Yes mansked the acidic phase from mixed Harmala HCL after reduction with magnesium. The reason i did that is because i tried to seperate Harmine:Harmaline using sodium bicarbonate. And had 2080mg:220mg. This experiment proved a few things.
1) my Harmine:harmaline seperation was dirty tek. Maybe clean harmaline portion but the harmine was not.
2) that what is not mansking out, roughly now 1g, might be the reduced Harmaline.

I wanted to convert to HCL salts specifically, I dont see why it would interfere as the reduction was underdone in acidic conditions. I think recovery should be done under acidic conditions rather than basic as mag salts/hydroxides are soluble in water under acidic conditions.

I would of thought that the solubility of Magnesium Chloride in water, being higher than that of Nacl, itself being higher than that of Harmine HCL, would of helped the Manske.

I might try a more salt saturated solution to recover, to account for the extra Mg ions, with a further clean up manske if successful.

It has been a while since i have picked up a chemistry textbook so this may be incorrect way to approach this.

I wonder if THH forms complexes with magnesium ions. I think that using ammonia for the basic phase should help in this respect. When time is available (after some outdoor projects are completed) I shall be doing some tests with magnesium to confirm its behavior in harmaline reduction followed by precipitation with ammonia.

There is some precipitation/cloudiness to the solution so I'm just biding some time. a post from our very own 69ron on a seperate forum:

Quite possibly, i gave up on the recovery there.

To this one I acidified 0.5g harmaline with excess 5% acetic acid. 0.150g of Magnesium. 1:3 mol ratio. Waited for reaction to complete and to be clear, this took a few hours, filtered. Based out with ammonia, succesfully recovered 0.180g of grey/tan freebase. Solution was left in beaker, and more has precipped out.

Some thoughts, there was some reddish precip after the zinc reduction, very small amount similar to what i was seeing with previous experiment, could this be harmalol? Once the reaction is over and clear, this is not the end as it was still precipping a day later. I also didnt noticed the much colour change with harmala uv fluorescence whilst the reaction was going on. Due to the long reaction time i probably shouldnt of fitered whilst it was still ongoing.

255mg of Harmaline FB was added to 20mls of 5% acetic acid along with 80mg of magnesium ribbon. Continuously stirred until most of the magnesium was dissolved. Left to sit for a while. Precipitated out with ammonia and collected once settled.

180mg of reduced harmala freebase collected.

I attach a photo of the harmaline beforehand, the reduced harmala alkaloid next to a larger bag of harmine for colour comparison. Seems it got darker than the harmaline and even harmine?

Other two photos are of the beaker 1 week after collection, seems to grow darker. And a red and very dark brown precip in filter paper. Could be harmine-n-oxide from the harmaline initially? Unsure where the extra 80mg has gone but it seems too much to be initial harmine contam in the harmaline.

Are you suggesting the harmaline oxidized to harmine and then harmine-n-oxide during storage?
I think if the latter oxidation was likely to occur under typical storage conditions, harmine-n-oxide would have been identified as one of the constituents of P. harmala seeds.

Then, there is the question of whether the magnesium would have reduced the harmine-n-oxide back to harmine. And an even more interesting question: magnesium being a stronger reducing agent than zinc (reduction potential -2.37V vs -0.76V), can magnesium reduce harmine to harmaline? This could of course be tested, but perhaps a chemist can chime in and shed some light on the theoretical side of it? From what I understand, these reductions are actually a sequence of two reactions: (1) the metal reducing the acid and releasing H2, and (2) the H2 hydrogenating the alkaloid. FWIU, in the potential harmine -> harmaline reduction, the problem is not with (1) but with (2), and the metal's reduction potential doesn't play a role there - so the answer is no?

On a separate note, I like to work with larger amounts (like 1 gram or more) to minimize the relative losses (material getting trapped in the filter paper etc.).

No storage, this is all over a few days.

Is it possible for trace harmine levels in the harmaline fraction, initially seperated from full spec using soidum bicarbonate method, to be oxidised alongside the reduction of harmaline occuring?

What do you make of the colour of the smaller bag being the reduced harmaline?

I don't see how that would be possible.
Another thing is, the separation probably wasn't that good if sodium bicarbonate was used.

I don't know what to make of the product being darker. Did you confirm the reduction was successful? With UV, reagents (Marquis should be green for THH and brown for harmaline), a taste test? (harmaline fb is very bitter, THH fb doesn't have much of a taste)

An unsuccessful reduction can also cause losses if you cut off the precipitation at, say, pH 9.8, which is sufficient for THH, but not for harmaline, as some harmaline stays in salt form and gets discarded.

Good shout on the spot tests. My marquis and froehde has expired. Mandellin did show a similar but different reaction, between Harmine and the fraction in question.

https://www.dmt-nexus.me...aspx?g=posts&t=25771 - Endlessness post on spot test results.

