the harmine and stop the process when the harmaline starts forming. Using visual clues rather than measuring pH, which I cannot do accurately yet.

 

[Jees]

... I've seen harmine crystallize very much like harmaline and THH very much like harmine. Recrystallized on the slide however, they show their true nature...

That is exactly what I meant by saying it's not just pile-and-look. I've had wacky visual results with both in-vessel and in-situ crystallization.

One is solved, I've a satisfying workflow now for vessel-crystalized.
So for in situ you do not use a glass cover at all?(those small rectangle very thin glass things). I was doing drop stuff already but with not good enough result.

...I would have sworn Nexine to be DHH, but since it is not readily converted to THH, I don't have a clue anymore. Frodo, sorry I mean Jees, you are the only one that can walk the path to wisdom and liberate us from the dark abysses of ignorance :lol:...

In physical appearing, the difference with DHH is huge, both in suspension as is dried.
As for Frodo, did he really had a choice to refuse the whole operation?

How much nexine quantity was there compared to harmine/DHH/THH? Could it be harmane? Harmol? Harmalol? It looks loike sannnnnnnd......Thumbs up

I've never took weight because its soo fluffy I cared less. Not exactly professional I know
Well, if I encounter it again, I'll take ratio's

ijahdan great that you are trying also :thumb_up:
If I had no pH meter I would only rate the 5 cycled sodbicarb sodcarb procedure (page 22).

About those crystals you got on the bottom, I suppose also that these are not our crystal candidates of interest. Different behavior is very suggestive to different material.

And yes sodiumBIcarbonate will precipitate harmaline too. Therefore the 5 cycles method for good separation. Have you nailed the visual clues approach you're intend to use? I've never tried it really, I had this fancy pH meter to gleen on as you should too :lol:

 

[An1cca]

Update; I washed my harmine in water, let it settle and syphoned off most of the water (to remove any bicarb). Just out of curiosity, I added some ammonia to this water and was surprised when a lot of fine white powder precipitated. Thinking this might be bicarb, I added some ammonia to a saturated bicarb solution and nothing precipitated, so I assume it must be harmaline.

I too think that not all of your DHH was separated from the harmine. When I wash harmala alkaloids, I make sure the water is just a little basic. Just adding a small amount of ammonia will guarantee this and will evaporate in the end. Using plain water in my experience dissolves some of the alkaloid as can be observed by yellow coloration of your filtrate and (parts of) your residue.

I then redissolved the harmine with a bit of vinegar water and tried reprecipitating with bicarb. Nothing came out, even after much stirring and waiting for it to stop bubbling, and even after adding more dry bicarb.

This occured to me as well. What works for me is to keep on stirring until most of the carbonic acid is decomposed. Or just leave your recipient to stand. Harmine WILL precipitate in a concentrated bicarbonate solution.

So I added ammonia, which caused the solution to turn milky white. As it settled, I could see some brown precipitate (harmine?) gathering at the bottom of the jar, and lots of much finer white powder (harmaline?) settling on top of it.

The difference in color is caused by the 'cleaning' of the mother liquor by the first alkaloids to precipitate. This can be observed very clearly when filtering of fractions in a gradual pH-specific precipitation. The first harmine fraction is brown, while the following fractions (well before the cut-off at 7,5) are more off-white. So if you ran enough cycles, the whiter precipitates on top are just cleaner harmine.

Im thinking Ill redissolve this and try to precipitate again using ammonia, but just add drop by drop, hopefully being able to drop out just the harmine and stop the process when the harmaline starts forming. Using visual clues rather than measuring pH, which I cannot do accurately yet.

I agree with Jees that visual clues are too rough to give a proper separation. What I did observe though, was when filtering off multiple fractions of harmine, at a certain point the solution started to flicker. This was a clear indication of DHH starting to precipitate (and was microscopically confirmed). This flickering however was absent when most of the harmine was left in the mother liquor. So yes, visual clues will help you with separation, if you take the time and effort to filter out the precipitated harmine every so often. At a certain point, you will clearly observe flickering when tangential light is shone upon the recipient. At this point you can filter off your 'mixed fraction', base the mother liquor with excess ammonia/carbonate and filter off your pure DHH. The more fractions you are willing to take when nearing the cut-off, the smaller your 'mixed fraction' will be.

Good luck!

