The crystallization of psilocybine hydrochloride is much easier than previously thought. The most important existing techniques are at the end of this post. Problem of those is that they use chromatography as final purification step.
But that can be omitted!
The magic step probably was in the addition of the few drops of hydrochloric acid to the alcoholic extract. This produces the psilocybin HCl salt, which is insoluble in acetone and which forms nice big crystals.
It is also important to give each step in the protocol enough time. This is most obvious in the last step, the double acetone wash. The dark residue crystallizes by itself in the acetone after 12 hours!
I looked into this method to see if the green-blue-dark part of the extract can be separated from the psychoactive part. In this method that is not possible. The growing crystals absorb the pigment and then become transparent. The identity of the blueing reaction of psilocybian mushrooms still is a mystery to me.
Summary of the (tested&proven) method:
- harvest&dry the mushrooms/mycelial tissue
- turn it into powder (blender works fine)
- extract overnight with a mixture of ethanol and water (denatured 140 proof is fine)
- filter (vacuum filtration or 0.2um filter mounted on syringe)
- add a few drops of hydrochloric acid (aim at pH3)
- evaporate down to 1/10th of the volume (can be done in a large tupperware container) and put extract in a (tall) vial
- remove fats&resins with a solvent which is not miscible with water (cigarette lighter gas, paint thinner, naphta etc.). Just add the solvent to the extract, mix (slowly, not vigorous) and let it stand for a couple of hours. The solvent floats on top of the extract and can be removed by syringe or by freezing the water and pouring off the solvent.
- remove the rest of the gunk by adding acetone to the extract. Mix slowly and let stand. Again two layers will form. On the bottom of the vial is a dark layer. On top of that floats the acetone which is yellowish to greenish. Remove the toplayer by syringe or pipette.
- add new acetone. Mix slowly. Now the dark layer becomes real sticky. Let stand for a few hours and remove the acetone.
Final step: collect all the dark sticky residue and dry it slowly. Large transparent crystals will form. The more slowly the evaporation the bigger the crystals. The potency of the mushrooms can now be determined by weighing the crystals.
What a relief - Albert Hofmann's approach to use chomatography for the crystallization can be omitted. It is not a difficult technique but it needs a large volume of solvents and very specialized ingredients and reagens. But now I am absolutely sure that large crystals will form after a double acetone wash and simply allow the residue to stand overnight.
Further reading:
American patents 3183172 and 3192111.
Can be viewed at
http://patft.uspto.gov/netahtml/srchnum.htm
Popularized version:
Gottlieb, THE PSILOCYBIN PRODUCERS GUIDE (1976, 1997)
URL:
http://nepenthes.lycaeum.org/Plants/shrooms/shroom1.html
Albert Hofmann's
article 'History Of The Basic Chemical Investigations On The Sacred
Mushrooms Of Mexico', which appeared in the now hopelessly difficult to
obtain book TEONANACATL of 1976 (cut, paste&see
http://dogbert.abebooks.com/abe/BookSearch?AID=8244485&PID=453119&an=ott&sn
=
&tn=teonanacatl&ph=2
Quote:
"In order to preserve the possibly very sensitive, active principles, we
used only neutral solvents and the extractions were carried out at room
temperature. After the extraction of the finely-ground mushrooms with
chloroform, with benzene, and with acetone, the whole activity was still in
the mushroom material. The active principles were easily and completely
extracted with methanol. From the residue of this extract, inactive
constituents could be eliminated by treatment with chloroform. The remaining
easily water-soluble preparation was purified by precipitation of a
concentrated solution in water with ethanol. The activity remained in the
filtrate. The residue of the evaporated filtrate contained the active
principles enriched a hundred fold compared to the dried mushrooms. A
further concentration of the active constituents was possible by paper
chromatography. Using Whatman-I-paper with water-saturated butanol as
solvent, four zones were obtained, the nature of which was determined by
cutting the chromatograms into small strips, extracting the single strips
with methanol, and weighing the residues. In one of the four bands, the
whole activity was found in the form of an easily water-soluble,
halogen-containing powder. After treatment with silvercarbonate, elimination
of silver ions with H2S, and concentration of the aqueous solution in vacuo,
the substance crystallized in fine white needles. With the few milligrams
obtained in this way we made several tests. The new psychotropic principle,
which was named 'psilocybin,' elicited a violet color with Van Urk-reagent,
characteristic for indole derivatives.
For the subsequent isolation experiments, we could rely on this color test.
When paper chromatograms prepared as described above, were sprayed, after
having been dried, with a solution of p-dimethylaminobenzaldehyde in benzol
and put in an atmosphere of dry HCl gas, psilocybin produced a violet spot
with Rf 0.1. A weaker spot with a blue color and Rf 0.5 was observed,
corresponding to a second active principle, which we named 'psilocin.'"[end
