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Psilocin vs. Bufotenin stability against Oxidation Options
 
Brennendes Wasser
#1 Posted : 1/4/2023 12:51:11 PM

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So sadly currently I cannot find my original thread, where I was asking why the hell Bufotenin is stable for years, while Psilocin is accepted to be prone to fast oxidative decomposition.

Obviously if left non-extracted in mushrooms any enzymes can reversibly break down the Psilocybin/Psilocin again.

But even extracts of *pure* Psilocin were told to be non-rewarding, as also any (at least partially) refined material would quickly decompose.

An obvious answer would be that Bufotenin has a 5-Position -OH and for Psilocin it is at the 4-Position. But that is of course not the true reason behind that, so I was wondering in that thread what the hell that 4-Position would do. But I always thought the break-down is simply an equimolar reaction of 1 Tryptamin with 1x O2. And that really would not care too much about the OH- position.

Now since some years there has been research into the Psilocybin colouring reaction, where damaged tissue of mushrooms gets blue. Haven't read that articles except a summary, but I think the message was the tissue damage induces some oligomerizatiion of the Psilocin by oxydation. That compound is blue and therefore visible for us and may have a defending mechanism instead of the more obvious psychedelic effects of the Monomer that would scare off any intruder (except Psychonauts).

So here I just found a picture which is nicely demonstrating why the 4-Position is causing an oxidative reaction, which might not happen for Bufotenin. Therefore answering my question from 1-2 years ago. Probably you have seen something like this in that other papers, but here it's just easy to discuss the difference to Bufotenin - and that picture is cool:



Read the article here. It must be said that this picture shows only a Dimerization, which normally does not occur - it goes straight to Oligomers. But still it shows the possible construction of higher molecular molecules from plain Psilocin.

What you see is a Quinon-like structure, meaning a 1-4-conjugation of both Indol-Bodies. That is also called Para-Substitution regarding the positions of the Oxygen and the coupled sister-molecule. Now if you compare with Bufotenin:



As you can see there is no 1-4 AKA para conjugation possible. That is why this pattern would be restricted for Bufotenin.

Still it has to be said that the authors also found an 1,2-substituted pattern. That would be an ortho-conjugation. This substitution mostly is also favored by effects that lead to para-conjugations. So in theory that could be also possible for Bufotenin as you see in the picture. Still, this 1,2-conjugation would be not favored for both Psilocin and Bufotenin if you consider steric hindering - also in aromatic reactions a 1,4-conjugation is therefore still preferred chemically.

So as a potential oxidative break-down of either pure Psilocin or pure Bufotenin by ambient oxygen is not mediated by Enzymes (which can sometimes easily overcome otherwise problematic steric hinderance) the disfavoring of a 1,2-conjugation might explain why STILL there is no oxidation for Bufotenin, even though it could form this 1,2-chinon-like Dimer.

So that all is just speculation, but in any case Bufotenin does not degrade at all and this could be a viable explanation.
 

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downwardsfromzero
#2 Posted : 1/5/2023 9:37:02 PM

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Here's another psilocin dimer (the 2,2' dimer) attached. The hydrogens on the imine nitrogens can also succumb to oxidation - or rather, the electrons which they would leave behind can. (I've had these structures on my computer system since 2007, btw!)

The oxygen atoms in bufotenine do not support the same kind of conjugated bouncing around of electrons that makes psilocin so easily oxidized.
downwardsfromzero attached the following image(s):
Psilocin 2,2' dimer.jpg (6kb) downloaded 38 time(s).
Psilocin 2,2' dimer oxidized.jpg (7kb) downloaded 38 time(s).
Psilocin 7,7' dimer oxidized.jpg (7kb) downloaded 38 time(s).




β€œThere is a way of manipulating matter and energy so as to produce what modern scientists call 'a field of force'. The field acts on the observer and puts him in a privileged position vis-à-vis the universe. From this position he has access to the realities which are ordinarily hidden from us by time and space, matter and energy. This is what we call the Great Work."
― Jacques Bergier, quoting Fulcanelli
 
downwardsfromzero
#3 Posted : 1/5/2023 10:51:20 PM

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You got some more nice pics along these lines in this thread: New reason for Psilo blue-coloration? Pf course, that's not about bufotenine stability.

We can see there that 5,5'-dimerisation also plays its part in psilocin bluing reaction. The 5-position of bufotenine is blocked by the hydroxy group in this respect.

I didn't include the pics of the psilocin 5,5'-dimers from my files yet, so for the sake of completeness, here they are.
downwardsfromzero attached the following image(s):
Psilocin 5,5' dimer.jpg (7kb) downloaded 35 time(s).
Psilocin 5,5' dimer oxidized.jpg (7kb) downloaded 35 time(s).




β€œThere is a way of manipulating matter and energy so as to produce what modern scientists call 'a field of force'. The field acts on the observer and puts him in a privileged position vis-à-vis the universe. From this position he has access to the realities which are ordinarily hidden from us by time and space, matter and energy. This is what we call the Great Work."
― Jacques Bergier, quoting Fulcanelli
 
Brennendes Wasser
#4 Posted : 1/7/2023 1:57:30 PM

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Ah well that is indeed a quite big range of possible conjugations. But still the ortho-variant would be possible for 5-OH-DMT also. So not sure why that is not forming. Obviously we have a lack of enzymes here that could be involved, but as I wrote even pure Psilocin is told to degrade so that ortho-coupling reaction might then still take place?
 
 
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