Paradox
©
Fisana

Jump to content


Photo
- - - - -

Ethanol extract?


  • Please log in to reply
32 replies to this topic

#1 ConsciousFeeder

ConsciousFeeder

    Too rich the rich king.

  • Expired Member
  • 920 posts

Posted 13 August 2013 - 04:48 AM

Recently in my group of friends I've heard word about an extract that is being placed into chocolates. A friend said he ate probably the equivalent of about a small pill worth in size and said it was so strong that it almost felt like acid. He was assuming it to be an ethanol extract but I'm not certain. I know that alcohol extracts are possible just have heard the potency doesn't last forever it eventually degrades.

Was wondering if anyone had some insight into possible extract methods that have high psilocybin saturation levels for low amounts of liquid.

Another different friend was asking me yesterday if I knew anything about them and how they are made, they being the chocolate extract my other friend was speaking of. So a few friends in different crowds have ran into them.

I'd love to know a method to get an eighth dose in a half a tootsie roll or something like that. Would be ideal for me I'm thinking.
  • Haxcor likes this

#2 krookie

krookie

    Dalton's keeper

  • Expired Member
  • 370 posts

Posted 13 August 2013 - 08:22 AM

could you condense the ethanol with low heat? keep in mind in this day in age it may not be psyclibin but another chemical, many of which of milligram to sub milligram doses. tahts all ill say about that. just be cautious.

#3 permafrying

permafrying

    what

  • OG VIP
  • 1,695 posts

Posted 13 August 2013 - 08:43 AM

http://www.seanet.co...on/mycoalki.htm

Fallow the ethanol extraction method and reduce down to whatever desired potency. You could. Inject it into a hallow chocolate put into a freezer. The dehredation would be fast so you mine as well just squirt it into water and slam it down. If hit want to be able to hold onto it you need something airtight to keep it in while freezing

#4 Baby Squid

Baby Squid

    Gone Fishin'

  • Free Member
  • 224 posts

Posted 13 August 2013 - 09:05 AM

If the person making the extract had a rotovap or sep column... you could have some serious horsepower there. Consistent ETOH extraction is tricky and a larger scale distro that "makes the rounds" seems sketchy.

My bet is something else besides psilocybin if it's showing up in a lot of places. Ya could always do a reagent test to see for sure.



Edit: anything is possible, who knows what you have there. I have done an ETOH extraction and it is possible with just booze and evaporation but some times it loses potency, sometimes not...

Edited by Baby Squid, 13 August 2013 - 09:22 AM.
finishing the thought


#5 Haxcor

Haxcor

    Cellar door

  • Expired Member
  • 212 posts

Posted 13 August 2013 - 10:34 AM

I did a lot of research on this many years ago looking at the percentages of Psilocin and psilocybin extracted using different techniques. I came up with a 2 part extraction with methanol and ever clear(which are both polar). I would extract into the high proof alcohol first, then use the sludge and do another extraction with methanol. The methanol final product would be dried then added back into the alcohol extract for storage in a freezer. Light and heat will quickly degrade the contents I found. So keeping it in your car for a day in the summer heat is a no-no. If you are trying to just get the crystals then I recommend an extract with just methanol. It will be easy to boil off the methanol and then sit on a hot plate to get the rest off. Your end product will be pure. Now we know psilocybin is metabolized into psilocin when ingested, but you want to extract both along with the other alkalines when extracting. From what I've read you want a polar extract. You don't want a non-polar like naphtha, because you are not extracting oils or fats. Chocolates are a pain in the ass and messy(sorry just wanted to add that).

To wrap up there are some ways to make it into very small crystals. Some questions to ask about the chocolates to see if they were the crystals of god is... How long did the trip last and how quick was the come up? The extract is normally a very fast come up with being a full pledged trip within 30mins and completely gone and done after 4 hours(even at higher doses). With that being said the breakdown of chocolate could have extended those time, I'm really not sure. I guess you have to play around a bit. When doing this I use a hand pump and vacuum and a partial lab. The pump really comes in handy. I do not believe that this could be pulled off properly with out a vacuum pump, if you tried I'm sure you would leave a lot behind. I use grade 1 filter papers which are 11 µm.

Dangers! Do not think that just because you read something on the Internet you can do it. There are many dangers that I left out. I recommend doing research and understanding about chemicals and reading the msds is a must. Methanol is very flammable and you should never have a open flame or spark around it.

The reason why I'm pointing you in the direction of methanol is because it has no water in it. Even with ever clear there is water. If you are trying for pure crystals it would be very difficult it completely dry. If you would like a more step by step process I can write one up. I have tried it with both dry and wet they both work but either way they need to be crushed up very fine.

Enjoy and be safe ;) hope everything works out for you and sorry for the long read but I think everything I put is beneficial.

Shroomy vibes ;)
  • LordRigel likes this

#6 Defiance

Defiance

    Trainee

  • OG VIP
  • 1,386 posts

Posted 13 August 2013 - 11:07 AM

Oh good lord.

Those crystals aren't active. The pictures at the top of the website you guys linked to says that those crystals were produced from a 16g extraction. A big trip is like, 30mg of psilocin. If you can get two big trips out of 16g of dry mushrooms then reality says that there should be in the ballpark of 60mg of psilocin in a 100% perfect extraction. Whatever is in that picture, I'd bet just about anything that there is a lot more than 60mg of it.

If you read the thread you can see that one poster claimed 4g of crystals from 8 ounces of mycellium. If those crystals were pure then that mycelium has 500mg of actives per ounce, or 5mg psilocin per gram of mycellium. That would make mycellium nearly as potent as cubes, gram for gram. Eat some and see for yourself.

Everyone wants crystalline psilocin from mushrooms but the reality is that it's not going to happen (Edit: Without a lot of hard work and equipment. I'll help!). With only a couple of exceptions (fumarate) tryptamines don't really form crystals in their salt form that well. They're really hygroscopic and you tend to get gooey, oily residue.

