what source of heat? fire+possible hydrogen gas is not good idea.

Btw, how do you expect to assess if there was any change in your product? Do you have a control group (harmalas dissolved in vinegar and done the same process except no aluminium) ? Or what other ways are you considering? I'd get some reagent like marquis or whatever, and also I'd check out under UV light. But do with a control.

I'll be using a crock pot, so no naked flame.



I hadn't really thought that far ahead, tbh. My main concern at the moment is 1) Getting the Al foil to react with the vinegar, 2) precipitating Al(OH)3 with NaOH, 3) Dissolving the Al(OH)3 with excess NaOH. If all of the above happen with no problem, I can then start worrying about the harmalas. As for control group, my rue extract is already in freebase form, so the only reason to do anything to it would be to match the extra purification step undergone by the non-control. I don't know what marquis is, and I have no UV light, although I could get one on eBay from china for £1. Does THH glow at a different colour to the other harmalas? To what extent does the colour under UV depend on the acid used to make the salt?

Still no difference with heat. This made me wonder if the foil I was using was even aluminium at all, or if somehow it needed to be in very small particles. So I looked up aluminium powder on eBay, which I had previously been loathe to do because most of it that I had seen before came in the form of EXTREMELY fine powder, which would obviously be dangerous or at least impractical, and would probably slip through a coffee filter. Then I saw today that aluminium powder should NOT be exposed to water. In fact it's dangerous to even have it in the presence of moisture or air.

From one eBay seller:



Zinc appears to be far safer, but it's still flammable:



Sounds like a good job you didn't heat the vinegar! It seems if you take an otherwise harmless seeming metal and powder it, it becomes a fire hazard even in the presence or water or air! Looks like I'm going to have to order some (coarse) zinc powder and try that. It looks as though zinc is the only viable reducing agent for this. Unless there are any other reducing agent metals with amphoteric hydroxides, and I don't think there are.

Also from that MSDS:



Caution is advised!

it most certainly should, considering that there's no conjugation on the piperidine moiety of THH.

Thanks benzyme, with that kind of language you certainly live up to the title of "extreme chemical expert" Could you be so kind as to chime in on the aluminium dust issue? Can you explain why finely cut (supposedly) aluminium foil hasn't reacted with vinegar for me even after 48 hours, yet I read that fine powder (300 mesh or finer) should not be exposed even to air, and certainly never mixed with water, because of fire/explosion risk? Does this make aluminium an absolutely nonviable choice as a reducing agent? Magnesium is a no-goer, since magnesium hydroxide isn't amphoteric, and sodium obviously isn't too fond of water, so it seems that zinc is the only remaining possibility.

Sorry to ask so many questions, I'm just eager to try this, since the amphoterism of both zinc hydroxide and aluminium hydroxide should mean that the resultant THH freebase could be isolated using only NaOH without the use of any solvents.

I did some tests on some of the hypotheses mentioned earlier in the thread:

1. Added zinc dust to common 5% vinegar, observed small bubbles.
2. Let stand for 2 hours to allow reaction to progress.
3. Filtered out excess zinc particles.
4. Split solution into two containers to test two ideas:

A. Zinc carbonate + THH precipitate can be washed with acetic acid to dissolve THH, leaving behind Zn carbonate.
To test this assumption, I added a solution of sodium carbonate to the zinc acetate solution, precipitating zinc carbonate. Filtered out zinc carbonate and tried washing with acetic acid -> instantly went back into solution. So, this won't work to separate the THH.

B. Basify with concentrated NaOH solution to precipitate THH, zinc hydroxide stays in solution as sodium zincate.
To test this, I basified the zinc acetate solution with enough NaOH to bring it to pH 13. No precipitate formed so I assume that the zinc stayed in solution as sodium zincate. It looks likely that this will work to precipitate only THH, assuming that the high pH doesn't harm the harmalas!

I am currently testing this for real with 1g of mostly pure Harmaline, will update with results.

Interesting, thanks for sharing

Let us know how it works with the harmaline!

So, I finished the harmaline reduction, basing with NaOH. From a starting amount of 1.01g harmaline, the final yield was 0.29g of pure white powder, presumably THH. It is much whiter than the starting harmaline was (light tan) but has the same consistency.

