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

Migrated topic.
I now see that this idea has been up here before :)

The Day Tripper said:
To summarize-

Take pre-manske'd rue hcl's, preform a zinc/hcl reduction, another manske to get harmine hcl, freebase, collect thh fb w/ zinc/aluminum contaminants, dissolve in dry warm ipa, filter out any zinc/metals, then add concentrated hcl to precipitate thh hcl, and finally wash with dry cold ipa.
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I've never worked with dry ipa or hcl. But there is a first time for everything.
 
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.
 
Murklan post #629 said:
I get a bit nauseous when taking the THH-mixture orally at ~150mg, that is the first time I experience that with harmines. I usually take 200-220 mg of mixed harmine/harmaline and don't feel nauseous.
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Pure THH even at 300mg has zero nausea. The "weird harmine" being subjected to hydrogen gas is most likely what is causing your nausea, see below:

Downwardsfromzero said (post #635):
Without an actual chemical analysis we can only speculate what might happen when harmine is present during the harmaline/zinc reduction. Dimerisation or a similar coupling reaction is possible, where the harmine can trap a radical anion of the partially reduced harmaline. Perhaps the product of this kind of reaction is what has the nauseant effect. Emetine is a dimeric isoquinoline alkaloid although that doesn't necessarily count for anything. There are other kinds of dimeric alkaloids that do other things, and I would note that for emetine there are myocardiac toxicity risks. The main point still stands, being that if unknown dimeric or other oligomeric alkaloids are being formed in the harmine/harmaline reduction mixture we are dealing with unknown toxicity risks and this is something best avoided.
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Excellent analysis downwardsfromzero.

Downwardsfromzero asked if I would kindly address this question:

igorcarajo said:
On the topic of THH I wonder what happens if instead of separating the harmine from harmaline and then adding zinc to the harmaline to convert it to THH, one would add zinc to the harmine/harmaline mix. Would the harmaline convert to THH and the harmine remain intact?
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Great question igorcarajo. I don't recommend doing it that way as when harmine is reacted with teeny tiny hydrogen gas bubbles whether from zinc in vinegar or any other method (I've done this before to see what happens) it does remain as harmine but the harmine will give off a strange smell or odor indefinitely as if the reaction has some minor unknown influence on the alkaloid. It will even change the color of the harmine from it's very dark natural brown to a light tan shade. Even 300mg of pure THH made from harmaline has zero nausea, but this "weird harmine" subjected to hydrogen gas may cause nausea. Even left out in open air, it will continue to "stink the very faint strange odor". You also will not know how much harmine is mixed in with the THH making it impossible to dose correctly. The harmine when used this way also seems to impart a strange side effect of occasional minor drainage down the throat of flim, don't recommend the resulting "weird harmine". It's best not to have large amounts of harmine mixed in with the harmaline during the conversion to THH. It's not much work to separate the harmine from the harmaline with extreme purity using 10% janitorial ammonium hydroxide found at some hardware stores. Post #12 details the process with pics, what quality electronic ph meters to use, a cheap stir mantel, etc:

HPBCD DMT sublingually active under tongue
part 10: One way to make pure tetrahydroharmine (post #12)
hxxps://www.dmt-nexus.me/forum/default.aspx?g=posts&t=96861

The big box stores do not carry the 10% ammonium hydroxide but I am able to find it at an old mom and pop hardware store near the lake where I live, and it can be ordered on line. It comes in 1 gallon containers for a few dollars, pic on post #12. Keep in mind harmine and THH both glow blue when a bit is dabbed onto a cue tip pre-wetted with vinegar and smeared on a paper plate and held under blacklight. Harmaline glows greenish.

igorcarajo said:
Thanks. Why do you prefer to use janitorial ammonium hydroxide as opposed to something like NaOH? Also, what do you think about using sodium bicarbonate to precipitate the harmine, and then use a stronger base to precipitate the harmaline? That way you wouldn’t have to have a pH meter, calibrate it, etc.
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Great question igorcarajo. Sodium bicarbonate has a ph of 8.5, so when you use it to precipitate your rue hcl dissolved into water, you will end up with a mixture of not only harmine but a substantial amount of harmaline mixed in with your harmine.

Even though you will find teks here using this method, professional chemist will instead add milliliters of 10% ammonium hydroxide (you can find gallons of this 10% janitorial ammonium hydroxide at some hardware stores for a few dollars or more expensive on-line) using a pipette to slowly raise the ph up to exactly 7.0, where only the harmine will precipitate, with no harmaline in it. Now, from 7.1 to 8.0ph will precipitate a small middle fraction of harmine mixed with some harmaline, you will want to set this aside for a rainy day when you do another extraction, to add it back in to separate it further.