Scratching this one up to freebasing out the alkaloids whilst the reaction was ongoing.

It is now generally thought that, in the absence of a suitable catalyst, it is not molecular hydrogen (in the form of the now-discredited 'nascent hydrogen') that is responsible for reduction during dissolving metal reactions.

The dissolving metal transfers electrons to the neighboring solvent sphere and some of these electrons get passed on to the reductand, in this case harmaline, while others reduce the water to hydrogen. The gas which fizzes out is essentially being wasted.

The reduction of harmine to harmaline has been carried out with sodium in ethanol. The EMF figure I have for sodium under acidic conditions is +2.714V (an American book, so the sign is reversed on the other side of the Atlantic IIRC) so it would depend on the exact reduction potential of harmine whether magnesium would be strong enough a reducing agent for this reduction to happen with that metal.

[Incidentally, the reduction potential from magnesium under basic conditions is somewhat higher - closer to that of sodium at (now 'corrected' sign) -2.69V - although I would anticipate that the reaction of harmine would require a higher magnitude of EMF under basic conditions but the relative difference might be advantageous. It would also require a solvent such as methanol for the reaction to work. I can only imagine this reaction (Mg + 2 OH- → Mg(OH)2 + 2e-) will be slowed greatly by the insoluble by-product.

I rather foresee practical difficulties with the poorly soluble magnesium hydroxide that would be produced, not to mention the likelihood of it requiring refluxing in some alcohol or other - probably a mixture of methanol and ethanol with a little water. So, yeah, don't try this idea at home unless you have a decent lab there. This was just some thought experiment ramblings, sorry!]


I'm with you on the losses associated with downscaling. For these tiny experiments you want to use small kit like microscale sets and such.

Just one observation to add:

Sometimes after reduction and upon basification with ammonia, a brown, sticky mess precipitates, which traps the stir bar around pH 9, before the THH cut-off level.
It has happened to me a few times and I've had to continue stirring manually.

If vinegar is subsequently added to the collected precipitate, the THH dissolves, but the brown mess doesn't.

My guess is that it's impurities and it happens when the harmaline hasn't been cleaned enough by Manske. I always run the pre-reduction harmaline acetate through a coffee filter and it runs clean, so the mess must be the result of the reduction protocol (a reaction with zinc and then ammonia?).

And an unrelated question: could it be that one of the stereoisomers is less stable and reverts back to harmaline more readily than the other? In that case, the THH in caapi brews could be more stable than the racemic, synthetic THH, of which half would be unstable and oxidize quickly. But in that case, the process could be repeated, resulting in higher ratios of the 'natural' one with each iteration: 50%, 75%, 87.5% and so on. Perhaps even without the need for harmaline/THH separation in between.

Could you nail down if things were changed or different between no-mess and brown-mess situations? Change in concentrations of actives in the total volume perhaps?

I've only encountered the brown mess (total disaster type of mess) using carbonates, ammonia looked like a ticket to get around it, so far. It looks like it's conditions related, this brown mess problem. An1cca could use carbonates following VDS protocol very rigorous.

Initially I thought it was concentration-related, but in my last reduction the concentration was low and the mess still occurred. Adding water didn't help it.
That's why I suspect it has to do with cleanliness of the harmaline. I haven't taken notes to be able to compare the results though.

I also add a dash of ammonium chloride before basification, which may have an effect, but I wouldn't know in which direction.
Another variable is the HCl I add on top of the vinegar, to bring the pH to ~2.
Maybe I allowed too much zinc to dissolve, which led to more zinc salts and promoted mess formation.

Hi, read this entire thread and decided to do a magnesium reduction using acetic acid. I've tried zinc reductions before, and the only time I got decent results was using a test tube and swirling it manually for about 3 days.

Added 5g Mg ribbon to 150ml 7% acetic acid with 3000mg harmaline FB dissolved in a flask. I know this is an excessive amount of Mg, but I wanted to make sure I had enough to complete the reduction. Magnetic stirred on low speed for about one hour, plenty of bubbling. The bubbling suddenly slowed down and almost stopped, while there was still plenty of Mg ribbon left. I added more acetic acid, and the bubbling started again. Stirred for another hour, bubbling stopped and I left it for an hour. Filtered out the remaining Mg and measured PH at 4.8. Solution started with PH around 3.5 before reduction. The acetic acid reacted with the Mg, creating magnesium acetate and hydrogen, consuming itself in the process.

Based dropwise with ammonia 12% and got a nice clean precipitate, filtered and washed with ammonia 3% to make sure all magnesium acetate would dissolve. Dried and ended up with almost 4000mg of white powder. There is some Magnesium contamination in there, and I wonder if I should have kept washing it. Maybe water's ability to dissolve magnesium acetate is limited and I needed more liquid to fully get rid of it. Or there was some additional reaction between the THH and Mg, not sure. Anyway, the product is great and the reduction must have been close to 100%. We did toxicity testing by trying small amounts, and have used it in sessions several times with no bad side effects. Magnesium acetate is basically non-toxic, and you would need something like 861 grams of it for an LD50 dose, and the amount in a standard 200mg dose is around 50mg, so not too concerned. However, next time I will use more liquid and less Mg and calculate my moles.

