Preparation of crystalline THCA

[Old Gold]

Aha, sweet. I was almost wondering if they weren't your own replications. I just remember GWPharma mentioning Sephadex LH-20.

 

[G.O. Joe]

^ That was pulled from GW Pharma patent, correct?

No that stuff wasn't in the GW patent. This is from people at the University of Mississippi that were replicating the experiments and reviewing these patents

Aha, sweet. I was almost wondering if they weren't your own replications. I just remember GWPharma mentioning Sephadex LH-20.

No one replicated anything, and it's all from the patent except the column loading. 30:1 is 13.3 grams. Both the US and WO versions say 20 ml. of something liquid and representing 100 grams of herb of unspecified THCA content was applied to the column, they ended up with the 5 grams of THCA, and there are earlier mentions of a THCA starting material - but not how they got it or what it's for - that's 72% THCA and 17% THC, which sounds unlikely from a hexane extract, slightly acidified or not. The real experimental details like the flow rate and which fractions had cannabinoids are absent, and this is the case for every mind-numbing example given.

 

[Phineas Freak]

Non psychoactive and a powerful inflammatory.

Thanks for the reply. Thats what I read and thought too.

I tried a tincture made off a couple fresh undried buds. To my knowledge there should be mostly THCA present and no THC. I drank all and did wake up some hours later, so I am not absolutely sure it is psychoactive, but it sure had a strong effect. lol
I won't come across fresh buds before maybe next autumn, so I cannot try again soon.

Another thing I wonder is, shouldn't THCA as an acid be water soluble?

 

[live resin]

Another thing I wonder is, shouldn't THCA as an acid be water soluble?

The 2-carboxyl group by itself could be considered hydrophilic, but being next to the hydrophobic alkyl side chain on the 3 position, it doesn't change solubility of the molecule at all imo. Otherwise, everyone would be extracting fresh plant material with water to make live resin.

To make cannabinoids soluble you need to change that alkyl side chain or the phenolic hydroxyl group, or both. A carboxyl group in the 2 position would like hinder modification of the hydroxyl group, though I need to look into that more to be sure.

What is interesting about this though, is that when you start modifying the alkyl side chain to make it water soluble it also sometimes affects the psychoactivity of the molecule.

 

[Phineas Freak]

Thanks for your explanation.

While my a bit faded chemistry is good enough to follow you, I couldn't decide if you are right or not. But it sounds plausible to me.

THCA in the resin gland is definitely not water soluble in substantial amounts or rain or a waterhash extraction would dissolve THCA into the water.
It is of course just anectodal observation. But as you said:"Otherwise, everyone would be extracting fresh plant material with water to make live resin."


To make cannabinoids watersoluble it would maybe be easier to just dissolve them in glycerine and add this to water?
(Not interesting for you if you want to make live resin of course.)

What is interesting about this though, is that when you start modifying the alkyl side chain to make it water soluble it also sometimes affects the psychoactivity of the molecule.

Do you mean THCA would maybe get psychoactive, if made watersoluble by this method?

 

[live resin]

Do you mean THCA would maybe get psychoactive, if made watersoluble by this method?

No, THCA cannot be psychoactive as far as I know. The carboxyl group hinders binding at CB1.

It will increase or decrease the psychoactivity of the THC molecule (the strength and duration of the high).

For example, microgram amounts of dimethylheptyl THC will keep you "stoned" for 2+ days. Except "stoned" becomes something more like an acid trip, about +3 on the Shulgin scale. Cannabinoids are hallucinogens after all.

 

[Phineas Freak]

So in my test, maybe the alcohol contributed to the effect.

I would not want to test dimethylheptyl THC, or any other manipulated molecule newly on humans.

I am sure someone will.

 

[weedaholic721]

IMO semisynthetic/synthetic cannabinoid analogs, as well as other non classical CB1 and CB2 agonists, are a seperate field and if ingested by humans should be done so extremely cautiously.

Has anyone else succeeded in producing crystalline THC-acid? The Guild Extract company appears to have the process pretty streamlined as they are producing a fairly large amount. If you are attending the Cannabis Cup in L.A. they have a booth and have it available, it also is available in San Jose. The problem is they have kept their process secret as far as I know but as mentioned before it appears to be jist crystallized from a bho solution as Pangea has posted.