Also, even if you could get pure psilocin, the difference between a moderate dose (15mg) and a hell-on-earth-what-did-I-do-to-myself dose (75mg) is too small for comfort. Being off by even 20mg means being off by a lot. Unless you have a better scale than I do, you'd be better off making a solution and dosing by volume.

And that's what most people do. Extract mushrooms in vodka somewhere dark for a week or two, evap down so that for every 1g of dry mushrooms you've extracted you have 10ml of liquid, and take a shot (22ml) or two of it. Hell, make tea. Water is cheaper than vodka and psilocin is just as soluble in it. You don't need methanol or iso or any of that other nonsense.

And just for the record, psilocin is really prone to oxidation. Keeping it in solution keeps it safe. Now, if you were to acetylate it...

Edited by Defiance, 13 August 2013 - 11:44 AM.

  • LordRigel likes this

#7 permafrying

permafrying

    what

  • OG VIP
  • 1,695 posts

Posted 13 August 2013 - 11:12 AM

I should probably add the link I posted was for making an alcohol extract the crystals in the tek are useless

#8 Defiance

Defiance

    Trainee

  • OG VIP
  • 1,386 posts

Posted 13 August 2013 - 11:26 AM

And just so it doesn't seem like I'm totally tearing everyone down, let's talk realistically about how you would isolate crystalline psilocin from mushrooms.

Psilocin and psilocybin are both in mushrooms, but psilocybin is a prodrug of psilocin. When psilocybin is exposed to acidic conditions it undergoes a process called acidic dephosphorylation, and is converted to psilocin. So just by the nature of the extraction process you're going to end up with a pure psilocin extraction.

Not that that is really a big deal, except for that phosphate group is protecting the molecule from oxidation. So, unlike DMT, you've got to exclude oxygen from your extraction, especially if you have to evaporate. If you can't freeze precipitate (I don't know if you can) then you'd better be able to evap under an oxygen-free atmosphere. And that's hard to do without at least some equipment.

And after you get your freebase you still need to convert the psilocin to a salt that's stable and will crystallize, which for tryptamines means the fumarate. Again, fingers crossed that psilocin has identical solubility properties to DMT. If not, it's going to be a lot of trial and error.

None of this is impossible, but it is going to be harder than isolating DMT with an A/B, purifying it, and making DMT fumarate.

Edited by Defiance, 13 August 2013 - 02:15 PM.


#9 TVCasualty

TVCasualty

    Embrace Your Damage

  • Moderator
  • 15,092 posts

Awards Bar:

Posted 13 August 2013 - 12:20 PM

And just so it doesn't seem like I'm totally tearing everyone down, let's talk realistically about how you would isolate crystalline psilocin from mushrooms.

Psilocin and psilocybin are both in mushrooms, but psilocybin is a prodrug of psilocin. When psilocybin is exposed to acidic conditions it undergoes a process called acidic dephosphorylation, and is converted to psilocin. So just by the nature of the extraction process you're going to end up with a pure psilocin extraction.

Not that that is really a big deal, except for that phosphate group is protecting the molecule from oxidation. So, unlike DMT, you've got to exclude oxygen from your extraction, especially if you have to evaporate. If you can't freeze precipitate (I don't know if you can) then you'd better be able to evap under an oxygen-free atmosphere. And that's hard to do without at least some equipment.


That's one reason why I started adding citric acid crystals to my alcohol extracts. Another reason was I'd noticed that citric acid had the same qualitative effect on the trip as a lime juice soak and that dissolving citric acid crystals in blue water (mushroom tea) turned the water back to clear. I'd like to know what that means in terms of oxidized psilocin; does the acid change it into something else that's also inactive or does it "reactivate" the psilocin?

Anyway, so far I've noticed no drop in potency in a test batch w/ citric acid added that's around 5+ years old at this point; I'll take one measured shot per year and each one has gotten me to the same place so while that's not scientifically rigorous in my case it'll have to do for now (maybe Santa will finally bring me that gas chroma rig I've been asking for this year... :eusa_pray).

And freeze-precip'ing the sugar out works great for lowering the concentration of inactives in the mix which also helps boost its relative potency (along with reducing it, which also causes more sugar to crash out so the process can be repeated a few times).


Recently in my group of friends I've heard word about an extract that is being placed into chocolates. A friend said he ate probably the equivalent of about a small pill worth in size and said it was so strong that it almost felt like acid. He was assuming it to be an ethanol extract but I'm not certain. I know that alcohol extracts are possible just have heard the potency doesn't last forever it eventually degrades.

Was wondering if anyone had some insight into possible extract methods that have high psilocybin saturation levels for low amounts of liquid.


I'd like to see a pic of one of those little pills if possible. And if there was still liquid present you should be able to open it up and detect the presence of alcohol fumes.

Also, unless it was 100% ethanol then the water in it would wreck the chocolate if mixed into it while it's melted. And if trying to make liquor-filled chocolates then they need to be made with a "sugar-" or "starch-made" crystallized sugar crust as a "liner" or the liquor will dissolve the chocolate shell. Then they need to be sealed with confectionary fondant. So while extract-filled chocolates are possible and would be awesome, they would probably be very expensive if sold and only available in extremely limited quantities due to the labor and skill and expense involved in making them. Hmm, talk about an incredible Valentine's Day gift; a big gift box filled with a variety of mind-altering chocolates would be fun... :teeth:

This is a good source for learning how to make liquor-filled chocolate: http://www.chefeddy....led-chocolates/

(but with my luck I'd end up with the one that's full of cough syrup like how I always end up with the chocolates full of raisins or coconut that everybody leaves behind in conventional, non-psychedelic boxes). :eusa_snoo

#10 Solipsis

Solipsis

    Mycophage

  • Free Member
  • 115 posts

Posted 13 August 2013 - 12:27 PM

The big problem is that proteins are stuck to the alkaloids and apparently the complexes they form together aren't really stable when you try to extract. Purified psilocybin itself is apparently not that fragile though! I have several tryptamines e.g. synthetic 4-HO-DMT, 4-HO-MET, 4-HO-MiPT, 4-HO-DiPT and their acetoxylated cousins and if you take the proper storage precautions the stability is really not that bad.

