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Separating Harmaline/Harmine (and THH?)

Migrated topic.
endlessness

endlessness

Established member
Moderator Lab expert
(couldnt find a propper thread about this, if there is, sorry)


One can separate Harmine and Harmaline due to their difference in pKa

Harmine pKa: 7.7
Harmaline pKa: 9.8

This means as the pH raises, first harmine will precipitate, and after harmaline.

According to this thread, at pH 8.75 , one will have precipitated 92% of Harmine and only 8% of the harmaline..

Now two questions I have: Considering one doesnt have a pH meter, could sodium bicarbonate be added to precipitate the harmine, and then continue adding sodium carbonate to precipitate the rest of the harmaline? What pH can be reached with sodium bicarbonate?


The other question is: Is there any viable way of separating THH? Any info on pKa or solubility in different solvents?
 
@endlessness,

In theory yes, one can add sodium bicarbonate to reach a pH of ~8.5 and precipitate harmine, then add sodium carbonate to boost pH and precipitate harmaline. It should work in practise.

The only complication is that sodium carbonate/sodium bicarbonate mixtures form buffer solutions which resist pH changes (see attached paper). This should not be a problem, it only implies that more sodium carbonate will be required after the harmine precipitation.

As of THH, there is no info on its pKa, but we know its XlogP to be 1.9, so it can be precipitated as the freebase. What SWIM has been dreaming of doing (but never got the time/mood/materials) is to extract caapi, precipitate harmine and then THH. For some reason he believes (belief = unsubstantiated opinion:p) that THH's pKa is higher than harmine's. He may be way wrong however, if harmine and THH have similat pKas then it is not possible to separate them via selective precipitation.

(would be nice if someone with relatively pure THH could roughly determine a pH value at which THH starts precipitating...! The community would benefit massively)
 

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can one separate THH by its melting point? How would be a practical way of doing it? Apparently according to this interesting publication, the melting point of THH is significantly lower (199 degrees, or in TIHKAL 190), compared to the info I find on harmine and harmaline elswhere which seems to have melting point over 250 degrees


btw, it works perfectly to separate harmine and harmaline by just throwing sodium bicarbonate first to crash out harmine, and after filtering, putting more sodium carbonate.. The nice thing is no need to be exact with carbonate and neither with bicarbonate, just throw them in, as bicarbonate wont raise the pH more than necessary, and then later just throw carbonate till alkaloids crash out and then some more to make sure

On a side note, Phlux says that some of the harmaline doesnt crash straight away together with the harmaline that precipiitates soon after adding the carbonate, that some takes longer, some hours,... I didnt know so I was quick and few minutes later already filtered, maybe I lost some (though yield seems good anyways, but cant measure as its still drying after clean up), so you guys should be more patient,
 
endlessness said:
On a side note, Phlux says that some of the harmaline doesnt crash straight away together with the harmaline that precipiitates soon after adding the carbonate, that some takes longer, some hours,... I didnt know so I was quick and few minutes later already filtered, maybe I lost some (though yield seems good anyways, but cant measure as its still drying after clean up), so you guys should be more patient,
Click to expand...
That makes some sense; harmine freebase is much more water insoluble, whereas harmaline is very slightly water soluble (all these based in XlogP values). This may account for the extra time required for harmaline to precipitate.
 
someone here in the forum mentioned that THH doesnt precipitate in a manske... Can anyone with some THH check this by redissolving some in water and saturating with salt to see if it precipitates? That would be a very easy way of separating THH from the rest, just manske first, to get harmine and harmaline out, then freebase the salt-saturated harmine/harmaline-free liquid, and only THH would crash out
 
endlessness said:
someone here in the forum mentioned that THH doesnt precipitate in a manske... Can anyone with some THH check this by redissolving some in water and saturating with salt to see if it precipitates? That would be a very easy way of separating THH from the rest, just manske first, to get harmine and harmaline out, then freebase the salt-saturated harmine/harmaline-free liquid, and only THH would crash out
Click to expand...

I don't have THH, but I'm going to try what you said and examine the freebase yield, THH is the main alkaloid in rue after Harmaline and Harmine, so if anything precipitates out of the "salt-saturated harmine/harmaline-free liquid" it will be nearly pure THH. I'll report in a few days.
 
Eranik said:
endlessness said:
someone here in the forum mentioned that THH doesnt precipitate in a manske... Can anyone with some THH check this by redissolving some in water and saturating with salt to see if it precipitates? That would be a very easy way of separating THH from the rest, just manske first, to get harmine and harmaline out, then freebase the salt-saturated harmine/harmaline-free liquid, and only THH would crash out
Click to expand...

I don't have THH, but I'm going to try what you said and examine the freebase yield, THH is the main alkaloid in rue after Harmaline and Harmine, so if anything precipitates out of the "salt-saturated harmine/harmaline-free liquid" it will be nearly pure THH. I'll report in a few days.
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It'll be hard to find any THH in peganum harmala using kitchen chemistry. As far as I know there are only traces of it, if any.

If you 're willing to do that then you may start with b.caapi, which is a better source of THH. Also, i'm not sure how you'd do that from what you've described. It doesn't sound right at all.

You'll have to do A/B on caapi and pull the freebase alkaloids with DCM or chloroform. You then need to salt them back from DCM or chloroform using HCl or vinegar and evaporate it to get their salt forms. Then you'll have a cleaner preparation to play with.
 
Infundibulum said:
...If you 're willing to do that then you may start with b.caapi, which is a better source of THH. Also, i'm not sure how you'd do that from what you've described. It doesn't sound right at all.

You'll have to do A/B on caapi and pull the freebase alkaloids with DCM or chloroform. You then need to salt them back from DCM or chloroform using HCl or vinegar and evaporate it to get their salt forms. Then you'll have a cleaner preparation to play with.
Click to expand...
Non-polar solvents aren’t needed to pull relatively clean alkaloids from b. caapi. Take a look at this thread.

And as you already stated, caapi is a much better source of THH than rue. (I seem to remember reading that caapi can sometimes contain more THH than harmine?)
 
gibran2 said:
Non-polar solvents aren’t needed to pull relatively clean alkaloids from b. caapi. Take a look at this thread.

And as you already stated, caapi is a much better source of THH than rue. (I seem to remember reading that caapi can sometimes contain more THH than harmine?)
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Ah, yes - btw, excellent tek and pictures!

I'd go for solvents because I wouldn't be bothered waiting for all these precipitations to settle. Your approach is totally excellent though.
 
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