• Members of the previous forum can retrieve their temporary password here, (login and check your PM).

Harmalas - HCl solubility in hot and cold water

Migrated topic.

Michel

Rising Star
Dear All,
I would like to know if anyone has any datas about the solubility of Harmine, DHH and THH HCl salts in hot and cold water.
I found them enough soluble in boiling water to allow to re-x them just with water.
It seems that this hurts some specialists, so I would like to check with officials datas if possible.
Google did not find anything trust-able.
Thank you very much for your help !
 
Hard to get numbers on this :?: .

I promised you to check on your suggested hot/cold clean up method for harmalaHCL. I did not follow your funnel setup to make it easier for me, my HCL's did not needed any cleanup actually but this endeavor changed into trying experimentally to lift a veil on min and max concentrations where this system seems to work.

First establishing the minimal water needed to perform a kind of clean up, one should have at least some watery phase to poor of after the cold crystallization. If there's no (or too little) water to poor off, then there's also no cleanup possible.

In pic is 1 gr harmalaHCL drifting on boiling water awaiting some water to drop on.
First I added 5 ml of demin water that barely dissolved the 1gr. Once cooled there was no water layer to poor off, all looked solid.

Thus back in the pan, adding another 5 ml, all dissolved, back into fridge, after 12 hours aprox 50% was crystallized, hmm that goes slower than a manske for sure. Next day more was crystallized as in the second picture.

I decided this is too little water layer to poor off, this is no possible cleanup (tho I need none, its a simulation). I estimated how much water I should definitely need to have a layer poring off worth the name 'cleanup', and decided to go for 25ml in total, so added 15ml. This is now in the fridge and we'll see tomorrow how much its crystallized and how much water can be decanted.
 

Attachments

  • 001m.jpg
    001m.jpg
    207.4 KB · Views: 0
  • 002m.jpg
    002m.jpg
    208.4 KB · Views: 0
Hello Jees, thank you for your interest !!!
In my opinion and if I understand well, you get already an important result:
Jees said:
...
In pic is 1 gr harmalaHCL drifting on boiling water awaiting some water to drop on.
First I added 5 ml of demin water that barely dissolved the 1gr. Once cooled there was no water layer to poor off, all looked solid.
...
My experiment with the funnel was precisely to filter the saturated solution before it cools!; it sound complicate, but is really easy:
Assume that the 1 gr harmalaHCl solid is at the bottom of a funnel, sitting on the cotton ball. Then the boiling water is poured slowly. This water will dissolve instantly some solid xtals and pass through the cotton ball. So insoluble impurities are removed.
Now, to keep the funnel hot, one has to place the complete device in a steam bath (high pan + lid).

The other part of the cycle is also easy: after the filtrat cools and crashes cleaner xtals, the content is poured back into the funnel, (one can add a little cold water at this point to wash the xtals). So, the xtals are ready to cycle again. During this filtration, the solubles impurities are removed.
To keep the funnel cold, one has to place the complete device inside the fridge.

So here are the very few data that I found about Harmalas-HCl solubility:

- Harmine hydrochloride dihydrate
Hot water: "freely" soluble
20 deg C: 1/40 or 2.5 %

This info comes from burnt
He seems to have the same source as a paper of 1931: Microchemical Identification of Harmine and Harmaline. J. F. H.
Amelink. (Pharm. Weekbl., 1931, 68, 221-229.) found here and cited here:
The properties and reactions
of Mercks preparations, ( Harmine and Harmaline, are described. Harmine
is identical with banisterine hydrochloride, Cl,H1,0N,HCl.2H,0. The alkaloid
melts at 263 C. without decomposing. Harmine (the hydrochloric acid salt) is a
white crystalline powder; the solubility in water at 20 C. is 1 :40 and the solution
is slightly fluorescent.
I have no info about DHH, THH, Vascine, ...

The advantage to re-x the xtals without salt would be:
- cleaner product (no NaCl comtamination)
- smaller losses because much less water is used
- easiness of the process
- precision of the dose

In the original paper of Hasenfratz et al. of 1927, it is said about the Harmine & Harmaline hydrochloride salts:
... After separation the 2 salts are then further purified by recrystalisation of their salts.
but there are no details.

