So I was running some TLC plates on some crude conversion of harmaline to THH, and comparing that with caapi. Then I noticed the THH from the synth glowed very different than the natural THH.

Under 365nm UV light (normal blacklight)
Harmine: Purpleish dark blue
Harmaline: light cyan blue
Caapi THH: Greenish yellow
Synthed THH: Very faint barely noticeable cyan blue(t+1hr) to light cyan blue (t+24hr)

Under 254nm UV light (UV-C light)
Harmine: Strong blue
Harmaline: light cyan blue (very faint)
Caapi THH: Faint yellow (t+ 1hr) to light dark greyish spot (t+24hr)
Synthed THH: Dark navy blue

Funny enough, I remember testing some of FV's caapi copy and the THH it contained was from this same shine as the synthetic one.

I wonder if the effects are in any way different, the synthetic versus the natural one. I wonder about the different experiments done so far re: THH's pharmacology, and if this is of any relevance.

Here are the self-explanatory pics:

For me synthethic THH looks like mix of harmaline and natural THH. Probably the conversion isn't 100%, it's more like 30% or 20%...

Oh yeah definitely its a mix, there's even a tiny bit of harmine there too... I thought I mentioned that, seems not. Anyways, I did a crude conversion from a 98% harmaline to THH, using zinc and acetic acid but I didnt let it react for long enough, it was just a test run, hence why there's still plenty harmaline.

But still, the THH that is there, is clearly different than the THH from the caapi (which also has some harmaline there)

Banisteriopsis: A few of the published analytical accounts

Caapi alkaloids are mostly harmine, it should be blue, fats are fluorescing green-yellow (rapeseed oil is green), THH is green, harmaline is green (in 365 nm, I think that's my UV wavelenght, because it's colored violet). So it's fats and harmaline with a bit of THH. Seems legit...

Thanks for the link

Fats fluoresce green? Really? Got any source for that? By fats you mean fatty acids? Which ones fluoresce green?

That's interesting. Have to check if they appear in such TLC system, what Rf fats would have, if they appear as distinct spot. There were some very weak fluorescence spots between harmine and harmaline.

Also regarding the "bit of THH", its pretty hard to say quantities of alkaloids. You see normally with these plates, substances have their amount very neatly correlated with size and intensity of spot, for example dmt/nmt/gramine. So in those cases its quite easy to make a semi-quantification based on size of spot. But with stuff like harmalas, it seems for example that harmaline overshines harmine even when they have smaller amount, in 365nm uv. Also the shine seems to change quite a lot overtime. LSD too, degradation is too fast.

THH has 1 asymmetric carbon atom (position 1 in the beta carboline moiety) and its synthesis reduction from harmaline is not preferential to either, so the end-product is a 50:50 mixture of both stereoisomers. On the contrary, enzymatic conversions as occur within cells generally favour one over another stereoisomer (if either is theoretically possible), hence the difference between extracted and synthed THH.

I remember we had briefly discussed this in the past and it was nen that had provided some data that each isomer might have different activity?

Thank you for the post!

So now we need to go to literature and check any of the pharmacological data and see if it was done with natural or synthesized THH. Isn't it possible that one of the stereoisomers is significantly more toxic (or active, or beneficial) than the other?

You're welcome!



I doubt whether it'll be easy to source any data, but who knows? It is possible that one or the other isomer might be more or less toxic/active/etc compared to the other. We already know that only one out of the 4 LSD isomers only one is active. I also know nothing of separating isomers other than that it is very tedious and with no consensus strategy.

BTW, do you remember the the theory that THH might be forming during the very long brewing sessions? If that were the case, then 2 isomers would form (as it is in vitro and not in vivo formation), and these would be not distinguishable by gc/ms. Have you ever run a TLC plate of methanol soaked caapi vs synthed THH vs long boiled caapi?

Good thinking!

