Feel free to add any information you might find on different mushrooms, their habitats/geographical distribution, traditional uses, identification, cultivation, extraction, analysis etc.

I'll start:

(info below from Trout's Notes on Some Simple Tryptamines)

Psilocybin

Free base:
Stable compound. Colorless crystals. Hofmann 1971
pH 5.2 (in 50% EtOH) Merck 9th
More stable than psilocin. Shulgin & Shulgin !997
mp 175-180° Repke & leslie 1977
mp 185-195° (from boiling methanol) Ott 1996
mp 185-195° (from methanol) Picker & Rickards 1970
(Also in Perkal 1981)
rnp 185- 195° (dec.) (white crystals) Clarke 's 1986
mp 190° Mantle & Waight 1969
mp 218-228 (colorless needles from n-butanol saturated with water) Koike et al. 1981
mp 219-222° (6-angled plates from methanol) Troxler et at. 1959
mp 200-210° (dec.) Bellman 1968
mp 204-210° (rod-shaped crystals from methanol; after 10days in a freezer) [co-mp with reference material was 205-210° Leung et al 1965
mp 220-228° (crystals from boiling water) Ott 1996

Solubility:
White crystals '~fairly soluble in ·water" . Hofmann 1959
Readily water soluble. Hofmann 1971
Forms crystals from boiling methanol or boiling water;
Soluble in boiling water (1 :20),
Slightly soluble in boiling methanol {1 : 120);
Slightly soluble ("difficultly" in ethanol;
Practically insoluble in chloroform or benzene.
Merck 9'th
Practically insoluble in ethanol, chloroform or benzene. Hofmann
et al. 1958
"practically insoluble in the usual organic solvents'' Hofmann
1959
Insoluble in ether. Picker & Rickards 1970
Soluble 1:20 in boiling water; 1: 120 boiling ethanol. Pcrkall981
Many workers have successfully used cold or ,room temperature methanol for isolations.
Soluble in dilute acetic acid (as acetate) Clarke's 1986
Soluble in dilute acids
Soluble in di lute bases
Insoluble in butyl chloride
Lee 1985
Base is amphoteric. Hofmann 1959 (Soluble in acids & bases; can 't extract from either with organic solvent)

Hydrochloride:
Insoluble in acetone; insoluble petroleum ether; soluble in hot
ethanol; poorly soluble in cold ethanol. Isolate·d via crystal-
lization with cold from ethanol. Anon 2003


Unlike psilocin. wlllch is readily oxidi:ted, psilocybin is stable
enough to be detectable for many years in herbariums (Dried
psilocybin shrooms appear to remain usable for around 9 years
or sometimes longer if kept in proper storage; sbrooms wruch
contain psilocin o ften appear to rapidly degrade in storage)



Isolation:
Hatfield el a/. 1978
Hofmann e1 a/. 1958 & 1959
Koike eta/. 1981 (Using preparative TLC followed by a column of cellulose & also using an anion exchange resin.)
Leung et at. 1965 (via LC on a column of cellulose.)
Picker & Rickards 1970 (LC on column of cell ulose.)
Crude isolation from initial extract using cellulose column with Butanol saturated with water as elutant. Separated from baeocystin using silica gel column with n-propanol-5 % ammonium hydroxide (5: 1) as elutant. Leung & Paul1967

"Optimum extraction"
Homogenizing 2 minutes in 30 ml of methanol per gram of powdered pshrooms recovered all psilocybin . Perkal 1981
Repke & Leslie 1977 used n-propanol-5% ammonium hydroxide (5:2) on silica gel for preparative tlc. Elution was with methanol containing 5% aqueous ammonia.

Many workers have used methanol successfully. It appears that it works fine either cold or at room temperature.

One trend noted in the literature though, after the extraction is complete, the faster it can be processed to pure or concentrated material (with the minimal heat exposure possible) the higher the potential yield appears to be. This is likely due to degradation despite psilocybin being a fairly stable compound.

Butanol or ethanol combined with acetic acid and water also appears to be ao excellent extraction solvent.
Wurst eta/. 1984 made the statement that "Boiling ojji·uit bodies in water results in a quantitative extraction of psilocybin. The subsequent extraction ... with methanol did nor yield even traces." but provided no further detail.