Google found a post from another forum coming to the same conclusion here:
...
Manske it later if the vascine/vascinonine/etc bothers you, and you could prob re-X the product fairly easily by dissolving in a minimal amount of boiling distilled water, cooling, and watching xtyals pop out like crazy upon cooling. Even w/o salt though, i speculate this method would leave the vascine/vascinione left in the solution. There's a pretty big difference in harmala alkaloids solubility in water at hot/cold temps, and its part of the reason why manske works so well. Its almost like a freeze precipitation, and maybe adding an amount of salt (no where near manske levels to avoid contamination) could help along the re-x. That's where the crystal pay dirt is i think. Getting as much clean harmala salts as possible in minimal amount of boiling distilled water, and cooling it slowly, then into the fridge for a day or two with much less salt than used typically in a a manske or not at all. ...

So, let see if we can get more data...:thumb_up:
 
It is good that you now here elaborate better, so what you present is a two fold cleaning, one the cotton, two the re-x ing.

Usually I filter my liquid to death and beyond (in the acid state) before the first manske, making actually your cotton ball not necessary, I am almost sure my cotton ball (your style) would catch nothing. But I am willing to put it to the test nonetheless.

But what I also do and I suppose not everyone does: when my manske liquid (rich of salt) goes from the heating pot to the beaker to cool, here I coffee filter and always get some minor but still enough to catch grey stuff, so I supposed its due the salt somehow (regular iodine free kitchen salt) because before the salt there was nothing to catch anymore. Filtering this hot liquid is kinds of tricky because it cools in the coffee filter and start crystallizing, especially closer to salt saturation point. I usually bounce between 15 - 18 gr/100ml. Have to chase the filter sides with some little boiling water to free the filter sides of harmalas, the grey remains on the paper.
I think your system could replace my coffee filter here so I could go heavier on the salt saturation side. We'll see.
Thanks for the links 😉
 
burnt said:
According to the merck index. Harmine chloride dihydrate (the form you would get if you made it a salt with chlorine) is soluble in 40 parts water. That means 1 part harmine to 40 units of water. Freely soluble in hot water. The freebase is slightly soluble in water.

Harmaline freebase is slightly soluble in water. The chloride salt is also moderatelt soluble in water. No more details given.
So that is for 1 gr harmineHCL one needs at least 40 gr or 40 milliliter of water to dissolve it in at 20deg C, nice to know.
My experiment is now 1gr on 25 ml, so in fridge I should take all down to solid, the water leftover should be fairly free of harmineHCL, but we do not know about DHH and THH behaving differently.
 
Jees said:
It is good that you now here elaborate better, so what you present is a two fold cleaning, one the cotton, two the re-x ing....
Hello Jees, I am not sure that I understand your sentence.
In my experience, any "re-x" cycle has 4 steps, 2 of them being filtering:
1 - dissolve the x-tals (by raising the temp for example)
2 - filter the solution 1 and discard the insoluble impurities
3 - precipitate the new xtals from solution 2 (by lowering the temp for example)
4 - filter 3 to keep the new x-tals and discard the soluble impurities

Steps 2 and 4 are using the cotton ball as filter, to hold as less liquid as possible.

Those 4 steps are 1 cycle of re-x: from step 4 one can loop to step 1 again, and so on...
In two words: "Solve & Coagula" :)

I my experiment, this re-x process is just useful to purify the harmalas-HCl. So it starts with harmalas-HCl which have to be already synthesized by any way from the seeds by boiling, Mansking, free-basing, dissolving into weak HCl, or any combination of them giving at the end harmalas-HCl...
This is precisely what Hasenfratz did in 1927.

I do not have so much time now, but in few days I will post some pictures.
:thumb_up:
 
Wew here we go, sorry I could not use lesser words ;)

1, 2, 3 and 4 exactly as I thought :thumb_up:

I've not done 1 and 2 because my stuff was so clean already, so jumped to 3 and 4 with my pan-method because I focused on the fact if only that (3 & 4) would work for me at least.
But to be able to poor something liquid off in 4 then it must have at least some liquid to poor off, so that's why I went for 25ml demin water on 1.000 gr material (precision scaled), that according to your experiment, Burnt, Hazenfratz should crystallize.

