Why is NaOH destructive to Psilocin?

[OGGR]

In concentrated amounts of saturated water what is happening to the psilocin and psilocybe? also wouldn't this form some sort of sodium salt? Just wondering im reading alot of misinformation.

 

[.:Holy::Toast:.]

Why would you be submerging your psilocin in concentrated sodium hydroxide (NaOH, as a correction) might I ask?
And yes technically NaOH is an ionic salt but also a strong base so acid/base interactions are definitely possible, but I would say unlikely.
I doubt psilocin will be degraded by the basic conditions unless VERY concentrated, the hydroxyl at position four of the indole ring may undergo A/B interactions as phenol groups are slightly acidic, and the amine at the end of the hydrocarbon tail isn't likely to undergo A/B interactions (correct if wrong, is largely speculative)
Psilocybin may as well due to presence of phosphate group at the fourth position of the indole ring instead of the hydroxyl.
With that said if it is [the psilocin] in an ionic salt form the NaOH will convert it to freebase but considering your psilocin is likely naturally-derived it would already be in it's freebase state

 

[Solipsis]

I once proposed / thought of this:

but I don't know if its correct..

It also seems that some blue/black compounds may be formed which looking at indigo pigment is perhaps a sort of indole dimer - so a different reaction at the 1-2 position of psilocin with itself after base-activation?... that kind of structure seems more likely a candidate for such deep colors.

I'd better move this over to NSP - but too tricky

What do you mean by concentrated amount? Saturated with NaOH I presume? That would be a very strong lye...
You want to crash out a salt from a shroom extraction? I believe it is 'established' that psilocin is very sensitive and unfit for acid/base extractions because it would degrade along the way...

A sodium salt is not formed in any case until you solidify a compound via evaporation of the solvent or precipitation of the product indeed for example via saturation (though an issue then is: how to selectively crash out your product, not at the same time as other things in solution), until then you will just have kinds of inorganic ions dissolved in the solution, and for organic compounds it's typically an equilibrium: some part exists as charged ion, another part as the neutral uncharged form. The proportions of these parts shift depending on mainly the acidity and sometimes driven by one of these being involved in reactions that remove it from the equation.

Yeah if psilocin wouldn't degrade you might expect the possibility of a sodium salt, the sodium replacing a H+ on the 4-HO... but psilocin is a zwitterion. That 4-HO is an acidic / protic function having the ability to lose that H+, but the amine on the other end of the molecule can gain a H+ and is a base function. Having them both in the same molecule makes it a zwitterion in the state where they balance each other. This doesn't mean you couldn't make that sodium salt, but it does affect the equilibrium and you need a stronger base or make it at least basic enough so that virtually none of it is protonated at the amine. For a normal alcohol you'd only have to deprotonate the OH.

I guess it's something more easily considered for typical amino acids such as glutamic acid. Sodium glutamate is the sodium salt of it, a well known flavor enhancer... but glutamic acid does have a zwitterionic form.

 

[serotonin2A]

^That is exactly what happens to psilocin under basic conditions. There is a journal article that actually discussed this, tho I would have to really dig to find the citation.

NaOH isn't specifically required -- anything that raises the pH will cause psilocin solutions to turn blue. I can't remember the exact threshold but it seemed like raising the pH to between 8-9 was sufficient...

 

[OGGR]

Wow thank you all for your insight I didnt expect this! Ive been reading a bunch of half intelligent posts on various shroom websites, now I read yours and its amazing lol... So I was saying saturated solution, like 50 percent water 50 percent lye. only because ive seen post that say if you add too much it will destroy it. Also Albert Hofmanns patent on "Esters of Indoles" states he add .408 parts of psilocin to a 2 part water and sodium hydroxide solution, 50 percent by volume. then proceeds to dry it out to form sodium salts. but I was reading every where else saying that would be bad and I wanted to know why. Im sure I dont have to explain any more to you unless you want me to and or im allowed too, which would be awesome. No talking about chemistry in the other shroomerytopianexus forums, unless your talking about dmt lol hypocrites.

 

[EntheoDjinn]

Salty Mushies

FWIW, from an experiential personal perspective, when I was young and heavily into liberty caps, I would boil them in very salty water in the totally uninformed assumption that the psilocybin would more easily be dissolved in the saline solution. I would then strain them and make coffee sweetened with syrup.

I never noticed any difference in potency between eating them raw, mushroom for mushroom. I was always delightfully psycedelicked off my chump.

 

[tryp2fun]

I once proposed / thought of this:

but I don't know if its correct..

