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Psilocin freebase to fumarate - what did I do wrong?

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RigaCrypto

RigaCrypto

Rising Star
I am trying to convert some psilocin freebase to fumarate, because the former degrades very quickly (in a few weeks at RT). I did as following:

Note: I used 96% ethanol obtained from grains, with the rest water. I cannot get concentrated acetone or diethyl ether.
I dissolved 15 mg of fumaric acid in 3ml of ethanol.
I dissolved 50mg of psilocin freebase in 2ml of ethanol.
I mixed the solutions and shook them for about a minute.
I poured the solution on a tray to evaporate.

Now, it's been more than three hours since and the thin layer of alcohol should have evaporated. But what I am left with is a layer of oily colorless gunk that show no signs of further crystallizing or evaporating.

What did I do wrong?
 
First of all I should say, with apologies, that I know next to nothing about chemistry. Except for the kitchen teks I've used to extract DMT and harmala alkaloids.

So I (perhaps hastily) generalized from the facts that other 4-substituted tryptamines are stable in fumarate form and that DMT can be converted to fumarate and on this basis I tried to use a similar procedure for psilocin.

If my assumptions are wrong please excuse me and tell me so.

In the meantime, one lead I've got from a thread here is that DMT fumarate precipitates from acetone, but is soluble in ethanol and thus harder to crystallize. It was suggested in the thread that it is less soluble in isopropanol, and that perhaps it would be easier to precipitate from it. Is this correct, and could it be extrapolated to psilocin?

@soulfood - the psilocin is synthetic, but obviously it was not me who synthesized it :)
 
"and could it be extrapolated to psilocin?"

From what I understand no. Psilocin is a zwitterion and so you cannot have freebase or salt forms of psilocin. Im not a chemist though so wait for someone else who knows more to respond in detail.
 
OK, thanks. So 4-HO-MET, 4-HO-MiPT and all the other 4-substituted tryptamines can exist as fumarates (fact) but 4-HO-DMT can't?

I should also add that I cannot get acetone except very diluted with water. I can only get ethanol, isopropanol and hydrocarbon solvents
 
I am not trying to extract the psilocin. I already have it pure in "freebase" (more like zwitterion/internal salt, right?) form. What I am trying to do is turn it into a fumarate salt at the amine end, as referred to in this excerpt from TIHKAL:

"Here, as with the 4-HO-DMT (psilocin) and the 4-HO-DET entries, some care must be made with the use of the term "acetate" or "phosphate." As these materials are both bases (tertiary amines) and acids (hydroxy indoles), they are in effect internal salts. For stability, they are usually converted into salts (at the amine end) or esters (at the phenolic end), or both. In this context, the term "acetate" can mean either modification, a salt or an ester involving acetic acid. And, of course, a phosphate can be either a salt or an ester. I will try to append the additional term "salt" or "ester" whenever this ambiguity is possible. In all of these studies, the acetate is the ester, and some of these are free bases, some are the hydrochloride salts and some are the fumarate salts."
 
so benz is psilocin a zwitterion or not? I assumed that psilocybin was but that psilocin was not a zwitterion..but then last night people told me that both are zwitterions..so I am confused..
 
Yeah, so it seemed from the Shulgin quote I posted as well - "they are in effect internal salts" - referring to psilocin and ethocin.
 
So Benz, is it possible to freebase either of the molecules? I've read lots of conflicting info on this.
 
I don't know for sure.

after four A/B extractions (2 - 10g dry material) to a pH of 8 - 9, there was no active
product. based on the chart I posted, one would need to take the pH past 12 to get primarily free base. the problem with that is, it puts a negative charge on the O-, which may also render the molecule inactive. it's worth a try though. extract quickly after basifying

Psilocin chemicalize data

for a more detailed look at that chart data, click on Manage Calculations-> pKa
 
Seems to me like if you did manage to freebase psilocin, you would just have something pretty much identical to DMT. And if you did salt psilocin and did make psilocin fumerate? how would that differ much from how it already occurs in a nuturally salted form in the mushroom?

Seems like perhaps some high tech tail chasing. I could be wrong however becuase I know Jack about chemistry.
 
Psilocin is not by far identical to DMT, although I would say it is the most similar to it among the 4-substituted tryptamines. Psilocin shares the clarity and 'natural' feeling of DMT, in that on it you feel sober in a way only DMT matches. The psilocin trip feels 'real' and not drug-induced. It's hard to convey how it feels without going into detail, but I would say psilocin is more clear-minded and vividly visual than its homologues while retaining the spiritual depth of mushrooms, but without any of their side effects.