 

[Jees]

...I agree with Jees that visual clues are too rough to give a proper separation. What I did observe though, was when filtering off multiple fractions of harmine, at a certain point the solution started to flicker. This was a clear indication of DHH starting to precipitate (and was microscopically confirmed). This flickering however was absent when most of the harmine was left in the mother liquor. So yes, visual clues will help you with separation, if you take the time and effort to filter out the precipitated harmine every so often. At a certain point, you will clearly observe flickering when tangential light is shone upon the recipient. At this point you can filter off your 'mixed fraction', base the mother liquor with excess ammonia/carbonate and filter off your pure DHH. The more fractions you are willing to take when nearing the cut-off, the smaller your 'mixed fraction' will be...

This was something I wanted to say too, that visual clues might be possible, but one has to have experience in how a good separation looks like.

Another way I've succeeded once (and must try out more) is the visual separation during manske: at an exact amount of salting, the harmine will precipitate fairly fast as a loose powder at the bottom. Only after a long time after that, the DHH will start to form the very long needles. Too much salt spoiled this effect completely, but right on top then a real good separation is possible, sure good enough for our purposes. I can't state numbers like x gr salt on 100 ml because concentration of the alks and previous carried over salt play a huge role, the only way was to heat the soup really hot, add salt, dissolve, add salt,...., until you get & stay milky + precipitations at those high temps, then add some water to notch back step per step until half of that milk start to disappear, one must remain some definite mist. Done, your harmine only will drop out soon as powder at room temp. DHH much later as long needles. I think it was nexine free and there was done already a lot cleaning up when that happened. It was also a little batch, dunno how things work out on bigger batches. This approach needs some further testing but I found it good to mention the possibility already, maybe some people jump in to test along. But since I have that pH meter I'm not that much motivated to not use it.

* * *

The brown and the white precips I've seen that too, as long as they are not sticky spook goo Then I make nothing of it. It just covers the pH probe a bit but can be whipped of easily. Too bad that in some situations they can get sticky, something about concentrations and maybe CO2 too, VDS got around it (An1cca confirming). I wish I had so much material I could provoke and nail the true reason. Time will tell...

 

[ijahdan]

Finally figured out why I wasnt pulling much harmine with the bicarb. Went back to VDS paper and realised I wasnt adding nearly enough bicarb. He starts with 38ml water and 12ml vinegar to dissolve about 2g mixed alks, then adds 8g bicarb dissolved in 100ml water. I was adding about the same amount of bicarb to 500ml mixed alks in vinegar water!

So I started again, following VDS ratios (amounts adjusted for larger amount of alks) and also warmed the bicarb water slightly (only to about room temp, not enough to convert to carbonate) to help dissolve the right amount. This time, no problem precipitating. I'll do the carbonate pull next and then repeat 4x as in the protocol. Hopefully now this will work.

 

[An1cca]

I'm positive it will! How do you decompose your carbonic acid? By stirring? By waiting? By repeated filtering? By all three methods? Shaking would be an efficient method as well I guess, only a little harder to get your alks from the recipient later.

You see, if the carbonic acid isn't totally decomposed, it might be that the pH still makes it possible for some of the harmine to stay in solution. This isn't very plausible, given the fact that even most of the DHH precipitates out in each cycle as well, but I tink this is about the surest way to go. I eventually realized this after a cycle or three, so I hope that there is not much harmine contamination in my DHH. The LC/MS results will tell...

I'm having some interesting sessions with the different akaloids these last weeks. It's fascinating to investigate all the different ratios with their respective effects. There's enough research material for months or even years! For example, I have some strong arguments for thinking that THH does play a role in activating the nectar. In combination with harmine that is. But this is material for another thread in another place. The research done by VDS just made it accessible now.

Nice to have you on the team Ijahdan, good luck!

 

[ijahdan]

As far as carbonic acid goes, I stir vigorously at first for a few minutes and then again after everything settles. Then I leave with a loose cover overnight. This is mainly because I only have a short time to spend on stealthy chemistry sessions each night, but it probably helps everything to reach an equilibrium too.

Looking forward to sampling the different alks too. Hopefully next week sometime. Will try each one solo before combining and before adding any extras. Sublingual works well for me, and more economical...

 

[Jees]

...Nice to have you on the team Ijahdan, good luck!

I can't agree more.

Nice to see one progressing! To really do all this, then no doubt a thing or two will be learned :thumb_up:

 

[ijahdan]

Thanks Jees, and An1cca. Yeah for sure a lot of learning is taking place.

 

[Jees]

To all who survived 11 pages:
have you been paying attention?
What feast is this?

