Harmine, harmaline and THH from Syrian Rue. Verification and finetuning of the VDS-protocols

[downwardsfromzero]

murklan - did you see my edit?

[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.

Looks like a separation with phosphoric acid, ammonia and pH control should do the trick.

 

[murklan]

murklan - did you see my edit?

[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.

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

 

[downwardsfromzero]

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.]

 

[ava69]

Downwardsfromzero said:

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.

Good luck with your experiments downwardsfromzero, read over your work several times on page 33 and this page 34, I'll be reading even if not logged in, read you were at the end of a 1kg rue extraction, finished up my 8kg rue extraction a month ago, only do this around twice in a lifetime, so that I end up with enough THH to last a lifetime, as I use 300mg of it at least 3 times a month. It's a massive undertaking but like my grandmother the lifetime oil painter used to say, "just do a little bit every day, and soon you will be done."

P.s. The homeowner's association made me remove my 12 foot long x 4 feet high fence-line of heavenly blue morning glory only but a couple weeks before the flowers were to convert to hundreds of dark seed pods, what a drag...so I was unable to harvest the potent fresh psychedelic seeds from the vines which I grew in fertile soil, they couldn't stand the pretty flowers! Hope your morning glory made it all the way to seed. Take care, all the best, peace, love and music.

 

[downwardsfromzero]

Hi ava, thanks for your well wishes. How terrible to hear of your poor morning glories! It really beggars belief the pettiness we can encounter sometimes. I managed to get a few seeds from my plants that were in the sunniest location, the others I think got planted out too late after a failure of some early seedlings. I also think there may be a temperature/day length issue at my latitude. But more of that in the right thread.

The 1kg rue extraction really is an undertaking (and I baulk at the thought of an 8kg one!) but it was in part inspired by your THH reports, ava. It would help to be able to press the seeds and, despite serendipitously having found just the right bottle jack, I haven't rigged anything up yet. Instead I'm on about the ninth boil and still getting alklaoids - the size of my PC limits my boils to 1.7L at a time so I think next time I'll stick with a half kilo instead. State of play is I have three gallons of based tea, one of which has got to the point of a 2nd A/B cycle for the harmine fraction. I think my alkaloid concentration has been too high, which impedes crystallisation. My small-scale test on the Magnesium reduction went a lot more smoothly because of the lower concentration at the base stage.

There's also the question of rue tea's perpetual ability to precipitate ultra-fine black crud alongside its incredible foaming abilities. Both of these make vacuum filtration far more of a challenge than I anticipated, and I'm still puzzling over exactly how I'll be cleaning up my fritted funnels. Filter papers seem both to clog and to let through the fine particulates. The trusty cotton plug gravity filter has already demonstrated its worth in cleaning up the tea as it comes out of the PC and we'll have to see what it can make of the filthy-looking supernatant that gets syphoned off the precipitated alkaloids.

My putative magnesium ammonium phosphate which precipitated between pH 5.5 & 6.2 has remained undissolved in 96% ethanol, which is a good sign. After pipetting off, the ethanol had been evaporating in a Petri dish so we'll see if any harmine crystals appear there. It's beyond question that the low-pH precipitate here was MgNH4PO4, or at least largely so, simply because of the quantity in comparison with the higher pH precipitates totalling about 150mg (it was a 5g rue tea directly reduced with magnesium ribbon as a test so this is not entirely disappointing). The low pH precipitate amounts to some 2.02 grams - plus another amount which I've set aside from the very first ammonia diffusion precipitation (and which reminds me that they need weighing).

The question is whether my 150mg precipitate is harmaline or THH. I need to get a new pH probe so I've been relying on narrow-range pH papers for this and I've established that the two high pH (10-12/12-14) range papers have stopped working, presumably due to old age. It's therefore at present unclear whether my ammonia was getting to a high enough pH to precipitate THH, but there was a clear gap between the low pH precipitate and the high pH one. I was hoping to have titrated this but managed to break the tap key for my burette. Don't try cleaning your equipment when you're tired!

Because there was no clear harmine precipitate we are faced with at least a couple of possibilities - the harmine has perhaps become trapped in the MgNH4PO4, or maybe magnesium is capable of reducing harmine (which would turn out to be rather interesting). I'm pretty sure the seeds started out with some level of harmine present but this wasn't expressly tested so we can't exclude the possibility that there's simply no, or very little, harmine there although that seems rather unlikely. As Mark Twain once said (and Shulgin quoted him in this), "I love how science gives such an abundant return in speculation for such a trifling investment of fact."

