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

Migrated topic.
Jees, I have a lot of respect about your work on the matter of this thread, and I do not want to fill it with my stuff nor to proof that I am right and so on...
In fact, we are just speaking about Harmalas-HCl solubility in hot and cold water.
Please tel me if you prefer we move this discussion somewhere else.
The set-up described above, allowing at each cycle to do a hot and a cold filtration, makes very pure xtals. After few re-x cycles, let say 10, I am quite sure there no more any mesurable quantity of NaCl.
Anyway, I wanted to check your suggestion and I did some Harmalas-HCl without NaCl, from a very well washed freebase and HCl acid. I dried it and kept it open air at 80 deg for 2 hours after that there was no HCl smelling anymore. I dissolved the residue in a 95 deg hot water up to saturation, pH was about 6.5-7. This solution crashed at room temp. So NaCl does not seems to be the cause.
I will ask in the "FAQ" if anyone has some data about the solubility, then we will have a better base to discuss.
Cheers
 
If it is not salt doing the precipitation, then it must be concentration. Your method is certainly performed at a huge concentration we are not accustomed to. It certainly doesn't happen at the concentrations where normal manskes are performed. My personal guide is to target about 100ml for each gram harmalaHCL, at that concentration it is impossible to crash out harmalaHCL's in a fridge, been there enough and others too like exquisitus said.

Then another thing: we do not know how the quinazolines behave in your proposed cleaning up. If they also follow what the harmalas do, then its not cleaning up the way I like it to be, but we do not know that at this point. We do know that sequential manskes do rid of the quinazolines, and I am fairly sure one needs 5 at least to succeed in that for my liking.
Well maybe if your system works at high concentrations to also rid of them quinazolines, then this might be a valid route.

All this can be checked by performing a manske after your suggested series (which is only one manske followed by several hot/cold transitions), but then keep the filtrate of this latter manske and base it to see what falls out.

I will check your proceedings at high concentration levels and if I concur then we can certainly move it a separate thread :thumb_up:
 
Can't this just be a classic recrystallization procedure you're performing, Michel? Seems obvious that when you drop the temperature of a saturated hot harmala.HCl-solution, crystals will form. Like you suggested, solubility data might help us out here...

BTW, nice to have some more researchers digging into the wondrous world of harmala's, most welcome!
 
Then there is another unknown factor (if your system works): will harmaline, DDH and potentially THH follow alike? It would be a pity to loose one of them.
And also if each hot/cold run looses noticeable yield in general?
There's work to do 😉
 
BioTron said:
I went back and reread the results portion of the VDS paper. That is great, easier than I expected it to be. He pretty much wrote the tek. for us already, so long as his procedure is followed, the results should be(and thus far have been) replicable.
Click to expand...

Biotron, in my experience VDS's procedures are indeed correct, although it should be noted that I could only replicate his findings under CONSTANT STIRRING (I used an improvised magnetic stirrer) and under SLOW ADDITION OF BASE.

BioTron said:
As the addition of ammonia proceeds, the pH increases pretty rapidly until the first depression, then harmine precipitation occurs. Harmine precipitation continues to occur progressively slower up until the point just before the second depression. Looks like a safe bet would be to stop precipitating the harmine at about pH 7-7.5, then dropwise add more ammonia until the next drop produced no increase in pH(this is where I need to get me a microscope!), filter off the rest of the harmine, then go ahead and drop out the harmaline.
Click to expand...

I think the italics above should be: '...to stop precipitating the harmine at about pH 7.0, filter off about 95% or more of your harmine and continue adding ammonia dropwise until the pH crashes from above 7.5 to somewhere far lower, filter again to collect your 'mixed fraction' and then proceed with 'bombing out' the DHH.'

BioTron said:
BTW, those crystals grown from slow gassing with ammonia are gorgeous!
Click to expand...
I too was amazed by their beauty :love:
 
Jees said:
If it is not salt doing the precipitation, then it must be concentration. Your method is certainly performed at a huge concentration we are not accustomed to. It certainly doesn't happen at the concentrations where normal manskes are performed. My personal guide is to target about 100ml for each gram harmalaHCL, at that concentration it is impossible to crash out harmalaHCL's in a fridge, been there enough and others too like exquisitus said.

Then another thing: we do not know how the quinazolines behave in your proposed cleaning up. If they also follow what the harmalas do, then its not cleaning up the way I like it to be, but we do not know that at this point. We do know that sequential manskes do rid of the quinazolines, and I am fairly sure one needs 5 at least to succeed in that for my liking.
Well maybe if your system works at high concentrations to also rid of them quinazolines, then this might be a valid route.

All this can be checked by performing a manske after your suggested series (which is only one manske followed by several hot/cold transitions), but then keep the filtrate of this latter manske and base it to see what falls out.

I will check your proceedings at high concentration levels and if I concur then we can certainly move it a separate thread :thumb_up:
Click to expand...