 

[Jees]

It tast sooo bad, it really stands out :twisted:

 

[Jees]

Not one wrong reaction :lol:
:thumb_up:

Time to meet an unexpected visitor:

it was an alleged harmaline batch of which I felt that it needed some cleaning up. It got a rigorous active carbon treat and re-precipitation under pH control. An extra manske was in there too. Base of choice: ammonia 6%. I expected to meet only harmaline and a dash harmine to separate.
. At harmine level, nothing;
. at 7.6 a definite pH depression to 7.2 and back up to 8
I did not know what to think of this, it's too high for harmine for sure, but if no harmine then all is harmaline? (little did I know).
. So based higher than 8 and a second pH depression set in.
I'll be danmed, this last one is the harmaline.
So the first is something between harmine and harmaline, but very close just under harmaline.

I wanted to do that again, so I used muriatic acid to get pH 3.
Basing again, now adding that muriatic acid changed the pH game in a way that the 2 pH depressions were there but shifted higher 0.5 pH or so. Again a lesson that thinking in absolute pH values is pointless, it's always drifting on many factors and it seems to be sensitive for drift.

So,the first weighted 560 mg and the harmaline 300 mg. Of this harmaline you saw the pics in the former posts.

The mysterious 560 got a photoshoot too.

This is the archetype of this crystal, diagonal south-west to north-east, 2 in axis spear like lobes and where they fuse: a left and right lobe.

 

[Jees]

So it is very axial and organic looking, far from harmine or harmaline who are much more alien looking. It cannot be fern-forms from harmaline because those ferns grow different and in these conditions normally no fern growing takes place.
They let me think of space rockets out of very old comic books.

Here you see some variants who have 2 sticking forwards and backwards, a minority but noticeable present for sure.

Picture: nice 2 ones, flying together and carrying a harmaline pellet on the back, what are they going do with it?
:shock:

 

[Jees]

So a crystal with a unique pH depression, close to harmaline and therefore some harmaline pellets present. The degree of contamination is small.

 

[An1cca]

Fascinating! And nice pictures too! I've never come accross these specific double spears... But I've sure seen some weird crystal forms. Especially harmaline is a master of disguise. If I understand well, these crystals were obtained during basification of the complete mother liquor? What do they look like when recrystallized on a slide? In my experience, this is when the masks drop off and the crystals show their true nature. And does this mean we now have yet another alkaloid joining the game next to the Nexine? Were you able to get some more pictures of that one?

Anyways, you're doing a great job at keeping the 11-page survivors curious! :thumb_up:

 

[Jees]

It came of this batch of which I thought was harmaline alone with maybe some impurities, maybe some harmine, and I had it pictured before like this: pellets and little ferns, no spears at all before the cleanup action.

The harmine was already out of it I'm sure of now.

After the cleanup (manske, AC cook, pH monitored separation):
I'm pretty confident it had it's own distinct pH depression close to but juts under the pH depression of harmaline, so I guess it's no harmaline in disguise. If it does turn out to be harmaline it seriously had me fooled, time will tell.

I won't claim it came out of the seeds though. A candidate hypothesis: activated charcoal cook with Norit had 65% of my harmaline converted into the new spear-forms. When I checked my food grade Norit it also contained titanium dioxide (E171) and iron oxide (E172) so maybe these did 'a job' on the harmaline?? But oxides are usually no good reducing agents at all, so no THH for sure. IIRC you used Norit too? Does yours have these additives? The one I have is capsules against diarrhea with impossible fine powder in it, the cleanup job was amazing but a bugger to get the carbon out. Many filtering necessary. Speaking of which, I know there is a product that is used to "catch" the carbon powder but lost it's name, anyone?

I'm still having issues with my in situ's It's getting better though. I don't understand why I get still wild results on the harmaline, it seems to play it's tricks in my in situ attempts. I do get some ferns for sure but also a lot of freestyling until now, I suspect that my basing on the glass is simply too fast? I'd like to get very consistent results and tbh my vessel crystals are quite indicative and satisfying so far. But I must get it sorted in situ also. I'll try and post.

What a hobby

 

[Intezam]

Masaru Emoto was a Japanese author, researcher, photographer and entrepreneur, who claimed that human consciousness has an effect on the molecular structure of water....loike many Japanese ppl, he spent his life studying ice-crystals.....:lol:


He might've known or not why our crystal grow forked horns :twisted:
BTW they have very good charcoal in the Japans...the lands of chrysanthemum charcoal....

[YOUTUBE]

apologies for breaking with scholastic adaab....