Yes and no: in principle Manske of Harmine HCl followed by base for THH gives a certain amount of separation - although base separation of harmine and THH proceeds more cleanly anyhow. Harmine crashes at pH7 already, THH needs considerably higher. During a Manske some of the harmine will nonetheless remain in solution so in this case you might as well save the salt for your potatoes - unless, of course, you simply want the aesthetic pleasure of making the admittedly beautiful golden needles for yourself. Can't beat a good bit of crystal pr0n

With careful addition of base it may even be possible to observe a point where the putative impurities from the combined reduction might precipitate; if we're super lucky they'd have a pKa between that of harmine and that of THH but that remains to be seen. It does remind me of the goo enigma that is detailed somewhere further up in this thread, though.

I always thought pure harmine was off-white and the "dark natural brown" was impurities co-precipitating with it in rue extractions.
I don't know about harmine reacting with hydrogen and taking on a strange smell. But my preferred way, too, is to separate it from the harmaline and keep it to a minimum in the reduction vessel. It makes it less thick and easier to precipitate and clean up; it also reduces the potential for contamination. Another reason is that the harmine/harmaline ratio is a bit too heavy on the harmaline. A separation is therefore desirable and it's easier to separate harmaline from harmine than THH from harmine, due to the pKa points being farther apart and greater stability.

Thank you Jagube and ava69. I guess I just have to get a proper pH-meter and start separating then. I'm intrigued by THH and would like to know it better.

Got all the supplies now for the first experiment (ethanol, zinc, vinegar, sodium carb & bicarb).
I will go with the simplest route as described by endlessness. Full isolation is not important to me, as long as the THH content will be high enough to allow for a good experience without the usual harmalas nausea.

But I'm still not sure if I have to convert the harmalas HCL to freebase first?

You'll be performing the reduction under acidic conditions so either form will do. If it saves you a step, you could go straight with the harmala HCl - although the point of precipitating the freebase is to separate the harmine from the harmaline. For the reasons discussed above, this would be a better idea. It's advisable to use a single isolated substance for a chemical reaction in order to avoid unpredictable side reactions.

Ok, thanks.
A buddy of mine has a good electronic pH meter so hopefully I can get this separation to work.

The Van Der Sypt paper says on page 17 that “at pH 8.5 all the DHH had precipitated. Addition of large excess ammonia 12% solution did not lead to the formation of more precipitate”. OK, so I did that, and added ammonia until I got to a pH of 10. Then I filtered the precipitate and to the filtrate I added NaOH to get to a pH of 12, and then more stuff precipitated. It was a much smaller amount that the precipitate at pH 10, maybe 10%, I didn’t weigh it. Anyway, has anybody else encountered this? Is the extra precipitate that happens beyond pH 10 also harmaline, or is it something else? And if it is harmaline, wouldn’t it be more efficient after getting the harmine out to crash the harmaline with NaOH instead of ammonia? Thanks.

It could be something else, especially if you are at the begining and not done a lot of cleanups yet.

Thanks.

So how can you tell when the conversion from DHH to THH is complete? Liquid glows blue under an ultraviolet light? No more tiny bubbles rising from the bottom?

UV glow is iffy to me, since concentration and minor impurities can affect color a lot. Bubbles only mean how much acid is reacting with zinc independently of THH/DHH. The best way to check is with home TLC.

What does “home TLC” mean? Thin layer chromatography? I had no idea you could do that at home. What do I need in order to do that?

One question for ava69.
Thank you for all info you are bringing in to the forum.

Why do you seem to prefer zinc dust instead of magnesium ribbon? I'm hesitant because of the risk of metal contamination, magnesium seems safer and work just as good. Or?

Doesnt the VDS protocol answer this in a way? Given some proper filtration (cellite was suggested) before re-basing with ammonia, the ammonia does not precipitate any zinc compounds and is pretty much clean of zinc IIRC

Yes, I believe that the zinc way can be perfectly good if being done right. But magnesium just seems simpler, less risky and just as good. But perhaps I've missed something?

It's rather a pain to separate all the magnesium salts from the harmala alkaloids. Magnesium hydroxide precipitates with ammonia and redissolves in acid. One way around this is using phosphoric acid to dissolve the alkaloids, then precipitating with ammonia again. The residual magnesium should stay precipitated as magnesium ammonium phosphate when the harmalas are redissolved in phosphoric acid again, although I'm only halfway through a test on this (several gallons of rue tea had to jump the queue before they went mouldy!)