Hey Jees, what makes you conclude that you only get rid of vasicine-related compounds with 5 manskes? I'd have to go back to the results of my tests but im pretty sure after one or two manske you already had undetectable levels of those compounds.

Michel, when you said "The first Manske converts the FBs into their hydrochloric salts because they precipitate from the cold solution well actually they wont be in freebase form in solution, If it was a rue tea, either you added acid or the seed itself has natural acids, which means the harmalas will be in some salt form in solution. But excess NaCl will change whatever salt form it is in, into HCl salt, because it is a stronger acid. At least thats how I've understood it.


I may be reading it wrong but I think all of what you guys are saying can be simultaneously true. It could be there is some salt contamination after Michel's first manske to some or other extent, but its also possible that even with negligible salt contamination, harmala HCl could re-x in cold water. I haven't tested it myself but would be nice if other people would confirm it.

Also, did any of you guys test that yet with the separated THH?
 
Endlessness said:
Also, did any of you guys test that yet with the separated THH?
Click to expand...

...I wrote some experimental details and added some pictures of a THH-manske in post #112...
 
endlessness said:
...Hey Jees, what makes you conclude that you only get rid of vasicine-related compounds with 5 manskes? I'd have to go back to the results of my tests but im pretty sure after one or two manske you already had undetectable levels of those compounds...
Click to expand...
We might not have done same manskes in terms of concentration, salt levels, temperature, etc, so different outcomes are more than likely.

When I do a series of manskes then I usually base the filtrate to see whats gets (usually with exception of the first). Few days ago, after 5 manskes, I was still surprised to base out that typical slime layer at the bottom. After 3 more manskes the amount of slime was so little I called it enough. As long as slime bases out in the manske filtrate, I find my product getting cleaner at each step so I do not consider it overkill.

What is that slime? Perhaps it's premature of me to think of quinazolines only, you might have a point. There's perhaps more in the seeds than that, anyway whatever it is (maybe not quinazolines after all) I want it out because I see the product getting cleaner each time.
Why did I attribute quinazolines with that slime? Because the first manske filtrate, once based, here are certainly quinazolines rock'n rolling, and is one big slime layer, hence. Try to filter it, it's a big mess.

-

We know VDS is not a rookie in the matter, he also suggest 5 manskes in his paper, if not for reasons I do not know, or reasons he doesn't bother us with, the visual clue speaks proof enough that such a series gives really nice crystals.

Mind this thread is about pH-depression-separation/Zn.reductions and preparing for that exactly. For simple use of harmalas straight away, none of this purification drilling is necessary. Personal differences in goals can have immediate repercussions on workflow, heck I did years on only 1 manske with great result, but I was not trying to follow a VDS protocol back then. For me so far a good pH depression indication and very clean material goes hand in hand.
 
Michel, when you said "The first Manske converts the FBs into their hydrochloric salts because they precipitate from the cold solution well actually they wont be in freebase form in solution,...
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:shock: you are absolutely right! Its my mistake, it makes no sens since the FBs are not soluble. Manske converts the Harmalas natural salts present in Rue (or acetates if vinegar was used). Thank you to point it out, I will edit my post.
But excess NaCl will change whatever salt form it is in, into HCl salt, because it is a stronger acid.
Click to expand...
I am not sure to agree with this statement. I do not know why a stronger acid should displace a weaker one.
But if a product of a reaction leave the medium as precipitate or as gaz, then for sure the equilibrium will be displaced in order to compensate the loss of the product. Inside the liquid, the equilibrium looks like this:
Harmine Acetate + Sodium Chloride <=> Harmine Chloride + Sodium Acetate
When the temperature drops, Harmine Chloride start to precipitate making the equilibrium to move to the right side, which results in a complete reaction and precipitation. This is my understanding, but I am not chemist.
 
An1cca said:
...BTW, nice to have some more researchers digging into the wondrous world of harmala's, most welcome!
Click to expand...
Absolutely !!

Hey Michel when An1cca came up with OP there was no immediate acceptance also. Please do not consider it a form of "being hurt" as you put it in that other thread. What VDS found was quite in contrast with existing ideas about separating harmalas, before that only pKa based separation was widespread. All critics will fall in their place in due time, and as endlessness said everybody can be right given the different circumstances, we just have to dig it out by peer experiences. Glad you're around, we need investigating minds :thumb_up:
 
Jess..

We tested the precipitates after manske and they are mostly harmalas. For some reason harmalas dont all precipitate with manske.

Michel, you might be right about the equilibrium equation, I'm not a chemist either, I just learned from being in the Nexus and practicing :)
 
Thank you Jees.
My problem is to have only a 50 words vocabulary, so sometime I say the wrong one...:oops:
You did not hurt me anyway ! Peace !
 
endlessness said:
Jess..We tested the precipitates after manske and they are mostly harmalas. For some reason harmalas dont all precipitate with manske...
Click to expand...
Yes I knew of that analysis. My 8th manske filtrate got first based with ammonia to recover 170 mg of typical harmala crystals according to the microscope. So I agree, no doubt. But then based further with lye and then the slime precipitated instead of crystals. For me that is enough proof the slime is no workable harmalas, at a practical level. As much as I love analysis I also love my eyes. If the slime was harmalas, then why the cleaner product each time by continuing manskes?