But Houston we have a problem.
After 24 hours in the fridge all I got was this, see picture, the glass is still fogged due taking it out of the cold.
I pored the liquid off (straight without filtering so no volume loss) and got 20 ml, so 5 ml was evaporated.
I have now double the concentration of the aforementioned solubility limits (1:40) so all should have been crystallized. I don't know why this did not work. A too low concentration is now absolute out of the question, and I should not use lesser water to make it worth because else step 4 would be not workable as a true filtering step.

How much liquid in total do you use on how much material? So we can compare the concentrations used during the cooling stage.

I already got a hint at 10 ml, see picture again in previous post, that tiny amount of liquid that had not crystallized was way to dark (meaning full of non crystallized stuff) for my liking.

I had the intuition that this would happen, but now I see it happening, and now you also might understand why I was calling "impossible" in my first reactions to your suggested method. Now I am puzzled even more because you and the other sources you mentioned point in the direction that it should be possible. Mindlusion also mentioned it is very soluble in cold water which I see now confirmed.

I see only 2 ways from here:

1) burnt's mentioned 1:40 rule was about Harmine, I have crude Rue harmalaHCL that is like roughly estimated 50% harmine. Maybe the other 50% (mainly harmaline) doesn't follow the rules? Do you have success with crude HCl extract, meaning non separated (harmine/harmaline) harmala's?

2) as I've mentioned before in the VDS thread, it could be just as well salt retention from the manske that turns the multiple following crystallization processes into a semi-overlooked manske effect, making it crystallize in cold. My stuff however was centrifuged which makes the salt contamination very low, plus the fact that I do not work with saturated salt but just 15 - 18 gr/100ml in the (final) manske, which prevents potential salt contamination by 50% compared to using saturated salt.
I know you do not follow the likelihood of salt retention on many passes, but what can I make of all this?

I feel a bit blind about what happened, I only have guesses.
Now for me you understand I feel not much motivation to carry on with this tech :oops:

There's one thing I might check, that is I have Harmine (I suppose its like 90% or better in purity) and see how that behaves. It's FB so I would first make some HCL's of it and proceed same experiment with. Just to see how it compares to crude rue extract. But I feel a little dulled for the moment I think you can guess. Even if that works a little better, it likely is not enough to drag me over the line to really use it tek wise.

All thoughts very welcome.

-

PS.1: people who perform multiple manskes usually have a standard like using e.g. 20gr/100ml or whatever, but forget about the salt retention they keep carrying along, making their true salt levels a notch higher than thought. In my case this never happens as I stop adding salt on eye sight which makes it very clear when to stop adding, so my potential salt retention from previous step(s) is embedded. I am not against using full saturated in general, but my reasons to trust eye is like I said in previous post and always end like 15 - 18 gr/100ml when afterwards checked on the salt used. I don't suggest to copycat the 15-18 number blindly as acid and especially concentration in the manske plays big role when crystals start to form.

PS.2: there was someone here who followed a Hazenfratz thingy accurately (forgot exactly what tek/steps but iirc a concentration that was way off) and found it complete non workable. Why is a mystery, but just telling.

PS.3: please drool over the wonderful bokeh porn of last picture, I have a new pic tool Fujifilm X-T2 😁
Guys sell your DSLR's while you can, mirrorless is on the move.

PS.4: maybe this thread belongs better in the Harmala section? To be moved?
 

Attachments

  • 03nogo.jpg
    03nogo.jpg
    199.1 KB · Views: 0
  • 04nogo.jpg
    04nogo.jpg
    179.8 KB · Views: 0
I think they key in manske is the solubility of HarmalaHCl in cold water. Jees noticed in this thread that there is a finite solubility and that is why excess Cl- ions matter.

If someone could measure the actual solubility of HarmalaHCl in cold water it could be helpful to optimize the manske setup of the initial HarmalaH+ and Cl- concentrations.

At 20C, we have the 1:40 number which I think means ~0.1M (?). I think in cold (~4C) water solubility drops down to ~ 0.05M based on manske behavior and the equilibrium equations behind it. Would be great if someone had the actual value (or could measure it). A plot of solubility vs. temperature for different HarmalaCl (Harmine, Harmaline, THH) would be awesome.
 
Back
Top Bottom