Full procedure:
1. 1.01g harmaline added to 200ml vinegar, dissolved to form bright yellow solution
2. Added a few grams of zinc dust, let sit for 4 hours, stirring occasionally. Solution stayed yellow.
3. filtered out zinc dust.
4. Combined with 200ml of 2M NaOH, white precipitate instantly formed.
5. Let settle for 1 hour in fridge, solution is now clear.
6. Filtered solution through several coffee filters, then washed the filters with a very weak solution of sodium carbonate (maybe could just use water?) twice to get rid of as much strong base as possible.
7. Collected material from filter paper and dried at 150F in oven, then massed.

I'm not sure where the missing harmalas went, because even if the conversion wasn't successful they should have precipitated out. They might possibly be destroyed by the high pH used, or might have been lost when washing, though that seems unlikely. A small amount (<20mg) was unrecoverable from the filter paper. Any ideas?

Hmmm, interesting... Not sure where it could have went, all I can think of is filter paper, or that your harmaline wasnt so pure to begin with? I don't think THH is unstable under these conditions.

By the way, whenever you do such experiments, I recommend having a control group also, to really know if the differences are merely due to reprecipitating, or due to the reduction.

Do you still have some of that harmaline? Now how do you pretend to go about and checking if conversion worked? Do you have any reagent such as marquis etc? What about UV light, do you have some?

I'm fairly certain the harmaline was mostly pure, it had been isolated from rue, filtered maybe 20 times total through 3 base-manske cycles, then separated from harmine by doing 2 successive base precipitations.

I feel like an idiot - I immediately started another batch without saving any of my harmaline to use as a control. I plan to be more observant of color changes this time, and I will let the reduction run for 24 hours. Will have to wait until I extract another batch of rue to do a true comparison.

I don't have a true UV light, but I did shine an LED flashlight (which I think emits some in the UV) through the solution, and it had a blueish tint to it (solution was yellow in normal light), which I think is indicative of THH, right? Otherwise, I don't really have any way to test (other than bioassay, which I am hesitant to do).

you should compare the color with a control, dissolving same quantity of harmaline vs the supposed thh, and see how different they are.

otherwise its impossible to say if something is happening or not...

or you should look into tlc / reagents.

Well, the preliminary results from my second try are in. From 2.69g of harmaline, I repeated the procedure, reducing with zinc + acetic acid for 24hrs, then basing with NaOH to ph 13. The first collection netted 1.05g of white powder, for a yield of ~39%, better than the previous 29%.

However, there's still some small particles floating in the solution that made it through the filter, so I'm waiting for those to settle and I will try to get them again, so the final yield may be as high as 50%. Edit: grand total of 1.30g white powder recovered, or 48% yield.

I have some marquis reagent on the way so that I can confirm that this powder contains THH. I definitely noticed a change in the solution after the reduction though, it went from an amber yellow to kind of a greenish-yellow color. Plus, a solution of harmaline will stain glass yellow if you swirl it around, while the solution post-reduction did not have this property (nor did it stain the filter paper yellow). It seems like the THH doesn't have the strong dye properties of harmaline/harmine.

My only ideas for what could have happened to the missing harmalas are (1) my harmaline was very impure, seems unlikely; (2) high concentration of NaOH destroys some of the reaction product; (3) not all of the THH precipitated out of solution when based. None seem particularly likely, except that as much as half of the harmaline turned into something other than THH, because otherwise it should have come out of solution.

I should note that the final filtered solution had a color kind of like watery beer, so something of note was still in solution, though it might have been acetate or zinc compounds. It didn't seem to have any of the previously noted fluorescence.

hello

just putting my 2 cents in.

did a zinc reduction of half a jar of harmalas, separated into two jars and did the same procedure of acid base and salt precipitation with the one variable being the zinc powder.

the resulting "thh" was significantly more yellow than the norm, i then took two seperate 10mg allergy tests, one just because, and a second one to check if a problem with watery stool was caused by it.

then took 200mg.

no perceptual distortion, no locomotive impairment, improvement on spelling ability, some light nausea that passed without incident, a little bit of shaking of vision left and right at one point and late cev of simple patterns.

this stuff is very calming but not sedative, it would be an excellent antidepressant in the right dose given that it neither numbs you nor acts like happy pills, it does cloud your mind a bit though (probably caused by build up of other hormones because they are not being broken down) and it does have a hangover at that 200mg.

all said the main thing is this counteracts the normal pacing around caused by pure harmalas, a combination dose between thh, harmine and harmaline in the correct proportions would probably provide an excellent inhibitor combine the effectiveness of the the latter two with the calm of the first.

all said once that ratio is found cappi effectively becomes redundant and with pharma you should in theory be able to have the same experience profile as if you drank the tea.

also side note, we need to make a thread about post harmalas hangover recovery tips, head still feel a bit heavy, but that said even after 12 hours the calming effect seems to be maintained a bit.

very fascinating stuff, thank you for making this thread and helping me through this endlessness.

and thank you everyone for reading all the way down to here, hope you all have a great day, even if it is months from now that your reading this.


