Hi friends,

Thinking of brewing some caapi for use on its own, and preferably I'd like a lot of THH in the brew. I've done the Mg metal + HCl tek before to convert harmaline to THH, and I was wondering if I could simply add the HCl and Mg to caapi powder or if that would be risking the reduction of molecules aside from harmaline/harmine which might then become toxic. Anyone have any idea? How would you rate this approach on a scale of stupidity ranging from 1 (brilliant) to 10 (insanely stupid)?

Thanks for your time.

It seems Zinc is not able to reduce harmine, I've no idea if Mg would.
Could you please point (link?) to the Mg + HCl tek you did on harmaline? I suppose it's not much different than working with Zn but just curious for the details.
Thank you very much.

Yes I'm quite sure I had success with harmaline but not sure if harmine would work. It was quite simple, I just dissolved the harmaline in dilute HCl and added a ribbon of Mg. Reaction was obvious with lots of heat and bubbling, and when it was done I basified and dehydrated the filtrate. A friend had it analyzed at a third-party lab and was satisfied that it was mostly THH, tho I did not personally see the results. But I did bio-assay and it felt very clear like THH, nothing like harmaline.

Anyway, the question is whether this would be dangerous with whole caapi, considering all the potential chemical changes to the various molecules in there.

AFAIK there is only very little harmaline in caapi. Most is harmine and thh. The harmine will not be reduced by Zn or Mg with acid. I don't see the point of doing this with caapi.

Hmm ok but would it be dangerous? Guess there is no way to predict..

The trouble with trying to reduce a whole brew is not only that you are potentially modifying unknowns, it is also the amount of chemicals you'll be adding to the brew that will remain afterward. Unless you finally make an extract, which IMO would be working in the wrong order.

I'm pretty sure the resulting tea will be a wretched drink. Magnesium salts cause flushing of the intestines - diarrhea is an understatement - and hydrochloric acid is not exactly tasty. You could neutralize the acid, but it would still taste bad.

If you want to do a reduction, isolate first, then reduce, then work up and isolate again.

With due attention to the stoichiometry, the magnesium would take care of that.

Other than that, extract and isolate first, then reduce - as pitubo says.


Now this has made me wonder what sodium in ethanol would do for harmine (that would be a somewhat dangerous procedure for the novice, so only attempt it if you have the appropriate laboratory skills and experience!)


To reduce harmaline in a tea, you could try adding ascorbic acid - vitamin C - before boiling instead.

Thanks pitubo for the warning. I will forget the idea.

And thanks downwardsfromzero for suggesting ascorbic acid--but from what I've read (which might be old info on here), ascorbic acid hasn't been shown effective at reducing harmaline, except according to professor8's single experiment. If it were effective, tho, I'm thinking it would be dangerous to add ascorbic acid to a caapi tea or a rue tea given the potential for other chemicals being reduced into unknowns... just as with the Mg tho maybe to a lesser extent. I'm pretty sure I already have made caapi and/or rue tea with ascorbic acid in the past. Didn't notice any special effects but that doesn't mean anything.

I've been wanting to try this, but AFAIU in order to use ascorbic acid as a reducing agent, it needs an alkaline environment. Perhaps this is best exploited by adding ascorbic acid to chacruna or mimosa tea. Especially the chacruna might benefit from this, since it has lots of dmt n-oxides.

I agree that DMT-N-oxide would be a better candidate for ascorbic acid reduction. Sometimes I become overly optimistic (delusional) when up past my bedtime!

Does ascorbic acid merely fail to act as a reducing agent in an acidic environment? Or will it even become (very) weakly oxidising? All told, we'd be looking for a hydride or electron donor to a protonated harmaline, which, to my mind at least, suggests somewhere around physiological pH. Best sleep on that

I should leave it to a skilled chemist to answer these questions.

On reviewing the matter, I found a reference claiming that the oxidized form of ascorbic acid, dehydroascorbic acid, is unstable at neutral pH. Since the oxidized and reduced form are in equilibrium, this decay would drive the reaction (oxidation of ascorbic acid and reduction of eg. harmaline) forward.

Another reference states, in relation to the reduction of p-quinone, that the reactive species undergoing oxidation is the deprotonated acid.

Ascorbic acid easily reduces iodine to iodide or Cu2+ to Cu in acidic or neutral conditions, it seems that the ascorbate ion is the reactive species, there will always be some amount of ascorbate ion though, even in basic conditions.

It seems to be a reductant for a substrate that is very willing enough to accept an electron. Iodine is a pretty strong oxidizer. Benzoquinone is another good example, it is also a weak oxidizer, it has a strong desire to aromatize, and it is often used as an 'electron sink' in some (photo)catalytic reactions. This 'electron sink' drives the reaction. For the reaction with benzoquinone, It appears to go through a radical mechanism, a hydride and then a proton transfer, which is typical in the reduction of benzoquinones.

I've always thought that the oxidation of harmaline to harmine might go quite easily, since it is only 2 electrons away from becoming a highly aromatic molecule...

In the reverse, there is not much to drive the formation of THH, I attempted to reduce harmaline to THH by boiling with ascorbic acid, the results were not very promising :
https://www.dmt-nexus.me...&m=781300#post781300

I tried this one too, unsuccessfully.

https://www.dmt-nexus.me...spx?g=posts&t=72078

Though I think it was a problem with the process, this reduction should work... plain sodium in ethanol are hard conditions to control... It reacts too fast with the ethanol. The reaction can be slowed down by using a 5-10% sodium mercury amalgam. Though definitely not a viable route by any means, you don't want to even bother with mercury salts. Though I do want to try it again out of curiosity, using some sodium amalgam.

---

Oh yeah, as for the OP, while magnesium has a high reduction potential, stronger is not always better. It has a number of properties that make it unsuitable as a reducing agent in organic chemistry. Its highly reactive towards air and water, (forms oxide layer very fast) amalgamation doesn't reduce its reactivity much either. It is a powerful agent, in water free conditions, it can reduce alkyl halides to form organometallic complexes (grignards), usually activated with iodine.

It has very limited use, though I have read about Mg/MeOH as a reducing agent (activated with iodine), in some cases it is stronger than Zn/AcOH, this intrigues me I think it would be worth trying out. Though Mg/HCl, I have never once seen this used, I assume to its unsuitable properties... So I doubt your conversion was successful, but maybe it does work.
Also, the utility also has to do with the complex the metal forms in solution, it finds niche uses such as the pinacol coupling.

In comparison, zinc is an extremely versatile reducing agent, it can be modified in many different ways to suit the needs of different reactions.