Where did the harmine go? Has THH been precipitated? Will I ever be able to afford some decent laboratory equipment? The experimentation continues...

 

[downwardsfromzero]

Another update: I've found the harmine! Here's what happened...

After redissolving in phosphoric acid the solids that were precipitated from the initial reaction by ammonia diffusion (described elsewhere on the forum), magnesium ammonium phosphate ('MAP') was precipitated in three fractions by dropwise addition of aqueous ammonia (specific gravity 910 when fresh, which it wasn't). The initial solubility test was carried out on a small sample from the 0.64 grams of dirty off-white precipitate which had started to form at pH5.5. [The typical harmala crud had had time to settle slowly on top of it while it stood overnight.] Evaporation of this solution left but the faintest oily smear on the evaporation dish. Near UV light (from a 'spy pen' toy) produced no visible fluorescence on the dish. The residue when redissolved in ethanol gave only a faint line of yellowish-green fluorescence along the light beam, indicative of the inevitable presence of harmaline contamination due to incomplete washing.

The second fraction, comprising 1.22 grams of clean, white precipitate on a par with titanium dioxide in appearance, formed between pH 5.5 and 6.0. It settled out quickly, giving an indication of its higher density. This was a large hint that it was more dense than the organic fractions could be. An ethanol solubility test help confirm this - the white solid remained undissolved as far as could be discerned and the supernatant produced no noticeable fluorescence with the spy pen except for the unavoidable harmaline traces. The powder also felt noticeably gritty in comparison with many organic substances.

The third fraction formed at around pH 6.2. The 0.16 grams of beige powder settled more slowly and was noticeably brown compared to the whiteness of the previous fraction as it formed. It became much paler on drying. The ethanol solubility test cleaned up the white powder a little and the solution gave a faint deep blue fluorescence which could be considered characteristic of the tiny amount of harmine present.

***So, yes - there's the harmine, it seems.***

There was also an insoluble fraction left over from the initial ammonia diffusion precipitation. This seems to be basic magnesium carbonate, as there was an effervescence on washing it with phosphoric acid. I'll be doing a few more tests on this material later today.

One more thing to bear in mind when working with ammonia and phosphoric acid is that ammonium phosphates will exert a buffering effect. This, combined with my apparently lousy narrow-range pH papers, makes the pH values quoted above maybe less than reliable. The fact that the harmine apparently precipitated at pH 6.2 could be down to co-precipitation effects with MAP that will have been present as a fine suspension of crystallisation nuclei, or could be that the pH papers couldn't cope with the conditions of buffering, strongly coloured solution, and the evaporation of ammonia from the papers at PH >7 which really hampers measurement of higher pH using this method.

Good news is I'll be trying out a self-build pH probe to test with my ancient pH meter. More on that elsewhere, when it happens.

 

[downwardsfromzero]

I've unilaterally decided to sticky this thread as it's pretty useful and tends to disappear down the list as time goes by.

Hopefully it'll act as a reminder on some of my science projects that got sidelined last summer.

 

[An1cca]

Nice research you're doing here, downwardsfromzero!

A cheap microscope will already give you a lot of useful information on the identity of harmala alkaloids. See elsewhere in this monster-thread...

Best wishes also for a revealing 2023

 

[downwardsfromzero]

Nice research you're doing here, downwardsfromzero!

A cheap microscope will already give you a lot of useful information on the identity of harmala alkaloids. See elsewhere in this monster-thread...

Best wishes also for a revealing 2023

How did I miss this? Thanks, An1cca - hope you have a fascinating year too!

 

[Brennendes Wasser]

I was searching again for my THH conversion notes that I got from somewhere on the forums and they tell to just stirr Harmalin in Zinc + Acetic Acid for 1,5 h.

Then I went back to the VDS Protocols and they stirr for some hours and then to continue to stirr for 6 hours. Quite a difference

So what is the concens of how long to stirr? I used that 1,5 h back in the days and my melting point was pretty exact. Still is there a short finalized protocol everybody uses, that is hidden inside those 30+ pages?

 

[An1cca]

That will depend upon your DHH concentration and the surface area of the zinc. If you're in a hurry, you can check under uv-light for the blue fluorescence of THH that is easily overpowered by the green of DHH. Or do a recrystallization in-situ on a microscopic plate of a drop of solution and verify the absence of DHH-like crystals.

 

[Brennendes Wasser]

I read that fluorescence info many times, but thought if it's a mix of both I would still not know about how much I have and/or still need to convert.

So that means even traces of DHH will make it green and absence of green will indicate conversion must be complete?