____________________________________________________________


waited to add one next day note.

if anyone knows the half-life of thh this would be very useful information, the effects in a more subtle form persisted for more than a day after, though it might have be placebo, with the calm like effect being retained well past noon the next day and a sensation of "mushroomness" to the heaviness of the head (a thinning of the weigh in lower parts of the brain with the heaviness still being retained near the top)

this effect i have not experience before and it makes me wonder what, if this is not an maoi, it is actually doing because (and im just speculating here) i highly doubt that the half life is more than 8 hours and there has to be a hormone that is either being elevated or depressed which is taking much longer to return to normal levels than the "inhibition" ceasing should take to break down.

what ever is happening, presuming that its effects are reversible a single 200mg dose will put you in this calm/attentive but heavy-headed state for more than a day, a great deal longer than its sister compounds are active.

if the only side effect profile is this heaviness then i think this stuff could be very useful, but how exactly i dont know since i do know what it is doing chemically.

also on the uv subject, the thh and the harmalas it was converted glow at different colours when put under a uvlamp, the thh on its own is more yellow then what it was converted from in standard light and in turn is more yellow/bluish under the uv light compared to the green of the original, somewhere between harmala green and quinine blue. please forgive the crude explanation i don't have any was to really examine it except by just looking at it.

thank you.

excellent, thanks for sharing!

So asking anon on the chat, he said he checked a control vs the supposed thh with UV light and they did shine differently.


So with the recent experimentations, seems we found that THH does precipitate with manske, so therefore manske is a good way of separating THH from zinc, and also using lye to precipitate freebase THH also works, when usinc excess lye, which leaves zinc soluble in water.

A lot of good data, thanks everybody for sharing, and keep sharing if you do more tests

I tested some of the previously produced white powder with some marquis reagent and it turned green, which according to this thread means there is likely the presence of THH. I think it's a safe assumption that the precipitate formed by basing with NaOH after reducing harmaline with zinc and acetic acid is indeed THH (or at least contains some).

I plan on trying the manske route sometime to see if the yields can be higher than what I've been able to get with the base precipitation.

Great work, thanks for sharing!

anonenium wrote:
..THH is a mild to moderate SSRI (selective serotonin re-uptake inhibitor), according to Callaway..don't have the reference at hand, my apologies..
it has very little if any MAOI activity..but in conjunction with MAOIs (as in caapi) it probably has synergistic effects..

thanks for the interesting work all contributors..!

I've been trying the manske route to precipitate THH after reducing harmaline with zinc+vinegar. So far, I've not had much success. There is some small amount of precipitate (maybe 30mg?), but nothing more and the solution is still the same yellow color that it started with.

I started with a concentration of 100g/L of NaCl, waited 4 hours - small amount of precipitate but nothing else.

After 4 hours, upped the concentration to 150g/L, waited another 4 hours - no further progress.

Finally, upped it to 200g/L, then waited for 10 hours - there's slightly more precipitate, but this might just be the same particles in solution settling out.

My preliminary theory is that the small amount of precipitate is leftover harmaline which didn't get converted during the reduction. I tried to recover it to test with marquis reagent, but there was so little that I wasn't even able to get a tiny bit to test with out of the filter paper.

I would have to say right now that THH does not come out of solution in the presence of NaCl. However, on a positive note, the manske process can be used to remove any remaining harmaline from the solution before basing with NaOH, to obtain THH of higher purity.

I later based with NaOH to recover the THH like I previously did and tons of white precipitate immediately formed.

anonenium, what were the exact conditions where you were able to manske THH, and are you sure the compound you recovered was THH?

..an interesting experiment would be to combine verified THH with harmine/harmaline (vs just harmine) to see what possible synergy could be happening in ayahuasca..
also, doing the prolonged boiling experiment on just harmine or harmaline to see if this is what led to THH detected in ayahuasca brews (as mentioned by Snozzleberry in his MAPS talk)