Bringing the ph above 8.0 with more milliliters of ammonium hydroxide will then precipitate only pure harmaline, with no harmine contamination, when this very pure harmaline is then further reduced to tetrahydroharmine (reduction is a chemical term which means hydrogen addition) it is extremely pure THH, with phenomenal results, it is odorless, no side effects, glows blue under blacklight when a bit is dabbed with a cue tip pre-wet with vinegar and smeared on a paper plate, it also imparts a lingering metallic taste when smeared onto tongue. Interestingly, pure LSD also glows blue under UV light and is said to also impart a metallic taste.

Once your done precipitating your harmine (1st) and your middle fraction (2nd) and in the end, get to precipitating the harmaline only (3rd), you can raise the PH to as high as 10 with a little bit of added ammonium hydroxide (add several milliliters), and your harmaline will all precipitate very quickly. Don't worry you can't overdo the addition of the ammonium hydroxide when precipitating the harmaline, it's completely safe. Ammonium hydroxide has a natural ph of around 10.0, so you can't overdo the addition of it.
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hxxps://www.sciencedirect.com/topics/medicine-and-dentistry/tetrahydroharmine

"Hallucinogenic Plants in the Mediterranean Countries"
Ioannis D. Passos, Maria Mironidou-Tzouveleki, in Neuropathology of Drug Addictions and Substance Misuse, 2016

From above article: "The content of dried seeds of the plant in harmine is about 4.3% w/w, 5.6% in harmaline, 0.6% in harmalol, and 0.1% in tetrahydroharmine."

Unfortunately, there is less than 0.1% THH in rue seeds (next to nothing), but THH is the 2nd largest alkaloid in Caapi used in traditional Ayahuasca. You will need to convert the harmaline you extract from the rue seeds directly into tetrahydroharmine using the procedure here, uses all over the counter chemicals, same yield as TIHKAL (75%) but TIHKAL THH synthesis uses hard to obtain chemicals, some of which only chemist are able to obtain. The procedure on this post is a process I developed myself many years ago so that anyone can do this at home.

All you need is vinegar, 10% janitorial ammonium hydroxide from your local mom and pop hardware store, and zinc dust from pyrotechnic places. If you don't have a vacuum pump, the above post #12 in the link explains how you can use a cotton ball stuffed into a funnel instead.

Post #1 of above link details the experiences using this very pure THH which I have used literally around a hundred times, which few people have tried. I've used this pure THH for a decade, it's simply divine and quite incredible, I value it as highly as I do mescaline.
 
ava69 said:
I don't recommend doing it that way as when harmine is reacted with teeny tiny hydrogen gas bubbles whether from zinc in vinegar or any other method (I've done this before to see what happens) it does remain as harmine but the harmine will give off a strange smell or odor indefinitely as if the reaction has some minor unknown influence on the alkaloid. It will even change the color of the harmine from it's very dark natural brown to a light tan shade. Even 300mg of pure THH made from harmaline has zero nausea, but this "weird harmine" subjected to hydrogen gas may cause nausea.
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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.
 
Jagube said:
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.
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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?
 
vin9x said:
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?
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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.
 
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.
 
igorcarajo said:
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.
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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?
 
igorcarajo said:
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?
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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.
 
Loveall said:
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.
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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?
 
Post #12. I may be a long term chemist, but I developed this many years ago so that anyone can do this at home. I actually went into a trance state after a death and received the information from a divine source on how to do this, as I was stuck at one point for weeks on end with no solution. No fancy chemicals or equipment needed like TIHKAL THH Synthesis. Due to the hundreds of Spiritual centers in South America needing these plants, Caapi is increasingly being harder to find. You can do this with normal coffee filters and cotton ball stuffed in a funnel. Tetrahydroharmine (THH): she is as valuable as mescaline, can't do without her. Diamondlike shimmering in her beauty.

In brews analyzed by the UDV, Santo Daime and Shuar Indian, THH levels were at the same high levels of harmine in the plant. Somehow, over their day's long cooking process perhaps using vitamin C (hydrogen doner) in the cooking, the THH would attain levels found as harmine in the plants. Harmaline levels often found zero but always very low (0 to 30mg levels) in a typical brew. Just google tetrahydroharmine wikipedia and read the studies attached at bottom.

Now once you have your harmaline freebase...

1) place 10.5 grams of harmaline in a 1 liter pyrex cup style glass
2) add 900ml vinegar
3) add 40g zinc dust in the pyrex glass too, use 40g zinc dust per each 10.5 grams of harmaline. You will see tiny hydrogen bubbles rise to the surface.
5) place beaker solution on a magnetic stirrer with stir rod and spin entire solution slowly
6) spin for 1.5 hour, then let solution sit for 1 hour without spinning so the zinc dust can settle to the bottom. The solution will have turned from a beginning dark green color to a transparent like golden color after it sits 1 hour after the 1.5 hour spin. Use the end of a cotton q tip to place in solution and dab on paper plate in front of blacklight, the smear will now glow light blue when transition is done...