 

[An1cca]

If it's blue, it can't hurt to let it react for another hour. If it's green, you're sure you're not yet there. If you don't have a microscope, I've seen an interesting technique that points a common laser-pointer at a hanging drop of solution. The image is magnified hugely on the wall behind it. You could try this with your solution and please report back if it works...

Good luck!

 

[q21q21]

Hi everybody (long time no see for some Nexus OGs).

I've been getting back into tripping every few months h recently just with LSD and 4-ACO-dmt cause my new wife (1st wife, not 2nd) is a reliable and enthusiastic trip sitter. In the past I've only done 2 pharmahuaca trips and one was sub-threshold and one was unplanned ego death which scared me off for over a decade. I feel after my recent wonderful trips I'm ready to revisit pharma with better planned dosage but I want to have a large stock of THH and harmine (not sleepy harmaline) so I don't have to be nervous to "waste a trip" with a scarce supply of harmalas. I have several grams of DMT, that's not an issue.

Anyway, enough preamble. I'm unfortunately living in a country that prohibits the sale of zinc powder and other threads have said that pellets simply won't work. I've done the harmine harmaline separation before and will be careful to do 3 different PH pulls to get relatively high purity harmine and harmaline before the THH conversion of the latter. Technically I could risk getting some zinc dust from eBay but paying over $100 for something that not only is cheap but is illegal and could be blocked by customs leaves me with the magnesium route.

I copied every post in this thread after the mention of a theoretical magnesium tek to convert harmaline to THH into deepseek AI and it produced what you see below. Can you chemists and people much more chemically knowledgable than me check what it outputted for likely errors and let me know what would be the best plan for my THH production?

Based on the extensive forum thread you provided, here is a step-by-step "tek" (technical guide) for converting harmaline to tetrahydroharmine (THH) using magnesium. This summary prioritizes methods from posters who actually tested the magnesium reduction and reported their results, with an emphasis on safety and practical considerations.

---

Magnesium Reduction Tek for Harmaline to THH

Important Notes & Disclaimers:

· This is a synthesis of community-reported experiences. Undertake at your own risk.
· Key Safety Advice: Do not perform the reduction on a mixed harmine/harmaline extract. Several experienced members (e.g., ava69, downwardsfromzero) report that exposing harmine to the reduction conditions can create unknown byproducts that may cause increased nausea and have uncharacterized toxicity. Always separate harmaline from harmine first.
· Metal Purity: Use the highest purity magnesium you can find (e.g., 99.95% lab grade ribbon). Avoid zinc unless it is certified free from heavy metals like lead and cadmium. Magnesium generally has lower heavy metal contamination.
· Separation is Crucial: This tek assumes you are starting with reasonably pure harmaline freebase, having already separated it from harmine via careful pH-based precipitation (e.g., using ammonia to pH ~7 for harmine, then to pH >9-10 for harmaline).

---

Step-by-Step Procedure

1. The Reduction Reaction

· Materials: Pure harmaline freebase, distilled white vinegar (5-10% acetic acid), magnesium ribbon (or clean turnings), magnetic stirrer & stir bar, glass beaker.
· Ratios: Use a molar excess of magnesium. A tested and successful ratio from BongQuixote is 0.15g Mg ribbon per 0.5g harmaline. Another (Nachooo) used 80mg Mg for 255mg harmaline. A good rule of thumb is a 3:1 to 4:1 molar excess of Mg.
· Acid Volume: Use enough vinegar to fully dissolve your harmaline and allow for stirring. For a few grams, 100-200ml is typical.
· Process:
1. Dissolve harmaline freebase in vinegar in the beaker.
2. Add the magnesium ribbon. Reaction is rapid and exothermic. Significant bubbling (hydrogen gas) will start immediately.
3. Stir magnetically on low-to-medium speed. The vigorous reaction will subside as the acid is consumed (typically within 30-90 minutes). Let it stir for a total of 1.5 to 2 hours to ensure completion.
4. Monitor: The solution color will change. The intense green fluorescence of harmaline under UV light will diminish. When complete, a sample smeared on a plate and viewed under UV may show a faint blue fluorescence (characteristic of THH), but the main indicator is the loss of the strong green glow.
5. Let the solution sit for an hour after stirring stops to allow any undissolved magnesium to settle.

2. Filtering & Initial Cleanup

· Goal: Remove solid magnesium and magnesium salts.
· Process: Carefully decant or filter the reaction solution to separate it from any remaining magnesium metal. Coffee filters or a cotton plug in a funnel work. This filtrate contains your THH (as acetate salt) and magnesium acetate.

