Hi and thanks for reading.. I have a question..
If I convert a mix of harmine and harmaline using magnesium ribbon to obtain a mix harmine and THH, Can I separate harmine from THH later using different Ph precipitation like is usually done with harmine and harmaline?
Does anybody knows the PH precipitation point of THH?

I'm curious to know to. Even if it's quite ok for me to have it as a combination.

It should be more straightforward than separating harmine from harmaline; on the basis of its molecular structure THH should require a higher pH to precipitate than harmaline does. There should be a thread somewhere around here where this separation has been tested out but I haven't searched for it yet.

One thing I'm not fully certain about is the practicalities of the post-reaction separation of the alkaloids from the magnesium salts. Magnesium may not redissolve in ammonia the way zinc salts do.

An outline idea might be to crash everything with sodium hydroxide, which should yield freebase mixed harmalas plus magnesium hydroxide, followed by a quick rinse in distilled water and then the Ethyl Acetate Approach for Harmala minus the need to add any lime. Hopefully the freebase alkaloids will separate nicely from magnesium hydroxide paste that way.

Another approach would be to try precipitating the magnesium as the practically insoluble magnesium ammonium phosphate.

What was your plan with regard to this issue, Nachooo? Perhaps if you were to control the pH exceedingly carefully you might see a precipitation of harmine first, followed by magnesium hydroxide and then the THH - but it might turn out rather messier than that (in all likelihood!)

Thanks for the info.
I was going to use ammonia to precipitate the harmine raising the ph until about 8, and then filter the harmine freebase and add more ammonia until about 10-11 ph to precipitate THH...
I though ammonia washed magnesium salts...

So to avoid magnesium salts...after disolve the magnesium, just crash all with sodium hidroxide...rinse with destilled water, let dry it, then lets say..I collect about 5 gr of freebased harmine/THH with magnesium hidroxide..so I should do mini pulls with Ethyl Acetate and after that add some citric acid to recover pure harmine/THH citrates and after that precipitate with ammonia the harmine first and the THH the later...to separate the akaloids?

Seems too much work..maybe is better the zinc route...and doing mini pulls of EA over a few grames of freebased harmalas seems quite complicated..

Well, you may end up with the magnesium hydroxide as a nanoparticle emulsion from which would be possible to separate the precipitated harmalas by decanting and filtration. I just think it will require a bit of experimentation.

It's one thing is to avoid ending up with a solution containing too much of one of the magnesium salts which you then ingest - they are pretty effective saline laxatives although with a normal dose of harmalas this is unlikely to happen. If you do end up with magnesium compounds in your solid harmala products it will affect your ability to weigh them accurately and they'll seem relatively weak.

If it's any consolation, I have cleaned up residual harmala hydrochlorides from recovered Manske salt crystals after evaporation by using a couple of quick ethanol washes in a filter funnel. Exploiting the differential solubility in various solvents is advantageous but of course your idea of fun may differ.

It would be nice to know if you can actually separate the harmala alkaloids from magnesium salts using ammonia, so by all means have a try but be prepared for some magnesium hydroxide to precipitate. It won't mean your extraction/reaction is ruined - you'll just need to do a couple more steps to purify your products.

Great that you both have ideas on how to separate it. Now I don't mind a bit of magnesium hydroxide but it's nice to get it as clean as possible.

I try to understand how and if THH will work with a manske, It seems like it from other posts here.

OR I'll try to wash the THH/Harmaline with ethanol and filter out the THH. If I understand things ciorrectly.

Just an update to this question: good separation of magnesium, at least from the THH, can be achieved by basing with ammonia or sodium hydroxide, redissolving everything in phosphoric acid and carefully basing again with ammonia. The magnesium precipitates as magnesium ammonium phosphate (MAP) between around pH 5.5 and 6.0. The end of this fraction, at around pH 6.2 comes down with the harmine. With even more careful pH control and a larger extraction size it may be possible to get the harmine to crash without any MAP.

Above pH 6.2, nothing comes down until about pH 8.0 - 8.5, giving a nice window for collection of the THH and any remaining harmaline. These higher pH values are a bit tentative as my pH measuring capabilities were limited to narrow range pH papers. The high range papers did not appear to be working, giving no response even with sodium hydroxide solution.