For direct consumption, the simple extraction of chopped or shredded mushrooms with water and lime juice (or citric acid) works extremely well (color of the resulting solution is tawny not blue) Heat & cooking time should be minimized (2X of 15 minutes or less of simmering each) as prolonged cooking is neither needed nor desirable. Works well in a microwave if allowed to stand following the each heating.

Hofmann et al. 1963 used a methanol extract, concentrated it to a low volume and cleaned it with petroleum ether. Heim & Hofmann . 958a had taken a residue from a methanol extract and cleaned it up with a successive series of solvents: petroleum ether, chloroform & chloroform-ethanol. The remaining residue was taken into the least possible amount of water and more contaminants precipitated with the addition of absolute alcohol. The residue remaining after the evaporation of the filtrate, was then passed through a column of cellulose using butanol saturated with water to elute and selection made for the appropriate fractions. For smaller quantities they used butanol saturated with water on ascending paper chromatography to separate.

Gartz l986a used dried powdered shrooms (2 gm) and extracted for 4 hours with petroleum ether (30 ml) and ether-chloroform ( 1 : 1) (30 ml) prior to soaking the recovered mushroom mass in methanol (100 ml) for 24 hours and isolated using preparative TLC with n-propanol-watcr-acetic acid (10:3:3) on 30 em ofkicsclgcl.
Neal eta/. 1968 found that using I() ml of methanol for each dried and powdered gram ofshroom shaken (mechanical) for one hour and this perfom1ed twice produced a clear solution but exhausted the marc of any detectable tryptamines.

Pederson-Bjergaard et al. 1997 used dried pulverized mushrooms (100 mg) in 3 ml of methanol in an ultrasonic bath for 15 minutes: repeated with 2 ml of methanol, to obtain a 98% extraction efficiency.
Christiansen et al. 1981 found methanol (hot) worked acceptably but only 91% of the psilocybin was extracted. They raised this to 98% by using 10% 1N ammonium nitrate in methanol. (They used 2X 30 minutes extraction times with a rotary mixer using a high potency mushroom.) (They also determined beat-drying shrooms removed 92% water by weight.)

Christiansen & Rasmussen 1982a used hot methanol to extract& Methanol- Water- 1M Ammonium salts (240:50: 1O) for preparative chromatography. (Buffered to pH 9.6 with 2 N Ammonia.)

" Psilocybin extraction": Taken from Anonymous 1992 as posted on the Internet. Printed in The Entheogen Review 3(2): 4.

Claimed to be derived from page 97 in Olah, Gyorgy 1970 Le Genre Paneolus: Essai taxonomique et physiologique.'(This work is currently unavai lab le to me so unable to verify.)

1. Dry the mushrooms (caps or mycelium).
2. Crush or grind to a powder.
(Note: For each of the following solvents use twice the dry
weight of the powder or enough to cover the powder well.)
3. Shake then allow to stand 30 minutes in Chlorofom1.
4. Filter and discard the Chloroform.
5. Shake then allow the residue to stand in Acetone
6. Filter and discard the Acetone.
7. Shake then allow the residue to stand in Methanol.
8. Filter.
9. Repeat 7 and 8 twice more.
10. Discard residue.
11. Combine Methanol extracts; evaporate to dryness.
The final product is a crude extract said to be a whitish-grey
crystalline substance. [Psilocin, if present, will be lost in step 4.]

Hofmann 1971 comments; " The synthetic production of psilocybin is much more rational than obtaining it from the mushrooms." [He was working with shrooms that contained 0.2-0.4% psilocybi]

Beug & Bigwood 1981 commented that extraction at higher temperatures or in a Soxhlet caused partial or complete loss of psilocin but generally less than a 20% loss of psilocybin. Methanol extracts stored at - 5° showed little changes after more than a year but within a few month storage at room temperature lead to

Interestingly, it appears that dried mushrooms with PSOH should be kept stored under freezing conditions, to prevent degradation, while those with ONLY PSOP or trivial amounts of PSOH can keep their potency (when dried) for many years even at room temperature.