3. Precipitating THH Freebase

· Materials: Household ammonia (5-10%).
· Process:
1. To the filtered solution, slowly add ammonia while stirring. A white/grey-tan precipitate will form. This is THH freebase co-precipitating with magnesium hydroxide [Mg(OH)₂].
2. Continue adding ammonia until the pH is basic (pH >9). Ensure precipitation is complete.
3. Let the precipitate settle (refrigeration overnight is best).
4. Filter the precipitate. This crude product contains THH freebase contaminated with magnesium salts.

4. Purifying THH Freebase (Critical Step)

Magnesium hydroxide is amphoteric and will re-dissolve in acid, complicating cleanup. The following methods have been suggested or tested:

· Method A: Acid/Base Re-precipitation (Recommended by downwardsfromzero)
1. Dissolve the crude precipitate from Step 3 in a minimum amount of dilute phosphoric acid (or vinegar). This will dissolve the THH and any Mg(OH)₂.
2. Slowly re-precipitate by adding ammonia dropwise with careful pH monitoring.
3. A very white, dense precipitate of magnesium ammonium phosphate (MgNH₄PO₄) will form first, around pH 5.5-6.2. Filter this off and discard.
4. Continue adding ammonia to the filtrate. The THH freebase will precipitate at a higher pH (likely >8). Filter, wash, and dry this precipitate for a much purer product.
· Method B: Ethanol Wash (Suggested)
1. After the initial ammonia precipitation (Step 3), wash the filtered precipitate with anhydrous or high-proof ethanol (e.g., 95%+).
2. THH freebase is somewhat soluble in hot ethanol, but magnesium salts are not. A cold wash may help remove impurities. This method may require experimentation.
· Method C: Manske Saltation (For HCl Salt)
· Dissolve the crude freebase in dilute HCl to make THH•HCl.
· Perform a standard Manske saturation with NaCl. Note: Reports indicate THH•HCl is less likely to precipitate in a Manske than harmine•HCl, and may take longer or require more salt/concentration. This method may not efficiently separate THH from magnesium salts.

5. Final Product

· The final purified THH freebase can be used as is, or converted to a salt (e.g., HCl) by dissolving in the appropriate dilute acid and gently evaporating.
· Yield: Expect a ~75% mass yield from harmaline freebase (e.g., 1g harmaline → ~0.75g THH freebase). The product should have a cream/off-white color, not the darker tan of crude rue extracts.

Key Insights from Testers:

· Speed: Magnesium reduction is fast (1.5-2 hrs vs. 6-24 hrs for zinc).
· Contaminant: The main challenge is separating magnesium salts (Mg(OH)₂, Mg-acetate) from the THH, as they co-precipitate with ammonia. The phosphoric acid method (Step 4, Method A) is specifically designed to solve this.
· Safety: Bioassays by BongQuixote and Nachooo reported successful conversion (absence of harmaline side effects like strong nausea/tracers) and positive THH effects (reduced anxiety, smoother experience). However, they also noted the importance of purification to remove magnesium salt contaminants.
· UV Check: Loss of harmaline's strong green fluorescence is a good indicator of reaction progress.

Final Recommendation: For those attempting this, the phosphoric acid purification step (Method A) is highly recommended based on downwardsfromzero's analytical approach, as it provides a chemical means to separate the magnesium from the desired alkaloid.

 

[q21q21]

Hey everyone, I ended up trying the conversion but it seems to be failing. The green glow is persistent.

I ended up using magnesium granules because the ribbon was very expensive (20x more by weight!) and it was suggested in another thread.

I started with 2g of somewhat-pure harmaline (I think, I will use a different technique seperation method next time) and 450mg of magnesium granules. It was about 15C on my rooftop and the reaction proceeded for 2 hours with strong stirring before the granules were gone. Although small amounts sometimes seemed less-green or even blue, after smearing it somewhere else it looked bright green still. I tried 3 hours more and 200mg more magnesium and continued for 3 more hours, but the UV color was the same. I though that maybe I could try basing and look more carefully for a color change but as I washed the coffee filter with distilled water and shone the UV light on it I exclaimed "Nobody would ever call that blue...."

The freebase harmalas (whatever they are) as well as the precipitated magnesium salts are sitting in the coffee filter upstairs and I'm not sure where the mistake would be. Even a harmine contamination wouldn't cause this persistent bright green from my understanding.

Any ideas????

 

[Icon]

Congrats on your marriage!

I can't help with the conversion, but I think it would be reasonably easy to powderize zinc. It's really soft, about as hard as a fingernail. A zinc ingot and a file should work well, or sandpaper.