People have guessed at the identity of the bulky but inactive crystals derived from a super basic extraction: they are probably sugars.

Psilocin exists mostly intracellularly and extracting that would indeed make a mess. I would personally prefer to just work up psilocybin, then when all done dephosphorylate and try to crystallise as fumarate or tartrate or something.

Extracting psilocybin should not be done with anything acidic because A) yes it will dephosphorylate and B) acetic acid extractions have been shown to be inferior to lower alcohol extractions anyway. Unfortunately acid/base extraction workups are out of the question.

I am personally going to first try a work-up to precipitate psilocybin using calcium but I really doubt that I can get the proteins loosened up to let that happen. If it doesn't work I will try the full work-up described by - I think - Hofmann, using a column.
I'm not sure if a small portion of the free psilocybin can be crashed out with freeze precipitation...

That I would like to do a full purification is probably because I am a geek who wants to yield crystals but there is really not much benefit compared to a liquid extract. If extracted with ethanol it is simple because you can consume it as is. But a bit better would be extracting with methanol (shown to be the best solvent), then evaporated and redissolved with ethanol.

#11 Haxcor

Haxcor

    Cellar door

  • Expired Member
  • 212 posts

Posted 13 August 2013 - 01:18 PM

That I would like to do a full purification is probably because I am a geek who wants to yield crystals but there is really not much benefit compared to a liquid extract. If extracted with ethanol it is simple because you can consume it as is. But a bit better would be extracting with methanol (shown to be the best solvent), then evaporated and redissolved with ethanol.


This is what I have done a few times and works great. Psilocybin can be freeze precipitated and you can see the fruits of your labor when you do this. I would love to see some other work trying to keep the Psilocybin in tack without converting it.

#12 Defiance

Defiance

    Trainee

  • OG VIP
  • 1,386 posts

Posted 13 August 2013 - 01:32 PM

The big problem is that proteins are stuck to the alkaloids and apparently the complexes they form together aren't really stable when you try to extract.


Silliness. Look at DMT, all mixed in with tannin. Tannins bind to and precipitate alkaloids, and they form insoluble base complexes, but we can still extract DMT just fine. Proteins are insoluble in water, but we can still make tea just fine. I think you've been spending too much time at the Nexus, 69ron loves to talk about complexes.

Edit: I will say this though, SOME psilocin is probably all bound up in proteins, and that's probably why occasionally people get blown away when they drink the bottom shot of extract.

People have guessed at the identity of the bulky but inactive crystals derived from a super basic extraction: they are probably sugars.


Yeah they've almost got to be some sort of sugar. If there's even a bit of water in your solvent, if you use 70% iso, the crystals won't crash out. Whatever they are, they're clearly very soluble in water and insoluble in alcohols. Sugars have always seemed like a good guess to me.

There's one way to know for sure, right? Grab the potassium permanganate and get a torch...

Psilocin exists mostly intracellularly and extracting that would indeed make a mess.


If it's so hard to extract, again, why does making tea work so well? I don't buy it without proof.

Extracting psilocybin should not be done with anything acidic because A) yes it will dephosphorylate and B) acetic acid extractions have been shown to be inferior to lower alcohol extractions anyway. Unfortunately acid/base extraction workups are out of the question.

I am personally going to first try a work-up to precipitate psilocybin using calcium but I really doubt that I can get the proteins loosened up to let that happen. If it doesn't work I will try the full work-up described by - I think - Hofmann, using a column.
I'm not sure if a small portion of the free psilocybin can be crashed out with freeze precipitation...

That I would like to do a full purification is probably because I am a geek who wants to yield crystals but there is really not much benefit compared to a liquid extract. If extracted with ethanol it is simple because you can consume it as is. But a bit better would be extracting with methanol (shown to be the best solvent), then evaporated and redissolved with ethanol.


Take pictures!

That's one reason why I started adding citric acid crystals to my alcohol extracts. Another reason was I'd noticed that citric acid had the same qualitative effect on the trip as a lime juice soak and that dissolving citric acid crystals in blue water (mushroom tea) turned the water back to clear. I'd like to know what that means in terms of oxidized psilocin; does the acid change it into something else that's also inactive or does it "reactivate" the psilocin?


Now THAT is interesting. From what I understand you'd need to do a proper reduction to "reactivate" the oxidized psilocin. I wouldn't have predicted the color would change back to clear. I think the hydroxyl at position 4 would oxidize, but I know that amines can too. They may behave differently depending on which one oxidizes? Maybe you don't need a reduction if the hydroxyl oxidizes?

The safe money is that you're just destroying it, but if it was still active...

Well, I don't know.

And freeze-precip'ing the sugar out works great for lowering the concentration of inactives in the mix which also helps boost its relative potency (along with reducing it, which also causes more sugar to crash out so the process can be repeated a few times).


I just feel like we're purifying an alkaloid like we would be purifying a cannabinoid, which can't toggle between salt and freebase. We can wash and wash and eventually, probably, get something pretty pure. But we should be able to do it faster with an A/B.

I think the reason nobody has pulled out crystals is because nobody evaps under inert atmosphere or vacuum and they oxidize. Combined with the fact that tryptamines really don't crystallize very easily anyway. But maybe I'm wrong and we really need to avoid acids, wash out the impurities, and run a column.

I'll believe the first person to get crystals, I guess. Has anyone tried to distill it out of solution?

Edited by Defiance, 13 August 2013 - 02:10 PM.

  • Haxcor likes this

#13 Haxcor

Haxcor

    Cellar door

  • Expired Member
  • 212 posts

Posted 13 August 2013 - 04:18 PM

I like what your saying defiance and it makes a lot of sense. You have way more background in the lab then I think I would ever have. If you have a method that you think would work please let me know i would love to try it. I would love to get some stable crystals. Or even just something stable if possible. If you can write up a lab tek I would love to try it out.
  • Defiance likes this

#14 Solipsis

Solipsis

    Mycophage

  • Free Member
  • 115 posts

Posted 13 August 2013 - 04:29 PM

Silliness. Look at DMT, all mixed in with tannin. Tannins bind to and precipitate alkaloids, and they form insoluble base complexes, but we can still extract DMT just fine.