I can tell the reduction is good, since I get no harmaline effects, no tracers, no ringing in the ears, no nausea. With my zinc reduction attempts I always ended up with some unreduced harmaline, which is easy to spot during consumption.

Note on the brown goo: I always get this during my second or third manske. Nasty looking goop at the bottom of the jar with the good stuff sitting on top. I filter it out at that point, and assume it's impurities, possibly pigment. It doesn't come back later in the process. I am pretty diligent with my boiling, filtering and manske, so it takes me about a week to do a batch (1 day boiling, 2 days filtering, 4 days manske), but the end result is worth it.

Thanks BongQuijote for the report. The first successful harmaline->THH reduction with magnesium report on the Nexus!

Magnesium itself has low toxicity and I wouldn't worry about it, but metals tend to be contaminated with heavy metals like cadmium or lead. I haven't heard of magnesium being contaminated, but it would be nice to get more data to confirm that it's safe.
A bioassay is not good enough a toxicity test, as the effects of heavy metals accumulate in the body and can cause problems later on with repeated exposure. A heavy metal detector would be helpful.

IME zinc reductions are often incomplete due to insufficient acid. That's why I like to add HCl.
It may be that with magnesium, being a stronger reducing agent, less acid is needed to complete the reaction within a reasonable timeframe.

Thanks! Since the reduction consumed all the acid, twice, I think it's wise to use more or stronger acid. The shorter reduction period is probably due to Magnesium's higher reactivity.

Good point regarding heavy metal contamination. I attached the sheet from the package, and I don't see anything concerning, but you guys may know better.

About the only sensible reason I can think of why this would be the case for THH in solution is if somehow there is an enzyme - or, by extension, a living organism - which preferentially metabolises one enantiomer over the other. I doubt the intrinsic handedness of neutrinos would have much of an effect within the normal time scale encountered in the laboratory .

The exception to this is with consideration of the crystallisation process. THH will, in all likelihood, crystallise more readily as the single enantiomer rather than the racemic mixture. This means that the energy state of racemic THH crystals will be a tad higher than that of the stereochemically pure compound, thus making the reactivity of the former a tiny bit enhanced in comparison with the latter. [This idea is stated in absence of my being aware of any experimental evidence for it.]

Given further consideration, one other possibility for the racemic THH being unstable in solution is if the pairing of enantiomers allows an autocatalytic decomposition process which would be stereochemically forbidden in the case of the pure, isolated enantiomers[, subject to the same caveat as above.]

BongQuixote - I love your nick!

Welcome to the Nexus and thank you for your fantastic opening contributions. [EDIT: I see you're not actually completely new to us. Were you a full member before? Do you remember what threads/topics you posted in?]

At some point in the (hopefully) not too distant future I'll be giving the magnesium reduction a try as well. It will be great to be able to compare notes.

Yes, I used to be a full member, probably been here 3-4 years or so on and off. I was pretty active in the DMT extraction threads when I was working out my tek. I do have some additional notes on VDS after doing it a bunch of times, so I'll post those in a few days.

A, perhaps, relevant question becomes:
Do harmala hydrochloride magnesium chloride double salts crystallize out in a manske when there are magnesium salts present?

Basing a mix of harmala acetates and magnesium acetate gives you a mix of harmala base and magnesium hydroxide. Ammonium salts are noted to dissolve the normally insoluble magnesium hydroxide but, clearly, in the above experiment not all were dissolved. Doing a manske on the resultant solid product would place magnesium acetate/chloride in a situation to associate with the alkaloid in the same way it does with ammonium salts and produce a crystalline double salt when the excess salt pushes the harmalas out of solution.

I suppose the experiment would look like this.
• Dissolve some harmala hydrochloride
• Add some magnesium acetate, chloride or sulfate to most of that solution
• Save a portion of the above solution and do a manske on the rest, dissolve the vacuum filtered crystals in water
• Make a stock solution of a soluble basic phosphate, fluoride, or oxalate
• Add the precipitant to the magnesium-free solution, see if the harmalas precipitate [if they do then you'll need a different precipitant]
• Add the functional precipitant to the magnesium-containing solution, see if the magnesium precipitates [if it doesn't then the alkaloid double salt is keeping the magnesium in solution and you'll need a different precipitant]
• Add the functional precipitant to the solution of mansked alkaloid. If no precipitate forms then no magnesium survived the manske, if precipitate does form then a saline-insoluble harmala-magnesium double salt does form in the manske crystallization.

I think I got all those details right, its bed time