Psilocin:

Free base:
White oil; then crystallizing
mp 103-104° (white crystals from ethyl acetate/ hexane)Shulgin & Shulgin 1997
mp 173-176° (prisms from ethyl acetate) Troxler et at. 1959
mp 173-176° (plates from methanol) Ott 1996
mp 173-176° (white crystals) Clarke's 1986
mp 173-176°(dec.) Perkal1981


Very sensitive to oxidation. Hofmann 1971
Forms plates from methanol; very slightly soluble
("difficultly" in water; unstable in solution, especially alkaline solutions. Merck 9th
Slightly soluble in water.
Soluble in methanol [See note by Kysi lka & Wu rs t 1990
below], ethanol, chloroform. Ott 1996
Soluble in ethanol and in dilute acetic acid (will be as acetate)
Clarke's 1986
Soluble in ether. Koike et al. 1981
Soluble in dilute acids
Soluble in dilute bases
Soluble in butyl chloride or chlorofonn [or others?]
Lee 1985

Crystal structures monoclinic Weber & Petcher 1974

Chloroform \ Water Partition coefficient: 5.52
Gessner et al. 1968 (this had been manually changed in the UT library copy to 3.30; Migliaccio et at. 1981 also gave this latter figure as that reported by Gessner)
Octaooi-Water partition coefficient: 0.68 (uncorrected);
1.45 (corrected for ionization)
Migliaccio eta/. 1981

pKa 8.47 (N); 11.33 (OH) Migliaccio et at. 1981
(Degrades above pH 7; Casale 1985)


Isolation:

Hofmann et al. 1958 & 1959
Cold & room temperature methanol have been employed by multiple workers successfully. Butanol or ethanol combined with acetic acid and water also appears to be an excellent solvent.

For direct consumption, simple extraction with lime juice and water works ex tremely well (color of solution is tawny not blue.)

Mushrooms were soaked for half an hour in methanol
( 15 ml for 2 gm of material) The methanol was removed and the residue dissolved in a 0.1 K sodium hydroxide solution (25 ml). This was then extracted with butyl chloride (25 ml) Evaporation of the butyl chloride apparenily left relatively pure Psilocin. (Alternately the butyl chloride was extracted with a dilute acid and the Psilocin migrated into the acid phase for spectroscopic purposes.)

There was no mention of the % of efficiency for either the initial extraction or any steps of the subsequent

Dried powdered mushrooms (210 gm) were combined with dilute acetic acid ( 100 ml) in a beaker. glacial acetic acid then used to bring the pH to 4. The beaker was allowed to stand for one hour and then heated for 8- I0 minutes in a boiling water bath. (Or until solution temperature reached 70° The beaker was then cooled to RT using running water and vacuum filtered through glass wool. After the filtrate was brought to pH8 using concentrated ammonium hydroxide, it was quickly extracted
twice with 50 m1 of ether. (Psilocin degrades at pH >7 hence the need for speed.)
To prevent emulsion formation they recommended a gentle mixing and not shaking.
After separation and combining, the ether is then dried over sodium sulfate, filtered and evaporated w ithout heat under nitrogen.
The greenish residue was crude Psilocin. White crystals were obtained by recrystallizing from Chloroform-Heptane ( 1 :3).
The product was said to be "reasonably pure." Casale 1985 (No indication of efficiency)

Kysilka & Wurst 1990 commented that due to the use of methanol as an extraction solvent by many workers, a lot of the published figures for PSOH content and prob-
ably notes of its absence were likely to be low or erroneous. They found that replacement of methanol with 75% aqueous ethanol and use of a longer extraction
time (160 minutes) provided them with an increase in yield. Ga1tz on the other hand apparently claimed completely opposite results

Hasler eta/. 1997 foun d addition of ascorbic acid to PSOH effectively prevented oxidation at RT but was inadequate for use during autoclaving.

Perkal 1981 found that purging with nitrogen dramatically helped prevent degradation of Psilocin. He also found it to be unstable in alkaline solutions but morestable than psilocybin under neutral or acidic conditions. Storage in the dark helped preserve his mushroom's activity even at room temperature.

Beautiful. A lot of info--and a lot contradictory.

We DO know beyond any doubt that hot water extraction is efficient and easy, since trip effects of mushroom tea are about the same level as direct ingestion of an equal quantity of dried material.

Soon I'm going to try some comparisons involving:

1) tea made steeped in boiling distilled water vs made with citrus juices added to water.
2) dried and reconstituted tea vs tea immediately used.

I'll post here when I have sufficient results (at least a month, for several tests, using personal "bio-assay" ).

Here's quite a bit of practical extraction work from Psilocybe Fanaticus himself.

Thank you for this thread

hey, nice thread for beginner like me..
thanks!