It also seems that some blue/black compounds may be formed which looking at indigo pigment is perhaps a sort of indole dimer - so a different reaction at the 1-2 position of psilocin with itself after base-activation?... that kind of structure seems more likely a candidate for such deep colors.

I'd better move this over to NSP - but too tricky

What do you mean by concentrated amount? Saturated with NaOH I presume? That would be a very strong lye...
You want to crash out a salt from a shroom extraction? I believe it is 'established' that psilocin is very sensitive and unfit for acid/base extractions because it would degrade along the way...

A sodium salt is not formed in any case until you solidify a compound via evaporation of the solvent or precipitation of the product indeed for example via saturation (though an issue then is: how to selectively crash out your product, not at the same time as other things in solution), until then you will just have kinds of inorganic ions dissolved in the solution, and for organic compounds it's typically an equilibrium: some part exists as charged ion, another part as the neutral uncharged form. The proportions of these parts shift depending on mainly the acidity and sometimes driven by one of these being involved in reactions that remove it from the equation.

Yeah if psilocin wouldn't degrade you might expect the possibility of a sodium salt, the sodium replacing a H+ on the 4-HO... but psilocin is a zwitterion. That 4-HO is an acidic / protic function having the ability to lose that H+, but the amine on the other end of the molecule can gain a H+ and is a base function. Having them both in the same molecule makes it a zwitterion in the state where they balance each other. This doesn't mean you couldn't make that sodium salt, but it does affect the equilibrium and you need a stronger base or make it at least basic enough so that virtually none of it is protonated at the amine. For a normal alcohol you'd only have to deprotonate the OH.

I guess it's something more easily considered for typical amino acids such as glutamic acid. Sodium glutamate is the sodium salt of it, a well known flavor enhancer... but glutamic acid does have a zwitterionic form.

I agree with the structure, but not the mechanism. This is an oxidation, so it needs an electron acceptor. You are not removing H⁺ from the OH and NH, but an H atom. Of course, O₂ is an excellent electron acceptor for the oxidation of psilocin. I'm sure the blue color seen when the mushrooms are broken is from oxidation of psilocin.

 

[serotonin2A]

So I was saying saturated solution, like 50 percent water 50 percent lye. only because ive seen post that say if you add too much it will destroy it. Also Albert Hofmanns patent on "Esters of Indoles" states he add .408 parts of psilocin to a 2 part water and sodium hydroxide solution, 50 percent by volume. then proceeds to dry it out to form sodium salts. but I was reading every where else saying that would be bad and I wanted to know why.

I hope this doesn't violate the no synthesis discussion...I limited my discussion to the topic of preparing a solution.

If you look over the patent...it seems like you are using way too much base. It says to combine 0.408 parts of psilocin and 2 parts (by vol) of a 1 N solution of NaOH. That isn't the same as 50% by vol NaOH. If Hoffmann used (for example) 408 mg of psilocin, then he would mix that with 2 ml of an aqueous solution containing 80 mg NaOH. At least that is how I read the patent. By contrast, it sounds like you are using 2 ml of a solution containing 1000 mg NaOH.

I don't think that he ever said that he isolated a solid sodium salt. In any event, exposure to base probably reduced the yield considerably.

 

[OGGR]

I hope this doesn't violate the no synthesis discussion...I limited my discussion to the topic of preparing a solution.

If you look over the patent...it seems like you are using way too much base. He combined 0.408 parts of psilocin and 2 parts (by vol) of a 1 N solution of NaOH. That isn't the same as 50% by vol NaOH. If Hoffmann used (for example) 408 mg of psilocin, then he would mix that with 2 ml of an aqueous solution containing 80 mg NaOH. At least that is how I read the patent. By contrast, it sounds like you are using 2 ml of a solution containing 1000 mg NaOH.

I don't think that he ever said that he isolated a solid sodium salt. In any event, exposure to base probably reduced the yield considerably.

Hmm I though he was saying a saturated solution which is 50/50 about for lye and water I dont know really. In either case he drys it out and dissolves the "sodium salts" in his example.

Edit: He says " 0.408 part [Psilocin] and 2 parts by volume of 1-normal aqueous caustic soda solution are evaporated to dryness.." so its more like 2 parts 1 N solution yes?

 

[OGGR]

hmm double post sry.. I want to add I see now he says "a hydroxy-indole of formula VI is first dissolved either in water containing one mole of a base, or in the form of a salt with an inorganic base in an inert solvent" you are right, I was trying to hard to decipher what he meant in example 1 and missed what he said before.