[EDIT: I just had a play with this; MgNH4PO4 powder dissolves in phosphoric acid but it does precipitate with ammonia at pH6 so it crashes before harmine (if you've left the harmine in) and this gives a good range of leeway if you're only separating it from harmaline and THH.]

Another possibility is to pick up the harmala freebase using a solvent such as ethanol. I'm just a bit wary of evaporating alcoholic harmala solutions as this is one way that "harmala red" forms. Using ethyl acetate would allow the collection of nice, pure alkaloidal citrates although it's not entirely clear yet if this would work for THH. Maybe an adequate precipitation of some harmala salt or other would also be viable from alcoholic solutions.

It would be worth checking how the few other members who've tried magnesium reductions went about recovering their alkaloids. Magnesium salts are relatively harmless but their presence would throw the dosage way off - and in teaspoon quantities they have a laxative effect (oh, yes!)

Thank you! I didn't know that Magnesium hydroxide precipitates with ammonia! In my trials I've not noticed any unwanted effects on 'the rear end' But now since I want to do this preperly it would be awsone is we could work out a magnesium Tek. Preferably without to much hard-to-get or prepare chemicals. I'm really busy at the moment (but not with gallons of rue tea ) so I'll have to dive in to this later next week. Good luck with the Rue!

murklan - did you see my edit?
Looks like a separation with phosphoric acid, ammonia and pH control should do the trick.

Yes I saw it but didn't go into it. Do you mean that if I use a harmaline/harmine mix and do a magnesium reduction, that I could use phosphoric acid in the reduction step (instead of acetic acid that I've used so far) or that I could use phosphoric acid when I want to separate the magnesium in another step after? Sorry if I'm missing something obvious.

When I got time I'd like to do (together with you if you'd like) a clear tell-me-like-I'm-five-year-old-chemist step by step guide

I did the reduction with acetic acid but after the first precipitation with base, re-acidified with phosphoric acid. I found this left a good number of cubic crystals of magnesium hydroxide/carbonate (they fizzed a bit) behind. [It seems the carbonate formed because the solution was left standing for several weeks and had sufficient access to the atmosphere to absorb CO2. In fact, the first precipitation was actually done by allowing gaseous ammonia to diffuse into the post-reduction rue tea, so that may have influenced the formation of the magnesium as well.] {Maybe the reduction could be carried out using phosphoric acid; if so this would make the magnesium removal step the very next thing that happens after the reduction, by adding just enough ammonia.}

Basing again with dropwise concentrated ammonia crashed out at first a relatively heavy, powdery, pure white precipitate of presumed magnesium ammonium phosphate, followed by the various harmala alkaloids in sequence (one of them floats to the surface but I was unable to recover this without dispersing it back into suspension).

The precipitate was recovered by filtration and redissolved in excess dilute phosphoric acid. [The first time around, this was a test to see if the (suspected) magnesium ammonium phosphate would dissolve in phosphoric acid.] A further, more careful addition of ammonia has shown that what I at least strongly suspect to be MgNH4PO4 precipitates at pH6, which means it should be possible to separate it from harmine if one is extra-careful. Separating it from harmaline should be very easy, and THH easier still. The main thing is filtering off the obviously very white precipitate that comes down at pH6 from adding ammonia to a phosphoric acid solution of the magnesium-reduction solution of harmala alkaloids.

I shall carry out a few more solubility and chemical tests in order to determine whether or not the first white precipitate is indeed an inorganic salt, but from what I remember in coming up with this separation method for magnesium that the precipitation pH is on par for that. One more thing is that boiling the MgNH4PO4 causes it to become crystalline so I'll be giving that a try as well. It could be that my pH measurement is off and it's actually harmine - but it's very white for harmine.

I hope this makes a bit more sense now, but feel free to ask some more - I'll be dropping by at least every few days to report developments so don't worry if I take a couple of days to get back to you.

[Edit: the best way to test a sample suspected of being a magnesium salt in this context, i.e. all the other possibilities are freebase alkaloids, is to blast it with a blowtorch. A magnesium salt will be non-volatile, unlike the alkaloids.]