Doing an ethanol wash on a mixture of precipitated magnesium hydroxide (or MAP) and one or more of the harmala bases should separate the harmala base into solution and leave the magnesium behind. I don't think it will separate harmaline from THH.

Great, thank you downwardsfromzero!

I now got a good Ph-meter and will try out your suggestions. Now I just need to order some phosphoric acid.

If I want to do more THH by magnesium reduction, I wonder how clean I need the harmaline to be. It would be nice to skip the filtering of rue and just to a crude extraction as Brennendes Wasser suggest here? But then doing a Ph-separation of Harmine and Harmaline. Or if some manske(s) are needed?

A chemist might argue, the cleaner the harmaline the better. Something we still need to test, though, is if harmine reacts with dissolving magnesium at all. There certainly seemed to be rather a small amount of harmine precipitate after my rue tea reduction but that's very likely to be down to poor recovery levels.

Good. I might try a Harmine / Harmaline separation on both an extract that had two manske and then make a new one following Brennendes Wasser. See how it goes.

If you succeed with separating a reasonably clean harmine fraction, could you perhaps see if anything happens with a magnesium reduction on it? Reaction size can be half a gram of harmine or even less.

Great thinking! Sould have thought of that myself. So we might see if someting happens with it in a magnesium reduction.
I can also get more harmine by doing a extraction from dark roasted rue. But I don't know how pure harmine that is.

ShamensStamen had trouble getting anything separated from the dark roast rue; did you succeed in this?

Yes I did!
But I did it just mostly to try it out and didn't keep notes of any weights. But might do another roast soon and then I'll be more carefull.

And even with my limited experience of separated harmine, I would say that the extract were just that.

That's good to hear. I look forward to seeing the details of your replication experiment. The figures should prove to be informative.

Do you think if you were roasting a fairly large amount of rue that you would have some way of collecting and condensing/resubliming (to be pedantic ) at least some of the vapours?

Hmmm, like a dry distillation. I don't have suitable equipment but I'm also interested it the vapors. I thought of using ice in a bowl on top of the roasting seeds, and see if anything can be collected. I also have a friend with a small lab that i could ask for help.

I'll get back to this
M

Indeed, it becomes a dry distillation once we start collecting the vapours.

The ice bowl idea is a good first start. I wonder if ice/salt slush would help prevent moisture from dripping down onto the roasting seeds less readily by freezing it. There are technical challenges when carried out at even a small scale, depending on how obsessive one wants to get about catching and identifying all the vapours.

We know that actives definitely vaporise from the seeds so catching them during roasting will help us to understand what's happening during the roasting process - vaporisation of harmaline vs. thermal decomposition, and how much harmine goes up in the vapour. A good-sized sample of the condensate would be worth sending off for analysis, I would think.

Have I used the keywords "headspace vapor analysis"? The basic idea would be to roast the seeds and direct the vapours straight into some analytical instruments (Endlessness....)

I've not reduced (be that with zinc or magnesium) an unseparated harmine/harmaline mix so far, but to get rid of the salts I would try basing everything post reduction {harmine + THH + the salts} to a really high pH.

I would then hope the {harmine + THH} are precipitated as freebase together and the salts going back into solution due the really high pH. Then decant/filter and wash the freebase with some water that has a pinch of sodium carbonate in it.

Then, being ridden of the salts, re-dissolve {harmine + THH} fraction in some acidic water, and separate these now under a more carefully pH rise.

So a bit of a 2 step thingy. Why? Because I presume the pH separation of harmine from the salts is more difficult than wished. By pH exaggerating in the first step we are much more confident to rid of the salts.

Comes to mind if one really wants the second step separation at all, why not considering it an already ideal harmaline+THH combo as is. But that's just a practical thought.

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The other method would be separating harmine from harmaline first, then only reduce the harmaline and precipitate the THH under a really high pH to rid of the salts due high pH. Wash products with sodiumcarbonated water. This is how I did it so far.

Harmine wouldn't accept the donor hydrogen like harmaline. It wouldn't do anything, that ring is locked down. But, with that said, you should be able to reduce the harmaline in an unseparated mixture of harmine/harmaline to THH and not effect the harmine at all. THH and harmine are even easier to separate than harmine and harmaline because of an even greater difference in the pH they crash out at.