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

[endlessness]

Thanks!

Yeah i think the numbers look high in DMT compared to harmalas. A 100mg harmala dose will not be properly inhibiting MAOs, so a big part of that DMT will be wasted. i find a higher harmala amount more beneficial, and lower amounts of DMT are needed for strong effects.

 

[Elrik]

Elrik, what is your source for "[keep in mind that the paper was reporting as freebase weights"

All papers report as alkaloid freebase weights unless explicitly stated otherwise, its a basic rule of science.

what is your source or logic behind these specific numbers: "for the harmalas multiply hydrochloride dose by 0,75 to obtain the freebase dose or multiply freebase by 1,33 to get hydrochloride"?

Yes, that is at variance to the numbers some people calculate when they neglect the fact that harmala hydrochlorides crystallize as dihydrates.
Harmaline base mw 214,26
Harmaline•HCl•2H2O mw 286,762
286,762 / 214,26 = 1,338
214,26 / 286,762 = 0,747
Very slightly different from what I said, and another very slight difference with harmine and THH, but three quarters and its reciprocal are easy to remember and get extremely close to the correct value. Few of us have scales accurate enough to measure the difference.

he did provide "loose guidance" for 3 out of the 4 religious groups... you need dosing for each and every individual brew

I agree. That said, they don't dose with the precision that we do and, unless you want to vacillate between very strong and very weak trips, its safe to infer that the stronger brews tended toward the lower dose of the specified range while the weaker brews tended toward the higher dose. This is how shamans titrate dose, they brew it to roughly the concentration they want and then try it to see if the dose for the average user should be a little low or high.
I would have loved to have specific dose for each brew for average user and notes on redosing incidence and timing, but the paper really does give quite valuable information despite any shortcomings.
In the end a person just needs to have a bunch of trips and decide what works for them, anyway.

 

[GordoTEK]

Just trying to close the loop on the chemistry here. Can anyone fill in the blank (chemical equation)? I have not actually seen this written out anywhere.

This is clearly a "hydrogenation" reaction with zinc (Zn) as the reagent, and hydrogen gas as one byproduct, but beyond that, I'm not completely sure what goes where. I like to have complete understanding of things I'm studying or working with...

Thanks!

 

[blue.magic]

Zinc reacts with acetic acid, forming zinc acetate and hydrogen. The hydrogen produced goes to DHH, eventually forming THH.

I think the exact mechanism is more complicated and chemists here will give you a better idea.

You can look at some recuction reactions to have an idea.

 

[An1cca]

The double bond at the right N-atom gets hydrogenated by addition of 1 H-atom to nitrogen and 1 H-atom to the methyl-bearing carbon-atom.

 

[GordoTEK]

Thanks, so I guess the balanced equation is:

C13H14N2O + 2CH3COOH + Zn = C13H16N2O + C4H6O4Zn
harmaline + 2 acetic acid + zinc = THH + zinc acetate

 

[An1cca]

Hydrogen doesn't react stoechiometrically here, so it's best to put the Zn and acetic acid underneath the reaction arrow indicating that 'in the context of zinc reacting with acetic' DHH gets reduced to THH. Something like the Pd-reduction on this page : Oxidation and Reduction in Organic Chemistry

 

[tregar]

Thanks Elrik, it's still plenty vision producing at around or less than a couple hundred mg in a brew. Moderation is the key with the brews. I personally can't stand possible nausea and balance differences with more than 1 and 1/2 brews.

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I can't even begin to describe all the healing benefits from it. Hundreds of people have been cured of drug addictions and severe depression. The Queen of the forest provides a new perspective on life, one with a divine purpose. Everyone has a divine purpose in this life with special abilities and gifts.