Tannins are not proteins. If tannins were the issue I don't think we would have the problem we have.

Proteins are insoluble in water, but we can still make tea just fine.


Not sure about this but I think oligopeptide proteins are not necessarily insoluble in hot water or alcohols or at the very least the proteins are denatured which means that they lose their tertiary structure which indicates that the intramolecular bonding is destabilised, allowing other bound or trapped molecules to be freed and dissolved. (Actually I am not sure if most proteins involved are actually enzymes that were busy using the alkaloids in metabolism, so they would have binding sites for them). Denaturing doesn't mean you can get rid of the proteins this way, you would still have the material, furthermore some lemon juice is often added to help with tea to aid the dissolution and/or dephosphorylation. (I believe that the more psilocin esters are turned into psilocin, the more you get the extremely short onset of effects since no prodrugs have to be metabolised).

You did give me an idea though: if I try my calcium method maybe I should do it at elevated temperatures to destabilise the proteins.

Anyway I kinda hope you are right and that you being right means that this calcium reaction has a bigger chance of success... :)

I think you've been spending too much time at the Nexus, 69ron loves to talk about complexes.


:) Your point being? Because I do think he has one.

Edit: I will say this though, SOME psilocin is probably all bound up in proteins, and that's probably why occasionally people get blown away when they drink the bottom shot of extract.


I think the reason for that is evaporation of solvent (especially alcohols) increases the concentration. It is a common phenomenon for extracts and liquid LSD.

Take pictures!


Alright, I will. :)

Now THAT is interesting. From what I understand you'd need to do a proper reduction to "reactivate" the oxidized psilocin. I wouldn't have predicted the color would change back to clear. I think the hydroxyl at position 4 would oxidize, but I know that amines can too. They may behave differently depending on which one oxidizes? Maybe you don't need a reduction if the hydroxyl oxidizes?

The safe money is that you're just destroying it, but if it was still active...

Well, I don't know.


I think the blue color indicates an unusual electronic state that causes the absorption of light and emission of mostly blue wavelengths. Maybe for a similar reason DMT N-oxide is yellow. So it isn't necessarily so that the indolol OH oxidises (this would make sense since grey blue or black colored tryptamines are typically still potent which would be weird if the indolol function was messed up). The oxide apparently binds ionically at the now quaternary amine - unusual electronic state remember?. So my theory is that the citric acid reacts with the tryptamine N-oxide using the acid functions to H-bond.

I just feel like we're purifying an alkaloid like we would be purifying a cannabinoid, which can't toggle between salt and freebase. We can wash and wash and eventually, probably, get something pretty pure. But we should be able to do it faster with an A/B.


Cannabinoids are not alkaloids nor bases (they have no amine function) so they couldn't be freebase or salt.

I think the reason nobody has pulled out crystals is because nobody evaps under inert atmosphere or vacuum and they oxidize.


If you read the literature you will learn that crystals don't tend to form until the chloride (there called halogen) is washed out first. You need silver salts to do that.

Combined with the fact that tryptamines really don't crystallize very easily anyway. But maybe I'm wrong and we really need to avoid acids, wash out the impurities, and run a column.


Also yeah, a column is necessary to purify. I don't think those chemists are doing it for shits and giggles.

I'll believe the first person to get crystals, I guess.


Challenge accepted. :D
I just hope I can raise the resources for the necessary materials.

Has anyone tried to distill it out of solution?


Ehh, the alkaloids are not volatile.
  • Defiance likes this

#15 Defiance

Defiance

    Trainee

  • OG VIP
  • 1,386 posts

Posted 13 August 2013 - 07:21 PM

Tannins are not proteins. If tannins were the issue I don't think we would have the problem we have.

Not sure about this but I think oligopeptide proteins are not necessarily insoluble in hot water or alcohols or at the very least the proteins are denatured which means that they lose their tertiary structure which indicates that the intramolecular bonding is destabilised, allowing other bound or trapped molecules to be freed and dissolved. (Actually I am not sure if most proteins involved are actually enzymes that were busy using the alkaloids in metabolism, so they would have binding sites for them). Denaturing doesn't mean you can get rid of the proteins this way, you would still have the material, furthermore some lemon juice is often added to help with tea to aid the dissolution and/or dephosphorylation. (I believe that the more psilocin esters are turned into psilocin, the more you get the extremely short onset of effects since no prodrugs have to be metabolised).

You did give me an idea though: if I try my calcium method maybe I should do it at elevated temperatures to destabilise the proteins.

Anyway I kinda hope you are right and that you being right means that this calcium reaction has a bigger chance of success... :)


You know, that's a good point. Proteins AREN'T tannins, they are temperature sensitive, and most teas are made hot.

But room temp alcohol extracts work too, and proteins typically aren't soluble in methanol or ethanol anymore than they're typically water soluble. For this theory to work, whichever protein is allegedly binding the alkaloid would have to be pretty special indeed.

:) Your point being? Because I do think he has one.


Haha, well you have more faith in him than I do then. He stopped posting here a few years ago when he couldn't back up his info about LSA complexes.

I think the reason for that is evaporation of solvent (especially alcohols) increases the concentration. It is a common phenomenon for extracts and liquid LSD.


Maybe. Or maybe insoluble proteins just slowly precipitate, and take some alkaloids with them.

Alright, I will. :)


I am looking forward to it, seriously. There are a few people here, myself included, who will go over your theories with a fine-tooth comb but we are really all dying to see results.

I think the blue color indicates an unusual electronic state that causes the absorption of light and emission of mostly blue wavelengths. Maybe for a similar reason DMT N-oxide is yellow. So it isn't necessarily so that the indolol OH oxidises (this would make sense since grey blue or black colored tryptamines are typically still potent which would be weird if the indolol function was messed up). The oxide apparently binds ionically at the now quaternary amine - unusual electronic state remember?. So my theory is that the citric acid reacts with the tryptamine N-oxide using the acid functions to H-bond.


