So we all know to be gently with your mushrooms - dry them fast and then store them airtight - Psilocin and Psilocybin wont stay forever. While not having infinite shelf life it is told that the phosphate is still a good protection in case of psilocybin.

So Psilocin is quite unstable. But in terms of mushrooms this is believed mostly due to the reversible nature of the enzymes that built these goodies, so thats why to get your mushrooms water-free as fast as possible - makes sense.

But then there is still no working extraction method for Psilocin / Psilocybin. The reason is always given by: It is just unstable and will be destroyed while attempting it.
Also it is told that you will never be able to experience a vaped Psilocin experience, as it will just decompose by trying it.

But then there is Bufotenine = 5-OH-DMT, while Psilocin = 4-OH-DMT.

And 5-OH-DMT is super stable, long shelf life, no decomposition if its pure. Also you can vaporize it and definetly get an effect. So it is also not destroyed upon heating.

That really makes me wonder. Normally if there are isomers and they change in property, then its of course connected to their different structure. Now the only flexible part of these tryptamines is the aliphatic Me2N-chain. And in the case of 4-OH-DMT it is in a lesser distance to the phenolic OH.
So this is the only difference in structure and therefore this must be the reason for the occuring problems when facing Psilocin.

But now the question is: What should happen? I cannot imagine any senseful way how an interaction would destroy the molecule. Then again, it is told that "oxidation" causes Psilocin to vanish. But then again it does not in the case of Bufotenine.

Maybe at first O2 reacts with the Amine to form an N-Oxide and this may interact with the phenolic group to ultimately convert it and that mechanism is impossible for 5-OH-DMT?

Compare the relative positions of the phenolic hydroxyls and the indolic nitrogens. Take a look at how the electrons can move around in each case. Which one looks more susceptible to oxidation?

Can't see any difference

In both cases there could be an enone formation with an oxidation agent taking away H and electrons from that indolic N.



As the N is accessible from both sides via electron shifting, the range of conjugation is the same for both molecules - just via a different route. So based on that it should degrade at the same speed?

You're missing a key step in the oxidation sequence.
Refer to THIS psilocin article. Specifically look at the reaction plot half way down the page. It begins with a radical forming oxidation step, followed by C-C coupling ortho to the oxygen, then it repeats to make reactive polymers or finally oxidizes your way terminating the sequence to make blue dimer/polymer ketone products.
Its been some years since college but I suspect having the nitrogen para to the oxygen would inhibit the radical C-C coupling reaction and just having the nitrogen in that position would reduce the propensity for the phenol radical to form in the first place.
I never actually put this stuff to use so I'm very rusty

Indeed there is that interesting decomposition thing which causes the blue colour - I also posted about that here, but then apparently it was already up here before ;D

So this is of course a reason why mushrooms tend to get less potent if stored non-correct.

But nevertheless I was talking about the stability of just the isolated alkaloids. Apparently there is no way so far to get 100 % pure Psilo alks, but even extracts that seem quite near this state also tend to degrade. And I think these extracts dont include any mushroom enzymes anymore - so the decomposition of the coloring reaction cant take place. And even if these extracts would still contain residual enzymes, then they should be inactive as the extraction methods dont use aqueous media I guess (still, no idea about any Psilo extraction method, but again there is none 100 % working nevertheless).

So thats what I am wondering about: if there is a real reason why the structure of Psilo Alks make them more vulnerable.