In short, I would say it is the prototype of 4-substituted tryptamines and the essence of mushrooms without any of the downsides. And compared to DMT, I would say it is much more emotional (DMT leaves me pretty untouched in this department, apart from the unavoidable feelings of awe and / or terror) and inwardly spiritual. Also, it has beautiful and realistic OEV's, unlike DMT on which the world gets the alien plastic world look.

Too bad it isn't more widely available on the market. Although, if the tek for obtaining it from 4-AcO-DMT works, that shouldn't be an issue anymore.

It is a very special material but the freebase form is very vulnerable to degradation, which is why I am trying to convert it to fumarate.
 
The problem with pH 12 and stripping the proton on the phenol moeity becomes oxidation and the solvent for pulling. Na-O-C6H5 is not going to be very soluble in most non-polar solvents, at least I wouldn't think.

Oxidation issues arise from the air, such as ambient CO2 in the air which can carboxylate the ring usually done at high pressures though(Kolbe schmitt reaction), this is kind of a low priority. Phenolates also are susceptible to oxidation's from O2 and radical reactions(Ph-O-O-O-Ph is were termination ends iirc). So inert atmosphere(N2, Ar, etc) is recommended if a phenolate is the way to go.

edit:
Granted the reaction in the paper uses a catalyst and pure oxygen one can suspect and see that a similar schema is easily possible.
The mechanism of this reaction is well accepted(21) as involving one electron oxidation of the phenolate anion to generate the phenoxy radical which then reacts with molecular oxygen to form the para-peroxy-cyclohexadienone. Finally, loss of water produces the para-benzoquinone. Competitive reaction of the phenoxy radical with molecular oxygen at the ortho position would lead to the ortho-benzoquinone. The usual side reactions also involve the phenoxy radical, and ortho-para and para-para carbon-carbon coupling leads to the bis-quinone-methides, the bis-phenol, and eventually to polymeric materials (Scheme 2; to simplify the Scheme we have omitted ortho-ortho and ortho-para couplings).
_____________________________________________________________
21. Bozell, J. J.; Hames, B. R.; J. Org. Chem. 1995, 60, 2398.
Click to expand...
a07sch02.jpg

from - Oxidation of mono-phenols to para-benzoquinones: a comparative study
Oxidation of mono-phenols to para-benzoquinones: a comparative study
Marciana P. Uliana; Ygor W. Vieira; Maria Carolina Donatoni; Arlene G. Corrêa; Ursula Brocksom; Timothy J. Brocksom*
Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos-SP, Brazil
 
"And compared to DMT, I would say it is much more emotional (DMT leaves me pretty untouched in this department, apart from the unavoidable feelings of awe and / or terror) and inwardly spiritual. Also, it has beautiful and realistic OEV's, unlike DMT on which the world gets the alien plastic world look."

Lets be clear here, are you referring to vaped DMT vs oral psilocin?..or oral DMT vs oral psilocin?

Vaped DMT and oral DMT can be very different IME..while yes DMT is DMT the ROA does make a difference. Oral DMT and oral psilocin are very very similar. What you described above is more in line with vaped DMT and less with oral IMO..mushrooms and DMT both give things that same alien look with eyes open. With eyes closes neither vaped nor oral DMT looks plastic.

I would be willing to bet that if you could vape or ionize psilocin you would find it very similar to vaped DMT.
 
Yeah, I was referring to vaped DMT vs. oral psilocin. I don't have much experience with oral DMT.

As for the plastic world look, I was referring to the fact that on vaped DMT, the world becomes LESS detailed - objects lose their texture and structural details and turn into uniform colored blobs. I've had my picture of the world go all the way down to black and white pixellated low-res. DMT is the only psychedelic I've tried on which the world loses beauty and complexity rather than gaining them.

I will try vaped psilocin when I get around to it and post a trip report. A friend of mine tried it and said it was comparable to DMT in terms of speed and intensity of come-up. He tried 2-4mg (his scale was not very accurate) and said it was comparable in intensity to 24mg taken orally, which is in turn comparable to about 4g of mushrooms. He said it lasted about an hour plus another hour for the come-down. The trip itself however, he said was not identical to DMT and conserved the character of oral psilocin, including the wavy and complex visuals.
 
jamie said:
so benz is psilocin a zwitterion or not? I assumed that psilocybin was but that psilocin was not a zwitterion..but then last night people told me that both are zwitterions..so I am confused..
Click to expand...

Phenolic hydroxyl's are slightly acidic...making psilocin effectively zwitterionic, but not like say an amino acid which has a true acid (COO-) and a true base(NH3+).

The reason psilocin is so hard to extract is the amine side chain likes to bite back and hydrogen bond with the 4' phenol.

It is possible, but you have to precisely control the ph. You need a digital ph pen and the pKA information that benz posted above.
 
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