Can the cyclic amine oxidize as well as the tertiary/quaternary amine? Which is more likely to oxidize? I think it's the hydroxyl, right? If not, why not? I actually have a PM in to a buddy about this right now. Since DMT lacks the hydroxyl I don't know if we can compare the two?

Cannabinoids are not alkaloids nor bases (they have no amine function) so they couldn't be freebase or salt.


Exactly my point, so why are we purifying psilocin like it's not an amine? An A/B seems like the way to go.

If you read the literature you will learn that crystals don't tend to form until the chloride (there called halogen) is washed out first. You need silver salts to do that.


Where did the halogen come from? Did we introduce a halogen at some point in the extraction? Nothing in what I know about the biosynthesis of tryptamines leads me to believe it requires halogens? You said chloride, though, so maybe you're referring to salts in the substrate?

You sure don't need silver salts to distill out the alkaloid as a freebase. If that's true then maybe chemical separation isn't the way to go. I'd love to read the literature. Link it if you can.

Also yeah, a column is necessary to purify. I don't think those chemists are doing it for shits and giggles.


I had a buddy years ago who ran a column to purify just because it was more convenient for him with the particular compound. When you distill tryptamine freebases, because of their middling bp and propensity to crystallize you have to do things like carefully control the temp in the condenser and use a jacketed column to keep the distillate from crystallizing in the condenser and clogging.

Sometimes people do things because it's easier or because they have the gear for it, you know? Not because it's the only way.

Challenge accepted. :D
I just hope I can raise the resources for the necessary materials.


You and me both, this is interesting!

Ehh, the alkaloids are not volatile.


Other tryptamines can be distilled or sublimated as their freebase under vacuum. I don't think psilocin is THAT special. Everything is volatile with enough heat, and with enough vacuum you should be able to reduce the bp to below temps that would cause the molecule to degrade.

I guess what I'm getting at is, if a chemical separation isn't cutting it, what are our options for physical separation?

Edited by Defiance, 13 August 2013 - 08:01 PM.


#16 Haxcor

Haxcor

    Cellar door

  • Expired Member
  • 212 posts

Posted 13 August 2013 - 09:26 PM

You both are way over my head but I would like to ask why are you saying an a/b would work? Since psilocin is not a fat or oil what would be the point of a non-polar pull. Are you saying that doing a non-polar pull would take out the proteins and make it more pure? Thank you and sorry for the remedial question

#17 ConsciousFeeder

ConsciousFeeder

    Too rich the rich king.

  • Expired Member
  • 920 posts

Posted 13 August 2013 - 09:43 PM

Oh my so much wonderful sciencey knowledge already. I only have about five minutes to jump on and check for posts in the few threads I posted in yesterday and damn lots of talk in this post already. I am heading out to hang out with one of the friends I listed and will ask him more specific questions about the presumed extract and any more specific details he has tonight.

I will take the time to full read all your replies later this evening when I get home.

Love jumping on and seeing so many posts in a thread I started. :heartbeat

Keep it coming!

#18 Defiance

Defiance

    Trainee

  • OG VIP
  • 1,386 posts

Posted 13 August 2013 - 11:26 PM

You both are way over my head but I would like to ask why are you saying an a/b would work? Since psilocin is not a fat or oil what would be the point of a non-polar pull. Are you saying that doing a non-polar pull would take out the proteins and make it more pure? Thank you and sorry for the remedial question


Oh my, don't get too impressed by the jargon. We're still figuring out what we're saying too.

And yeah, I mean I guess my point is this. Psilocin is an alkaloid, and alkaloids have two forms. They can either be a water soluble (usually) salt or a non-polar soluble (usually) freebase.

But the other crap can't do that, right? So you can flip it back and forth and use the changes in solubility of the alkaloid to isolate it from the other stuff that can't flip back and forth.

That works really well with, say, mescaline and DMT. But nobody has been able to make it work with mushrooms. We're kind of split on why that is.

I think it's fair to summarize and simplify Solipsis' point as "I don't think you can do that, Defiance, and here's why..." and my point is "Well, you can do that with every OTHER tryptamine alkaloid..."

He can correct me if I'm wrong, but I think that's probably the gist of it.

And you always start good threads, ConsciousFeeder :greenboun

#19 Haxcor

Haxcor

    Cellar door

  • Expired Member
  • 212 posts

Posted 14 August 2013 - 10:31 AM

And yeah, I mean I guess my point is this. Psilocin is an alkaloid, and alkaloids have two forms. They can either be a water soluble (usually) salt or a non-polar soluble (usually) freebase.

But the other crap can't do that, right? So you can flip it back and forth and use the changes in solubility of the alkaloid to isolate it from the other stuff that can't flip back and forth.


so it seems like we are confused on how to go about this. If its neither a salt or a freebase then what else would we be looking for? If it was a salt we could change it over to a freebase and back with a strong base, true? Im not sure. I will try to find some of the lab reports that i followed many years ago. maybe they would help.

#20 Solipsis

Solipsis

    Mycophage

  • Free Member
  • 115 posts

Posted 14 August 2013 - 11:41 AM

Warning: super long post, including my theories and hypotheses on mushroom alkaloid extraction; also an attempt at elucidating psilocin oxidation reactions. I added paragraph titles hopefully to make it slightly less overwhelming.

(It's hard for me to discuss my thoughts freely without using technical terms. If anyone would like something cleared up, just ask.)
(And a disclaimer: I might be abusing the term adsorption, which is possibly meant for compounds that are bound on larger surfaces but I can't be bothered to use another word. : p )


You know, that's a good point. Proteins AREN'T tannins, they are temperature sensitive, and most teas are made hot.

But room temp alcohol extracts work too, and proteins typically aren't soluble in methanol or ethanol anymore than they're typically water soluble. For this theory to work, whichever protein is allegedly binding the alkaloid would have to be pretty special indeed.