7) Remember, once done with spin, let the solution sit for 1 hour, most (99.5%) of the zinc dust will settle to bottom, then filter solution above the zinc over a #101 9cm filter disc fitted to a vacuum flask with vacuum trap in series with your vacuum pump, this will give you a transparent golden color liquid, use this solution for next step.

Throw away any zinc dust you just collected on filter disc (be careful, don't throw zinc on top aluminum foil in garbage or it will smoke due to hydrogen loaded zinc, best to put used zinc in a baggie with water to keep it moist, keep away from aluminum).

The pump/vacuum filter flask & filter disc will remove 100% of any zinc dust. so in other words, filter pyrex beaker solution (takes out the zinc dust) over a #101 9cm filter disc fitted inside a vacuum filtration flask hooked up to a vacuum pump, with a small vacuum trap in series, in-between the filtration flask and the pump. A good pump is JB platinum DV-142N 5 CFM heavy duty vacuum pump.

Cool you are left with a 100% clear transparent with just a touch of golden very light yellow color with no zinc dust at all...now add (80ml of 10% janitorial ammonium hydroxide per 2g of harmaline)...so this means add 400ml of the 10% ammonium hydroxide to your solution...you will immediately see the thh crash out of solution as a white powder, place mason jar in fridge for at least 3 hours, the crystals will all be seen at bottom of mason jar. I like to let jars sit in fridge overnight then collect the THH at the bottom of the jars early the next morning. As you have already done quite a bit of work the 1st day.

9) you will collect 7.5 grams THH freebase on the filter disc sitting in your vacuum filtration flask once you pour fridge cold solution over a #101 9cm filter disc in your vacuumm pump, rinse THH with some hot or cold water. put filter disc of thh in a pyrex tray, scrape off and dry under fan.

10) always this will happen: exactly 75% is the yield, as I don't know why this is so...but it's a great yield still. Even in TIHKAL, the yield was similar, right at 75% as well.

11) The more zinc you use, the faster the reaction progresses, so 35 to 40g zinc means the reaction is finished by 1.5 hour.

I've looked at the #101 filter after filtration, hardly anything at all on it, truly only less than 1% of the zinc dust remains to be filtered after sitting for 1 hour.

If you don't have a vacuum pump/filtration setup: Personally, I believe the cotton ball in a funnel to be one of the greatest inventions of all time--and think it would work just fine for filtering out the remaining less than 1% zinc dust, remember 99.5% of the zinc dust falls to the bottom already after sitting for 1 hour after the spin mantel is turned off. What you are filtering is actually the less than 1% of zinc dust from the very bottom after sitting that gets kicked up back into the solution as you are decanting it off.

p.s. I also saw an episode of "Ancient Aliens" in which they discovered remnants of zinc dust inside one of the chambers, and they believe the Egyptians were making hydrogen gas using zinc and vinegar, speculating that the great pyramid was some sort of power generating device.
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igorcarajo said:
ava69:

Thanks for the kind words. My zinc reduction went well, I think. It glows bright blue under an ultraviolet light. I haven’t tried it yet, though.

I have experimented a bit with separating harmine from harmaline using your method of slowly basifying with ammonia and constantly monitoring pH, and I haven’t gotten a good handle on it yet. It seems tricky because as soon as stuff precipitates, the pH goes down. I think I added too much ammonia and I’m guessing that a bunch of harmaline precipitated with the harmine.

Also, are you sure that the 10% ammonium hydroxide is basic enough to precipitate all the harmaline? I’m asking because after getting the harmine out, I added a bunch of ammonium hydroxide to precipitate the harmaline, and some did precipitate. At that point the pH was 10.4 if I recall correctly. Then I filtered it and just for kicks I added some NaOH to the liquid and got the pH up to around 12, and some more stuff precipitated, not much but a little.
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First of all, congrats on your success! It is normal for the ph to drop down from 7.0 to around 6.7 or so as the solution becomes super saturated with harmine, right after you hit the target ph of 7.0 for harmine. This is completely normal. Always make sure you are using a really good meter like this one:

APERA INSTRUMENTS AI209 Value Series PH20 Waterproof pH Tester Kit, ±0.1 pH Accuracy (5,000 reviews). I've used 2 of these meters for a decade, supreme. Never use cheap made China made ph meters, ever.

Never necessary to ever add naoh at any point, you just add excess ammonium hydroxide (often several millilters), it has a natural ph of 10.0, and all the harmaline will fall out very quickly.

Good job, well done, it takes practice, but practice makes perfect.

Pic: 300mg very pure THH
 

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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?
 
murklan said:
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?
Click to expand...

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
 
merkin said:
[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
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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?
 
murklan said:
magnesium just seems simpler, less risky and just as good. But perhaps I've missed something?
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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!)
 
downwardsfromzero said:
[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!)
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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!
 
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