 

[GordoTEK]

So I found a reputable, accredited lab that specializes in small sample lead analysis, they can detect as little as 10 ppm from a "dust wipe" and also can process soil samples and paint chips. Since I am planning lots of experimentation with harmalas, I wanted more peace of mind about potential heavy metals contamination even though the concern was pretty low (I'm kind of a health nut). I sent this lab 5 different samples:

1) Harmine/THH mix, 150mg freebae "dust wipe" sample (typical single dose quantity).
2) Harmine/harmaline/THH mix, 150mg salt form "dust wipe" sample (typical single dose quantity).
3) EBay fine zinc powder (Zinc Dust Powder- 1 lb ZN Metal. 99% Pure 5-8 Micron) Sent the lab a 5 gram sample.
4) Ebay high purity zinc particles 99.999% pure Zn grain zincum grains
5) Amazon Reagent Grade Granular Metal Zinc, 20 Mesh - The Curated Chemical Collection

The detection limit was 10 ppm. Interestingly enough, all 5 samples including the cheap ebay zinc dust, came back as "under detectable limit" for the test. So there you have it, I guess you can pretty much take this stuff every day if you want to. Another person (DaBuzz) did broader testing for all major heavy metals and did not find any after removing the zinc salts (manske method), but his test did register contamination before removing the zinc salts (he used sodium carbonate as base instead of ammonia when doing his post THH reduction precipitation, which is NOT recommended, but at least he showed that the contamination can be pretty easily removed, which is good to know for anyone that does not have access to ammonia).

 

[downwardsfromzero]

Zinc reacts with acetic acid, forming zinc acetate and hydrogen. The hydrogen produced goes to DHH, eventually forming THH.

I think the exact mechanism is more complicated and chemists here will give you a better idea.

You can look at some reduction reactions to have an idea.

The hydrogen produced fizzes off as a by-product and (largely unavoidable) waste of reagents.

It probably goes something like this:
The metallic zinc is oxidised under the reaction conditions and gives up an electron to a harmaline molecule (let's call it 'Hm' for short) if one happens to be near enough. This forms a radical anion [Hm·¯] which promptly captures a proton from a nearby water molecule to form [Hm·H]. This neutral radical species then picks up another electron from some dissolving zinc - maybe the same atom - to form what is essentially a deprotonated version of THH [HmH¯], and then rapidly attaches to another proton from the aqueous medium, or rather two of them under the acidic conditions, to form a protonated THH cation [(HmH3)+, or THH.H+].

The radical species likely will be prone to trapping molecular oxygen so, while stirring will optimise contact between the zinc and the harmaline molecules, it's best to exclude oxygen through use of an inert atmosphere and/or a pressure relief device such as a bubbler (airlock).

 

[ijahdan]

Gordotek, did you test your samples for cadmium too? I believe this is a more common and abundant contaminant of zinc than lead.
You say your friend DaBuzz successfully removed zinc and associated heavy metals (which ones specifically?) by performing a manske, thats good to know. Were your samples containing thh based using ammonia, but not manske'd? You say they tested negative for lead but what about zinc salts (which could contain cadmium)?

Its great that youre doing these kinds of analyses. A safe and foolproof thh tek which addresses all these issues cant be far off now.

 

[GordoTEK]

Gordotek, did you test your samples for cadmium too? I believe this is a more common and abundant contaminant of zinc than lead.
You say your friend DaBuzz successfully removed zinc and associated heavy metals (which ones specifically?) by performing a manske, thats good to know. Were your samples containing thh based using ammonia, but not manske'd? You say they tested negative for lead but what about zinc salts (which could contain cadmium)?

Its great that youre doing these kinds of analyses. A safe and foolproof thh tek which addresses all these issues cant be far off now.

OK - so the reason I choose to test for lead and not cadmium is because the zinc I recommend (and will likely be used by most people following my recommendation) is ASTM D520 Type III specification, and if you look into that spec, you will see that the allowable lead (0.002%) is twice the allowable cadmium (0.001%), which I assume means lead contamination is likely higher than cadmium. The next reason is that both cadmium and the zinc salts are dissolved by ammonia and should not precipitate out (again, this is the primnary reason that ammonia, and not sodium carbonate, should be used for this reduction). Lead on the other hand, is not dissolved by ammonia. So I have no reason to believe any cadmium whatsoever will be in the final product, especially if no lead is detectable.

Regarding the testing that DaBuzz did, he just used this home water testing kit, so I have no idea how accurate that might be, all I can tell you is that initially it indicated "mid-range" (of its scale) contamination on dissolved THH sample that had been precipitated with sodium carbonate, he then did a manske, took the crystals, dissolved in a filter with boiling water, then precipitated with 2% ammonia, tested it again, and there was no indication of contamination with his 2nd round of testing using the same test kit. I don't really take much stock in this type of testing, but I suppose its better than nothing.