Protein properties and a possible explanation for adsorption of alkaloids

Alcohols can destabilise proteins (http://en.wikipedia....haotropic_agent) by messing with hydrophobic interactions involved in the tertiary (folding) structure of proteins. But that is probably not why you can extract alkaloids and proteins with alcohols, at least the destabilisation is not enough to disrupt adsorption enough to release stuff that is bound together - more on that in a minute.
The protein doesn't have to be that special to dissolve in an alcohol, proteins can have all kinds of solubilities depending on the polarity of the amino acid substitutions hanging on the outer side of the structure. The ones that do get extracted are probably the kind to have mostly hydrophilic amino acid sidechains on the outside and hydrophobic ones on the inside. I don't know where or how the alkaloids would be bound by adsorption. You would think on the outside because there the polar substitutions could interact with the zwitterionic psilocybin.
About what stuff is bound together, who knows, there could be glycoproteins or leptans, though I doubt they would amount to enough to be a legitimate party.
And who knows what degrades or interacts as a result of the extraction procedure used.

Here is a start.

I've also wondered about chitin for a while. As you might know chitin is a polysaccharide like cellulose fungal cell walls are built of - it is basically made up of sugars. Apparently in fungi these only form short fibrous strands, not huge chains. I am reading a patent right now (http://www.freepaten...om/4063016.html) about chitin having the ability to form complexes with lower alcohols like methanol.

What happens to fungal cells and cell walls when you dry mushrooms? A quick search seems to suggest that when mushrooms dry the cells lose more water than can be pumped in. I'm not sure how long cell plasma water is lost osmotically and if picked or dead mushrooms don't have functional water transport systems anymore. The fact or claim that you can revive dried mushrooms - if not cracker dry - by rehydrating them (like the Rose of Jericho / resurrection plant) , and the fungus can even start growing again seems to suggest that a desiccated state is more like extreme hibernation, and while prolific processes may be shut down the damage is limited like deflating a balloon with a bunch of gunk in it. :special:

Where I'm going with this is that if the dried mushrooms we extract from are organelles and metabolites (including our alkaloids) packaged in an envelope of chitin and other cell wall components (made up of all kinds of sugars and proteins, like receptors), and methanol turns the chitin into some pasty stuff

The chitin-methanol complex is a pasty, somewhat cheesy material that is stable at room temperature if kept in a closed vessel in the presence of a slight excess of methanol. However, in the open, it will lose methanol gradually as indicated above.


Wouldn't a lot of the psilocybin become trapped in macroscopic structures of shrunken cell-wall 'cheese', rather than on the scale of protein molecules?

Hopefully a hypothesis like that (but much more comprehensive and holistic) can be formulated using the educated guesses of some of my 'fellow colleagues' in this field as to the dynamics involved - I have some contacts, we can certainly use an bit of an interdisciplinary approach! Then maybe we can also come up with an experiment to put the hypothesis to the test.

For example, what would happen if you rehydrate your mushrooms when you want to extract them, then freeze-thaw them a few cycles for lysis (to make the cell walls burst), then extract with distilled water and see if psilocybin is dissolved and free enough to be precipitated with calcium chloride? That should show us what difference the drying and the addition of methanol make. If water is inefficient at least it would tell us something if we are able to make a small amount of psilocybin without the gunk.

If it doesn't work the psilocybin is perhaps bound or adsorbed differently, rather like what I suggested and what we discussed a few posts ago.
In that case we can just as well use dried mushrooms to extract, as per uge...

I'd like to pick up from here soon. :)
This is pretty exciting, I don't know if I am way out of my league here or how closely relevant these theories... but I will get some extra peer reviews and ask around if people want to cooperate and make this some serious rogue / clandestine research.

Haha, well you have more faith in him than I do then. He stopped posting here a few years ago when he couldn't back up his info about LSA complexes.


Oh, kinda like my wild theories, or... :neutral:

Maybe. Or maybe insoluble proteins just slowly precipitate, and take some alkaloids with them.


Sorry, I just got off the 'individual protein interaction' wagon again... me no gusta
Haha, just kidding.

I am looking forward to it, seriously. There are a few people here, myself included, who will go over your theories with a fine-tooth comb


I'm grateful for that, we're supposed to analyse, constructively criticise and verify stuff when we bounce ideas an theories off each other if we want to get somewhere. :)

but we are really all dying to see results.


Me too, that's why I said that I'm willing to seek academic assistance (online support and chem graduates / a controversially inclined professor off the books). If it turns out we are gonna have to just column the bastards like in the patent, soit, if we can learn and deduce whatever the hell happens during various extractions that would still be a really interesting results.

Can the cyclic amine oxidize as well as the tertiary/quaternary amine?


I highly doubt it, the cyclic amine is a secondary amine - N-oxides apply mostly to tertiary amines which have a different sort of electron distribution. The hydrogen on a secondary amine doesn't really allow electron withdrawal / donation to yield a quaternary amine. I think the hydrogen instead participates in stuff like H-bonding, being a good electron acceptor. I hope I got this right, my chemistry is a bit rusty and I don't have my degree. Although I aced Org Chem...
If you want to make an secondary amine N-oxide you need harsh conditions and reagents.

Which is more likely to oxidize? I think it's the hydroxyl, right? If not, why not? I actually have a PM in to a buddy about this right now.


I am working on some reaction mechanism pics of how I think psilocin oxidizes. It is a different kind of oxidation, no N-oxide is formed. The phenolic hydroxyl is an 'vulnerable' or reactive group, essential to the oxidation... but it is actually the fact that the indole is a conjugated heterocyclic structure that facilitates the rest.

Since DMT lacks the hydroxyl I don't know if we can compare the two?


Good point, the oxidation reactions are quite different, but nevertheless there are a few similar things going on namely that it just might be that in both cases the reaction is reversible (not sure, working on that) and the change in color is still indicative of certain electronic shifts that are a result of these oxidation reactions.

Exactly my point, so why are we purifying psilocin like it's not an amine? An A/B seems like the way to go.