I havent... Sounds like a mission for the interns

Some yes like α-Parinaric acid, but I don't think that it's in rapeseed oil. You could check it out or other oils like olive oil, or sunflower oil.

Palmitic acid and oleamide were two of the things that we also found on some caapi, would have to check how they appear on TLC and UV.

..chemist Jace Callaway wrote:

Interesting, so its probably not toxic since it's commonly drank in aya brews. The ones I tested were not brews, they were just cold soaks on the plant, I can compare with the brew sometime.

Just out of curiosity, where is that quote from, some paper, a talk, personal commun. ?

..it's from an Entheogen Review 1995 reply to a query about Calliandra pentandra..
the full quote (with other interesting bits n pieces) is here (acacia info p14)..

Very interesting!

Also this part from the acacia thread re THH:
If this were true, then THH from boiled and reduced caapi (ala traditional preparation), as well as extracted THH should look similar to synthed caapi. It would be very interesting to put this to test and also get feedback from people who have tried both boiled caapi and cold water-extracted (but not boiled) caapi.

Did you mean "then THH from boiled and reduced caapi (ala traditional preparation), as well as extracted caapi should look similar to synthed THH"?

It's early and I've had no coffee today...but the initial sentence was not filtering through my brain at all. Just wondering if the issue is in my brain or the syntax.

yup, I actually meant synthed THH! humans cannot synthesize plants yet!

It makes sense that one could induce epimerization with heat. To what degree? One would need to make use of a polarimeter and run back with an EE. I suppose different conformational isomers of THH could exist under different thermodynamic conditions as well. Without a reference or any semblance of proof other then "(s)he said so", it's anecdotal by definition.

I suppose if we are going by the notion that these UV light refraction differences are infact do to this effect and epimerization happens from heat. One could boil their natural product isolate as well as their synthesized one for a long period of time until a 'guesstimated' point in the equilibrium is reached. Spot them on a TLC plate and check. Easy enough experiment. Not really conclusive but it would be demonstrative.

A lot of stereoisomers have different biological effects... Separation of stereoisomers can be accomplished by several methods. The old-school way was to form salts and do recrystalizations using chiral acids and other techniques. More modern means go by chiral chromatographic methods, typically "enantiodiscriminating HPLC"$$$, or chiral stationary phases$$. Not practical for preparative purposes at least not without a large funding, but for analytical purposes it is feasible. Some CSP's are materials such as cellulose. Micro crystalline cellulose is easily made from paper by means of acid and base treatment... Or perhaps some nice thick paper for paper chromatography with a long elution path length.

Preparitive means of the desired stereoisomer for purposes of a standard are possible with stereospecific reagents. A typical metal reduction obviously will not satisfy this. Perhaps an enantioselective pictet-spengler with acetaldehyde and respective 6-meo-tryptamine is possible.

It's all worth investigating but personally I think the mystery in this is only the specific details. Useful for a chemist working on a similar substrate, but to the average entheophile it's probably a mouth full of marbles...

Interesting.

THH definitely would undergo acid-catalyzed epimerization. It occurs via an interesting mechanism, essentially a reverse Mannich reaction or Pictet-Spengler. When the amine becomes protonated in an acidic environment, the indole donates electron density and forms the iminium ion. This opens the ring and creates a planar environment. When the ring junction is reformed the carbon that used to be trigonal planar becomes chiral, so you are left with two enantiomers.

Woodward encountered this problem during the synthesis of enantiopure reserpine, a yohimbine alkaloid.


Here is a simplified model of the epimerzation equilibrium I drew in marvinsketch

Thank you for the post & pic & the bump Mindlusion, we wouldn't have found this thread otherwise (..we'd search up racemic but not synthetic)

One question remains:




If that is true, why would that happen? We don't understand in vitro here...e.g. why would it not be partly natural 'in vivo' THH and partly racemic THH due to perhaps presence of reducing agents found in river water and/or another component matter (aluminum vessel...etc)?