Hello wise Nexus, i seek your help.

I have tried dissolving 2.5grams of harmine in 30ml of water that contains 6% w/v citric acid and addition of 20ml of everclear to round my tincture up to a total of 50ml. Initially the harmine always dissolves fully, but eventually the solution turns clear with a precipitate at the bottom of the container.

What might be the reason for this, and is there an alternative recipe for harmala tinctures that works?

Kind regards

JUBU

My guess would be that it converts to citrate and dissolves in the water, then crashes back out after the addition of alcohol. Have you tried using only water with no everclear?

I've never tried making tinctures, but i have tried to dissolve harmalas in various solvents (i never really separated the harmine from the harmaline, but i'd assume the solubility issues are similar).

From my experience, harmala freebase dissolves in ethanol given some heat and time, but not well. i doubt even one gram would dissolve in 20ml. I have not tried dissolving harmala citrate in ethanol, but i am currently trying to dissolve it in PG (for vape juice), and it took 25ml of PG to almost fully dissolve 775mg of harmala citrate - attempt still ongoing, i kinda think it will work, but maybe i'm wrong and will have to add another 5ml to get rid of the last solids.

You might have better success with harmine HCl (which you can make by Manske). Again i haven't attempted to dissolve it in ethanol, but in PG, 1g dissolved in just 8ml within a few minutes with some heating, and didn't crash back out at room temp.

As HT already mentions, ideally you'd find the right edible anion (from your choice of acid) that keeps your harmine salt in solution once the ethanol is added.

On the other hand, you appear to have found a simple way of recrystallising harmine citrate. I bet if you warmed it up it would dissolve again and on cooling slowly you might well get some decent crystals. If that appears to be the case, best results would be obtained by transferring to a fridge and then a freezer. [Recrystallisation from aqueous ethanol like this is a well-established method of purification during lab prep work.]

How clean did the precipitate look? While this is essentially the opposite of what you were aiming for, it surely beats messing around with butyl acetate as I did - unless one happens to like banana-flavoured harmalas

Reason for this is most likely that volume of your tincture solution can't dissolve the alkaloids, so they precipitate (after some time or after cooling).

There is also a possibility that your harmine citrate is still dissolved in solution and precipitate is just some impurity.

Solubility of alkaloid salts are very often lower in ethanol than in water. Addition of ethanol (IPA or acetone also works in similar situations, of course not for tinctures) decreases solubility of salt, in your case harmine citrate, so it precipitates.

It's called Dual solvent recrystallization method and could be used also for purification of other salts of our interest, for example mescaline sulfate (or tartrate) could be re-xed from water/acetone or water/IPA mixture.

Your goal is to have your harmine still dissolved, so you should find different acid/salt form. Besides HCL, acetic acid is also a good candidate.

just for OP's clarity: You don't need hydrochloric acid to make harmine HCl. "Manske" process is done by dissolving harmala freebase in water with the aid of a little bit of acid (i use acetic), then adding table salt and letting everything cool then sit in the fridge overnight. This will grow beautiful HCl crystal needles that you can collect eg. in a coffee filter.

Not sure.

Try perhaps more citric acid?

IME a tincture works just fine if you shake before you use it, put your desired dose in a shot glas and dilute it with hot water.

Has worked just fine for me every time.

My mix contains more acid then harmalas by weight, though.

For further details feel free to send me a PM

Thank you all for your help and excuse my slow response, but I only get around to these kinds of experimentations every few days or even weeks.

There was a lot of precipitate and the tincture turned almost completely clear therefore I do think this was not just an impurity. The crystals looked jagged and dark, and a mineral in my collection labeled silicon carbide looks kind of like it. I would guess its quite clean...

The same day I initially had asked you guys for help I came across a german online store selling 500mg of harmine tincture in 10ml of 40% ethanol, without further specifications. I tried replicating the tincture with freebase, but even 20ml of vodka and a warm water bath wouldn't dissolve 500mg of freebase. As Homo Trypens pointed out maybe harmine hcl might dissolve more easily and its what i will be attempting next.

After several rue extractions im still not well versed with the chemistry behind it. When salting out there are two anions present namely chlorine and the acid and two cations namely sodium and the protonated alkaloid. Chlorine and the alkaloid are the two less soluble ions and they then form the precipitate salt, correct? What im really trying to ask: Is there an easy and intuitive way of understanding this process or is it one big rabbit hole and I shouldn't bother with it?

Your last paragraph describes the basic idea behind the Manske precipitation reasonably well, albeit crudely. It's to do with solubility equilibria, whereby each possible combination of cation with anion has a corresponding solubility product. Choose the appropriate translation of the wikipedia article to help understand this more easily. It's a rabbit hole worth even superficial exploration, since grasping the principles of chemical and thermodynamic equilibria is extremely useful when working with extraction and formulation like you are.