Psilocin is stable in dry solid form when stored properly, but it is quite unstable in solution like I said and as I will illustrate. It is possibly quite a pain in the ass to have the compound degrade while you mess with the pH, but moreover if this is not reversible you lose the product. I still haven't figured out if the oxidation is reversible like the citric acid observation would suggest.
It's possible that when you leave a 4-HO tryptamine just sitting in aqueous solution, the degradation is reversible (whether in vitro or in vivo) or at least there may not be rapid subsequent degradation reactions that totally ruin the compound.
I should mention that I heard that 4-HO-MiPT for one individual degraded in solution within a week (nothing was said about the potency). But I have also heard that people have had their tryptamine turn dark grey or black when a solid powder attracts water to eventually become goo (blue to black is probably the color change when in solution or in a water-containing mushroom)... but no change in potency was noticed.

Psilocin's primary oxidation reaction mechanism (supposedly)

Posted Image

I think this is the reaction mechanism for base-catalyzed psilocin oxidation. Later I will try to work on possible reversal and how citric acid might be involved (I am currently thinking it is just the exact opposite, acid-catalyzed reduction
A little explanation:
- having a base present (low pH) means that a lot of the water goes from H2O to OH- and methanol goes from CH3OH to CH3O- . The funny looking formula just means that if there is water, then during the reaction the basic hydroxide OH- accepts a H+ to form H2O, water. And if there is methanol, then during the reaction it goes from the basic methoxide CH3O- to CH3OH, methanol. Unless I am mistaken, in methanol the reaction would happen to a lesser degree / slower.

- What all the hooked arrows mean is the following (first background info):
Each straight line in the structures represents a bond held together by one electron belonging to the atom at one side of the bond/line and one electron belonging to the atom at the other side (an atom is often a vertex or angle where lines meet).
Each arrow represents an electron 'jumping' from participating in one bond to making another bond, that is one way covalently bound molecules like these organic chemicals swap atoms or entire groups. If you notice the colon : next to the bases, this is a lone pair which is a pair of electrons that just 'belong' to the atom next to it... without being involved in a bond. We normally don't draw them but oxygen (O) under normal circumstances actually has 2 lone pairs and nitrogen (N) has one. When they are involved in a reaction, we draw them. And again you can see the hooked arrow, showing here that the oxygens use their lone pair to form a bond with the tryptamine's hydrogens all by themselves.
(We call acids and bases that react only by donating or accepting a lone pair "Lewis acids and bases").
So basically what happens is that when the hydrogens are hijacked by the bases, simply put there is a chain reaction of electrons flopping over so that the bonds shift places. This interconnectedness is what we call a conjugated system. (In actuality the electrons do not jump statically but it is a distributed electron cloud which has a density that can shift more or less discretely.)

I really hope I am right about the mechanism and the oxidation product. Now in the meanwhile I'm gonna look one step further or check for a reversal reaction.

pH affecting equilibrium and the kinetics of oxidation

By the way, the chance of 2 base molecules simultaneously flying into their right places for this oxidation reaction is a lot lower than when you go to a higher pH. Let me explain: when you start raising the pH first the proton (H+) on the amine starts falling off to a large degree, leaving the basic amino group neutrally charged.
- At about a pH of 8.5 half of the psilocin should have have lost it's amine proton.
- This continues when we further raise the pH but now slowly the 4-HO groups also start losing their protons.
- It seems like the real value is not known or easy to find, but for the similar compound 4-HO-indole (lacking the entire amino chain psilocin has) half loses its proton at around pH 10. Then we don't have normal freebase psilocin but I guess you should call it psilocinate, it is also a base but not neutrally charged. On the 4-position there is now an -O-.
- For psilocinate, oxidation happens much easier, because the 4-HO has already lost its proton, so only the cyclical amine has to be 'attacked' and berived of its proton for the oxidation reaction depicted above to be completed.
- Also because the deprotonated 4-O- makes the molecular a bit polar it might stop feeling comfortable in a non-polar solvent. This sucks, if you want to extract freebase psilocin. So the pH needs to be just right, and even then a portion of the psilocin can start turning into psilocinate which readily oxidises.
- You must understand, the concentrations of each of these compounds in their slightly differing forms is in an equilibrium, like a seesaw with on each side countless molecules of a form of compound. They can exchange sides, converting into each other, tilting the seesaw / equilibrium.
Le Chatelier's principle tells us the following:

If a chemical system at equilibrium experiences a change in concentration, temperature, volume, or partial pressure, then the equilibrium shifts to counteract the imposed change and a new equilibrium is established.


What this means is that the entire system always strives to reach balance, homeostasis. If on one side of the equilibrium psilocinate is quickly getting oxidised, the equilibrium will shift to make more psilocinate out of psilocin. This keeps going on until the oxidative 'pit' has dragged down all your precious alkaloids.

Where did the halogen come from? Did we introduce a halogen at some point in the extraction? Nothing in what I know about the biosynthesis of tryptamines leads me to believe it requires halogens? You said chloride, though, so maybe you're referring to salts in the substrate?


Yeah that confused me as well, and I had to ask people... indeed this is just the chloride found in tissue from organisms, like minerals are yep. The word halogen reminds us of chlorine, which is not usually found in said tissue, heh. ;)

(years ago I wondered why, if LSD is destroyed by chlorine which can be present in tap water, can it survive our stomach which contains hydrochloric acid? Well in my native language, Dutch, often the word chloor (pronounced chlore) is used to describe the element involved, and I misinterpreted the claim to be that chloride in tap water destroys LSD. My question was not dignified with an answer for quite a long time and I thought it was a big conundrum... But, you probably guessed it right away, the harmless chloride is ionic Cl- while chlorine is elementary covalently bonded Cl2 and it is reactive.)


http://www.freepatentsonline.com/3183172.pdf[/URL]

I really wouldn't subject the alkaloids to strong bases and high temperatures like that. It's lame that silver is so expensive but other than that it is a lot easier and less work...
Maybe I can find some elementary silver cheap-ish to make a silver salt myself...

I had a buddy years ago who ran a column to purify just because it was more convenient for him with the particular compound. When you distill tryptamine freebases, because of their middling bp and propensity to crystallize you have to do things like carefully control the temp in the condenser and use a jacketed column to keep the distillate from crystallizing in the condenser and clogging.

Sometimes people do things because it's easier or because they have the gear for it, you know? Not because it's the only way.