For a historical perspective on psilocybin/psilocin and the mushrooms that contain them, Wasson gives us a good place to start. In 1962, he published a bibliography in the Harvard Univeristy Botanical Museum Leaflets covering a huge number of sources. Many of the entries, especially anthropological/historical ones, include a description of the source and the sort of information it contains.

I'm attaching the article to this post.


BibTex bibliography entry for the article:

..good idea for a thread endlessness..here's what i can add for now..

in https://www.dmt-nexus.me...aspx?g=posts&t=27807 nen888 wrote:

the so-called 'Hoffman technique referred to above is in fact

Le Genre Panaeolus: Essai taxinomique et physiologique par Gyorgy Miklos OLA'H Laboratoire De Cryptogamie du Museum National D'histoire Naturelle 12, rue de Buffon, Paris. Memoire hors-series No 10, 1970. Page 97.
"Dry the mushrooms.
This important step is most likely to cause the greatest loss of yield depending on how it is done. Crush or grind the dried carpophores or mycelium to a powder.
Shake and allow to stand (e.g. 30 mins) in chloroform. Use maybe twice the dry weight in solvents at every step, or enough to well cover the powder.
Filter and discard the chloroform.
Shake the reidue and allow to stand with acetone.
Filter and discard the acetone.
Shake residue and allow to stand with methanol.
Filter.
Shake residue and allow to stand with methanol.
Filter.
Shake residue and allow to stand with methanol.
Filter.
Discard residue.
Combine methanol extracts.
Evaporate methanol to dryness, preferably in a vacuum, although low heat will do.

This will yield a crude extract containing the active tryptamines, suitable for most purposes. This can be further chromatographed on cellulose etc. to give pure psilocin and psilocybin. The recommended solvents are n-Butanol saturated with water, and n-butanol:acetic acid:water (24:10:10). Anyone wishing to do chromatography should check the relevant texts for more detailed instructions."

however, i think this method can be improved on without the need for Chromatography [see further on]
..from the same thread quoted above:

..would be great to hear from anyone who's actually chromatographed psilocin/psilocybin etc..

and from Extraction Method for the Isolation of Isolation and Identification of Psilocin from Hallucinogenic Mushrooms, J. F. Casale ;J. Forens. Sci. 30(1), 247-250 (1985)


.

images below:
1. from [the mycellium-masters at] https://mycotopia.net/forums/bot...-crystal-psilocybin.html - psilocybin crystal needles;
2. from http://mycotopia.net/archives/d...us/messages/5/17249.html - less pure psilocybin xtals evapping;
3. from http://www.erowid.org/ar...psilocin.extraction.html - mass spec of psilocin[cybin] after isolation method;
4. microscopic image of psilocin and psilocybin crystals.

What about the fact that the listed melting point for psilocybin is above 220 C (vs 40 C for DMT--and boiling point AT LEAST twice as high)?

Is it realistic that people have vaped at such high temperatures? Is it realistic that the molecule can survive such high temperatures in an oxygen environment?

^..those melting points surely can't be for the freebase..? the quoted pH in the OP stats is 5.2..that's not FREEBASE..

?chemists...?

I suppose that's right. If you can get it into a freebase form it would be reasonable to expect physical properties somewhat similar to DMT freebase.

BTW, a bioassay test I carried out yesterday suggests to me that tea made in the usual way (from well-powdered mushrooms: steep, filter, steep, filter; making sure filters are ultimately squeezed for last drops) is actually only about HALF the strength of mushrooms taken in the usual way. I took a dose of powdered mushroom in plain, RT water, that was half the last dose I took as tea--and the effects were nearly identical (or even slightly stronger).

I'm quite sure about this. Keep in mind I am using the PE strain--I can only speak for that.

hi, newbie but oldie. but not a chemist, as such. just a meddler.
according to an old synthesis of Psilocybin http://www.erowid.org/ar...hemistry/psilocybin.html

isn't the phosphoroloxy aspect of Psilocybin (N,N-dimethyl-4-phosphoryloxytryptamine) what would make it naturally acidic? doesn't that make it like a salt of DMT? and then would basifying it effectively break off the phosphoros, hydrogen and oxygen? making it, well - dmt? or could pyrolisis do this? so i'm asking, isn't Psilocybin kind of like a form of DMT. also, i should have that old 1997 E.R. will post the Jim de Korne article when i can find it. i also recall him saying he had smoked psilocybin and it worked.