Michel said:
My problem is to have only a 50 words vocabulary...
Click to expand...
Language is tricky, peace indeed :thumb_up:
 
Michel said:
Michel, when you said "The first Manske converts the FBs into their hydrochloric salts because they precipitate from the cold solution well actually they wont be in freebase form in solution,...
Click to expand...
:shock: you are absolutely right! Its my mistake, it makes no sens since the FBs are not soluble. Manske converts the Harmalas natural salts present in Rue (or acetates if vinegar was used). Thank you to point it out, I will edit my post.
But excess NaCl will change whatever salt form it is in, into HCl salt, because it is a stronger acid.
Click to expand...
I am not sure to agree with this statement. I do not know why a stronger acid should displace a weaker one.
But if a product of a reaction leave the medium as precipitate or as gaz, then for sure the equilibrium will be displaced in order to compensate the loss of the product. Inside the liquid, the equilibrium looks like this:
Harmine Acetate + Sodium Chloride <=> Harmine Chloride + Sodium Acetate
When the temperature drops, Harmine Chloride start to precipitate making the equilibrium to move to the right side, which results in a complete reaction and precipitation. This is my understanding, but I am not chemist.
Click to expand...

Yes it has nothing to do with pka or HCl being a stronger acid, Cl- ion is what you are adding and it is infact an extremely weak base, many degrees weaker than the acetate ion. So with this logic it is actually the reverse... but this is not the driving factor in the equilibrium, concentration is.

Manske is a result of the common-ion effect , harmaline/harmine HCl is very soluble in cold water by itself, it is the large excess of chloride ion, that is having an effect on the equilibrium of total dissolved ions, to push out the HCl salt. So it doesn't matter how basic Cl- is, it just needs to accept a proton and it falls out of solution. It doesn't matter how basic Cl is at all because harmala/harmaline are where you are going to find the proton...

remember in solution there are no salts, it is a mixture of many different charged ion species

--

understanding this it is reasonable that not all the harmalas will precipitate as HCl salt with the manske, as it will only proceed to equilibrium. The common-ion equilibrium is not the same as an A/B equilibrium, which you can see with pKa curve can easily be pushed >99% by adjusting pH. What you could do to get more harmala out of the manske is collecting the first crop of crystals from the fridge, reheating the filtrate to boiling, saturating again with more salt and sticking it back in the fridge
 
Jees said:
endlessness said:
If you can do that again or still have some of that slime, lets test it :)
Click to expand...
Would be awesome, next batch I'll try to catch it. :thumb_up:
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Some of the manske "waste water" precipitate we had analyzed was slime from an extraction of mine, which showed to be mostly harmalas. I'd love to see what results of your slime show. My money is on harmalas, and my guess is it has something to do with harmalas being incredibly water soluble alks (consider how yield can be lost through washing FB precip with ph neutral water).
 
SB I really think your slime and mine is the same, and pitubo once mentioned having slime too, ehh whats in a word 😁
So it could be indeed another manifestation of harmalas besides crystal form, now I'm with you guys it's prolly no quinazolines. Can't beat analysis.

After the 5 manskes I got a dry weight harmalaHCl's, also after 8 manskes, and lost like 610mg over the 3, being 200mg loss over each manske on average or +/- 5% each time. Extrapolated I lost 1.6 gr over the 8 which is considerable. Ending now on 5.5gr HCl-form from 100gr dry seeds.

I know to be able to gain 97 to 98% yield on a A/B transition so that's half the loss than a manske. I had no A/B cleaning-up steps this time, first time doing so. Instead choose for more manske-ing. Since I've a better idea now, next time will be more A/B's initially till clean and minimizing manskes afterwards, back to my old workflow.
Thank you guy's :thumb_up:
 
endlessness said:
...
But excess NaCl will change whatever salt form it is in, into HCl salt, because it is a stronger acid. At least thats how I've understood it.
...
Click to expand...
Now I understand better what you said, and it seems that it is "also" right.
I found this very old answer from Infundibulum to you here:

Infundibulum said:
endlessness said:
what happens if a substance that is already in salt form (such as dmt in mimosa, hypothesized to be dmt tannate, according to 69ron), is put in a medium with another kind of acid (such as vinegar, or hcl).. Does the dmt change to acetate or hcl, for example, or does it continue being the original salt?
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Yes, in theory ACID + SALT -> NEW ACID + NEW SALT, so dmt acetate mixed with a HCl solution is going to produce dmt chloride and acetic acid.

This is the case when (as acolon said) dmt salt goes from "product of a weaker acid" to "product of the stronger acid"
Click to expand...

So we have tree effects which are all pulling towards the same direction:
- weak -> strong acid
- precipitation of a product
- common ion effect
There is no point to say that one is the right one and the others no, as I did...:thumb_up:
 
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