That's certainly true, I wouldn't claim that it is really the only way, but if freebasing would be the way to go you could just as well do an A/B extraction right?
But we covered that.

Other tryptamines can be distilled or sublimated as their freebase under vacuum. I don't think psilocin is THAT special. Everything is volatile with enough heat, and with enough vacuum you should be able to reduce the bp to below temps that would cause the molecule to degrade.

I guess what I'm getting at is, if a chemical separation isn't cutting it, what are our options for physical separation?


Possible problems with trying to vacuum distill freebase indolols bound to gunk

Not even sure how we came to mix up the topics of psilocybin and psilocin like this, since they need different approaches and don't have the same pitfalls - again read the patent.
In my opinion psilocybin is the main priority and if you wish to use psilocin, you can always dephosphorylate psilocybin right before you dose it although you might have to precipitate the phosphate with magnesium chloride to prevent ending up with psilocybin when you neutralize the pH for ingestion. Anyway I don't really mind discussing psilocin as well. Is it right that you hinted at someone vacuum distilling 4-HO-tryptamines or where they other kinds?
A possible difference with other situations is that I don't know if vacuum distilling actually separates the alkaloids from whatever gunk is bound or adsorbed to it. It might be like an azeotrope: for example water and ethanol are azeotropes but of the positive kind, meaning that you cannot simply separate them by difference in boiling point because:

Azeotropes can only form when a mixture deviates from Raoult's law. Raoult's law applies when the molecules of the constituents stick to each other to the same degree as they do to themselves. For example, if the constituents are X and Y, then X sticks to Y with roughly equal energy as X does with X and Y does with Y. A positive deviation from Raoult's law results when the constituents have a disaffinity for each other – that is X sticks to X and Y to Y better than X sticks to Y. Because this results in the mixture having less total sticking together of the molecules than the pure constituents, they more readily escape from the stuck-together phase, which is to say the liquid phase, and into the vapor phase. When X sticks to Y more aggressively than X does to X and Y does to Y, the result is a negative deviation from Raoult's law. In this case because there is more sticking together of the molecules in the mixture than in the pure constituents, they are more reluctant to escape the stuck-together liquid phase.[1]
When the deviation is great enough to cause a maximum or minimum in the vapor pressure versus composition function, it is a mathematical consequence that at that point, the vapor will have the same composition as the liquid, and so an azeotrope is the result.


Normal azeotropes are conventional liquid/vapor mixtures, but here we possibly have adsorption azeotropes. A similar phenomenon is observed with adsorption-bound compounds. I really don't know how strong this adsorption is, but I dare not hope it is less than considerable and consequential.
The hydroxyl group, the amine group and the pi-orbitals (electron clouds 'hovering' over the heterocyclic rings, often alocally that can enable two molecules that have them 'spoon' on top of each other) have intermolecular interactions that make psilocin molecules stick to other psilocin molecules. Why would the intermolecular interaction that binds psilocin to gunk - which can have all kinds of funky groups sticking out that match psilocin well - be much weaker?

To summarize: not only are 4-HO-tryptamines fragile enough to not even want to subject them to strongly basic conditions, adsorption azeotropy can cause bound psilocin to need much higher temperatures and stronger vacuum to be able to pull the bound protein with it. Even if it is able to break loose, I fear that at that point you would already be running at conditions that are horrible to your product.

You both are way over my head but I would like to ask why are you saying an a/b would work? Since psilocin is not a fat or oil what would be the point of a non-polar pull. Are you saying that doing a non-polar pull would take out the proteins and make it more pure? Thank you and sorry for the remedial question


Actually a non-polar wash is included in the procedure described in the patent by Ralf Heim (sorry it wasn't Hofmann, apparently this is some other guy named Hoffman, I guess I hassled the hoffs...).
It serves indeed to remove some kinds of proteins that have more hydrophobic groups on their outsides making them a bit (enough) partial to the non-polar solvent. And who knows what other biological material you can get rid off that way.

Oh my, don't get too impressed by the jargon. We're still figuring out what we're saying too.


Again sorry about that, each technical term describes a specific concept neatly. Look how long this post is, imagine if I tried to make myself more intelligible to curious layman lurkers by explaining it all. But like I said: if you ask me, I will try.

And yeah, I mean I guess my point is this. Psilocin is an alkaloid, and alkaloids have two forms. They can either be a water soluble (usually) salt or a non-polar soluble (usually) freebase.
But the other crap can't do that, right? So you can flip it back and forth and use the changes in solubility of the alkaloid to isolate it from the other stuff that can't flip back and forth.

That works really well with, say, mescaline and DMT. But nobody has been able to make it work with mushrooms. We're kind of split on why that is.

I think it's fair to summarize and simplify Solipsis' point as "I don't think you can do that, Defiance, and here's why..." and my point is "Well, you can do that with every OTHER tryptamine alkaloid..."

He can correct me if I'm wrong, but I think that's probably the gist of it.


I don't think you can do that, Defiance, and here's why...

Sure, you can do it with a lot of compounds that are not instable like indolols (which 4-HO-tryptamines are) or that have a protected 4-HO group, like the 4-AcO and 4-PO esters.
It's just in principle considered a bad idea to use procedures that make your product super vulnerable. It makes your procedure liable to side-reactions and loss of product, there can be any number of complicating interactions and it is just messy to have to figure out if you can salvage it and whether you have to do further unanticipated new work-ups which costs more material and time, and you can't really be so certain anymore how it will turn out, the experiment runs out of your control.
Granted, if this oxidation product (an indolone) is as far at it 'degrades' and it is also reversible, then it wouldn't be such a problem.

And you always start good threads, ConsciousFeeder :greenboun


Definitely! Thanks for initiating this even if this isn't exactly what you expected, anyway I'm pretty psyched if you can't tell. :amazed:
(edit / correction: would you guys mind if I copied posts from this thread on another forum - an Advanced Drug Discussion forum? Meanwhile I will ask mods there if they would mind...)

Edited by Solipsis, 14 August 2013 - 11:58 AM.

  • TVCasualty and Baby Squid like this




Like Mycotopia? Become a member today!