no.

phosphoryloxy (and phosphate) groups have a partial negative character because of localized electrons due to the oxygens, which are quite electronegative. the amine group has a partial positive charge. alkaline hydrolysis of the phosphate would leave an oxyanion (O-) at the 4-position..this would not be dmt.

thanks benzyme . i hope i'm wiser soon.

no it wouldn't

for one, the OH has its own pKa. there are three possible species of psilocin at its isoelectric point, none of them above 50%. deprotonating the amine at a pH > 9.37 means giving the OH a negative charge.
since the OH a polar side group with a proton donor and acceptor, it readily absorbs moisture and undergoes autooxidation from air. proximity to the beta carbon likely also gives it unique physical characteristics.

Wow, I feel like such a fool. I am already scratching my head and saying what the F. I ony thought there was good old shroom tea, Texas Tea. Drink of choice when camping. Hey it is finally winter in Texas and cold enough outside to relax by the fire and gaze at the stars. I am afraid if I have a freebase that I can not get as many friends to share in the experience with me.

Anyhow I wanted to add my two cents.

"psilocybin is stable
enough to be detectable for many years in herbariums (Dried
psilocybin shrooms appear to remain usable for around 9 years
or sometimes longer if kept in proper storage; sbrooms wruch
contain psilocin o ften appear to rapidly degrade in storage)"


I have had very good resuelts from dried and then ground P-Subcubenis for 8 years when it was stored in a vaccume sealed container and left in the gun safe. As good as day one if not better.

Hoping next time. I will have a huge harvest and store them away just like before.

First here are two very seemingly similar techniques for the isolation of psilocin:





Now I have some questions.

1: Firstly, why would it not be possible to simply precip from xylene with FASA?

2: I read somewhere that an ascorbate would still still degrade, and I think benzyme mentioned that a fumarate would not adaquately protect the psilocin? Is this correct?

3: I read that the psilocybin zwitterion behaves differently at a different pH, that it was also stable for days sitting at pH 12. Would it be possible to get it to migrate into something else at this pH in the same way as psilocin would into chloroform or preferably as mentioned above - can anyone confirm it works? - xylene.

4: Also what about changing psilocybin into some other salt form whilst still in solution then get it to migrate into an appropriate solvent? Would this be impossible because of the need to lower the pH too far with the appropriate acid ?

1. we do not know whether psilocin is soluble in xylene. The second quote says xylene should work, but you know how internet is... for starters bufotenine freebase, an isomer of psilocin, can be pulled with chloroform or dcm, but NOT xylene, so the odds are against using xylene atm, but who knows? worth trying though and FASA-ing it.

2. It's all theoretical predictions - not hard data. I would personally do psilocin fumarate and a pinch of ascorbic acid, then add ethanol to a final 40-50% and store in the freezer.

3. No, even psilocybin "freebase" (a loose term here to describe net charge = zero, aka isoelectic point) which exists theoretically at a pH of 4, is still waaaay too polar to be pulled with xylene or other non-polar solvent.


4. makes no sense, chemically speaking - a possible way would be to convert the psilocybin to psilocin and then to the stable 4-Aco-dmt, then pull. But I doubt the later would happen in the conditions of a crude mushroom extract and of course would require some good chemical expertise. It's discussion would also be not allowed in this forum nexus either...

I suspected as much but why is this? Dmt to Dmt acetate is just the same in terms of the rules right ? Though I think the necessary chem for stabilizing psilocin as 4-aco is not quite so common for the kitchen chemist.

EDIT: And for anyone wondering how long the alcohol extractions last on their own, RR of shroomery (shroomery? pshhh! ) said:



So it seems like the easiest way would be to just clean that stuff up as much as possible.

I would be very tempted to try the published extraction

An Aqueous-Organic Extraction Method for the Isolation and Identification of Psilocin from Hallucinogenic Mushrooms
J. F. Casale
J. Forens. Sci. 30(1), 247-250 (1985)

Sounds incredibly simple and reliable. They make no mention of inert atmosphere but that doesn't mean it isn't implied. I imagine ethyl acetate could be used instead of diethyl ether.

The other method orion also posted is the same thing just maybe more detailed.

If the FASA works, this could become a reasonable means for a laymen to acquire a reasonably pure psilocin extract. Think all that's needed is an experiment or three.