-Gordo

 

[downwardsfromzero]

Regarding zinc and cadmium contamination, a subsequent Manske reduction after the reduction will eliminate most if not all of the heavy metal contamination because their chlorides are soluble.

 

[endlessness]

So is it confirmed thh precipitates with a manske?

I remember this being an unsolved question a while ago, I might have missed test results poeple posted...

 

[GordoTEK]

So is it confirmed thh precipitates with a manske?

I remember this being an unsolved question a while ago, I might have missed test results poeple posted...

Yes, confirmed.

 

[ijahdan]

Regarding zinc and cadmium contamination, a subsequent Manske reduction after the reduction will eliminate most if not all of the heavy metal contamination because their chlorides are soluble.

But, according to wikipedia, lead(II)chloride is barely soluble in water. Also, do we know for sure that the Manske process converts other substances to their chlorides, as it does with harmalas?

 

[downwardsfromzero]

Regarding zinc and cadmium contamination, a subsequent Manske reduction after the reduction will eliminate most if not all of the heavy metal contamination because their chlorides are soluble.

But, according to wikipedia, lead(II)chloride is barely soluble in water. Also, do we know for sure that the Manske process converts other substances to their chlorides, as it does with harmalas?

Sorry, that was unclear. I meant the zinc and cadmium. If any zinc and cadmium salts were introduced into the harmala acetate solution as their respective acetates they should largely remain in solution while the harmalas precipitate, unless alkaloid-metal complexes form which co-precipitate with the harmala hydrochlorides. The tendency of cadmium to form complex chloride anions may mean that some cadmium might co-precipitate as harmala tetrachlorocadmate(II), although it's highly unlikely any solubility data exists for that group of compounds.

Precipitation of lead(II)chloride would be dependant on its solubility product being exceeded. It is the most soluble of the 'insoluble' chlorides (10.8 g/L @ 20 °C), with the solubility increasing markedly with increase in temperature. It appears any solubility data for lead (II) tetrachlorocadmate (II) is hard to find if it indeed exists at all, but I get the feeling that might not be terribly soluble either.

The precautionary principle dictates using high purity zinc is the wisest approach, but definitive data would only come from analysis for heavy metals of a zinc-reduced harmala alkaloid sample.

 

[blue.magic]

So is it confirmed thh precipitates with a manske?

I remember this being an unsolved question a while ago, I might have missed test results poeple posted...

Yes, confirmed.

It would be nice to know THH salt and sodium chloride concentration. Is it the same as with harmine/harmaline? I usually stick with 10-20 g/L harmala freebase and 10% salt, but I am not sure if that would work for THH.

I made THH.HCl precipitate just from water, but the process was too quick and Manske would be much cleaner.

 

[GordoTEK]

It would be nice to know THH salt and sodium chloride concentration. Is it the same as with harmine/harmaline? I usually stick with 10-20 g/L harmala freebase and 10% salt, but I am not sure if that would work for THH.

I made THH.HCl precipitate just from water, but the process was too quick and Manske would be much cleaner.

From DaBuzz's doc:
"You could purify separately or combine and do both in the one process.

Harmine and THH were combined and further purified first by dissolving it in hot acetic acid (vinegar) and adding an equal volume of hot saturated salt-solution and left to slowly cool."


So use enough hot vinegar to dissolve your alkaloid/s and add an equal amount of hot saturated salt-solution.

 

[GordoTEK]

Harmaline reduction to THH TEK
Thanks to everyone here who helped make this project possible. I hope a few people can put this to good use. THH is a compound that deserves more attention, and further research. Let me know if you notice any mistakes.

Content Index:

1:01 Why trade harmaline for THH?

2:50 Alkaloid analysis of numerous ayahuasca samples

5:42 The chemistry of harmaline reduction explained

6:26 Things you will need

8:19 REDUCTION BEGINS

8:43 How much vinegar?

9:42 How much zinc?

11:08 Hydrogen gas observed

11:34 First decant and filter

12:07 Post filter decant

12:34 Ammonia shake test

13:44 Alkaloid precipitation

18:01 Filtering out the alkaloids

19:05 Washing the alkaloids

19:54 Drying

20:55 Storage

21:17 Dosage Guidelines

22:18 Dangerous Interactions