I'm sure chromatograpy and isolates are the future. For now, its getting the methods out there so anyone with enough material and intelligence can produce isolates on there own. I currently lack material to achieve anything worthwhile.

 

[Pangea]

They probably recrystallize it after forming seeds from slow evap, its what I do and it can be done quick and easy.

Most processors could add the slow evap process to their regular extraction/purging process/routine by just adding a step between extracting and purging their product, they'd first form seed crystals on order of 10-30% of your total concentrate solution. The guild guys jumped on it quick they are for sure using the info ive shared, there is no secret and if they are not being open about it to capitalize on being first to market, thats not cool.

Price of crystalline thca should be the same as reg concentrates.

How many guys blast tube all day everyday? Instead of pouring or scraping into vac ovens first pour your solutions into mason jars, fill them at least half full, let them sit in a dark coolish area, my temps have ranged from 5 - 20oC, avoid sudden temp changes, avoid agitation, control evaporation speeds with jar lid and band, you can tighten it and release the preasure at different time intervals, this way allows you some more control vs a loose lid, once your jar head space pressure fills crystallization will slow/stop, until the pressure is released and evaporation can continue. After two to three weeks you will should have decent seed crystal formation, you can remove the crystals and pour the solution onto parchment for regular vac purge processing.

Imagine all the processers out there that could turn 10% of their product into pure thca just by adding a cost free step!

The recrystallization is easy, for simplicity and purity I recommend redissolving into distilled butane because of its low bp it will be basically impossible for there to be any trace residuals, if your seed crystals are nearly pure(no surface area contam, no internal nucleating contam particles).

Ive been able to redissolve purified seed crystals into butane, once the butane off gasses you form an amorphous shatter/glass that is clear and pure as can be. As soon as a nucleating force is exposed to the shatter/glass it literally explodes into pure microscopic crystals, expanding to many times its original covered surface area, instantly. Its really cool. The less pure the slower it happens, but its still quick and cool.

 

[cashish]

There are many reasons for developing chromatography methods for isolating cannabinoids, I am sure even if GW Pharm were aware of the simplicity involved in a method like ive shared they would still pursue and research other methods, there are utility and merits to different paths.

Ive shared it a few times, but guess I can be more detailed.

The recrystallization for purity part is pretty standard, the initial crystallization part is the first hurdle and just as simple. Its actually easier than making traditional BHO as it involves less steps. Instead of spreading thin and purging, collect it in a container/vessel that allows for slow, controlled evaporation, depth of the solution vs surface area is a important factor as is the headspace and lid for evaporation. A container like a graduated cylinder is ideal or a regular 250ml mason jar filled at least half full work as well. The larger the surface area the easier it is for the solution to crash, and also has other limiting factors. The solution viscosity is important as well, I vac my collection chamber down to -20, there is no liquid tane, I cannot pour out the solution, I scape collect it, but its basically like a No 1. maple syrup consistancy, very liquidy, very terpy, glass baster/droppers work well to transfer.

So recap,

1. Collect bho into proper vessel.
2. Store in proper area; consistent temp, limit light, limit vibrations, limit disturbances.
3. Wait until satisfied with crystallization amount.
4. Pour off un crystallized solution into new vessel to further form crystals(depends on state of solution) or pour/spoon out and treat remaining solution as if it was just extracted, so either vac purge or decarb for edibles.
5. Carefully collect crystals from the bottom of the vessel(probably where a jar has a advantage over a skinny cylinder)

I've been able to grow crystals in little 2.5ml vials with high terp varieties after they have been vac purged, just by leaving the lid loose.

I've had a crystal in a sealed solution of RO water since I first collected them, it hasnt changed. Ive had a few in indirect sunlight for 60 or so days with no visible changes. They are quite stable.

I am excited to see some really large crystals, they're going to look very cool!

Not sure I understand. Just collect bho solution into container without additional solvents besides the butane/propane mix?

 

[live resin]

The guild guys jumped on it quick they are for sure using the info ive shared, there is no secret and if they are not being open about it to capitalize on being first to market, thats not cool.

I don't think Guild Extracts uses this procedure for their 99.96% THCa.
Besides being uneconomical at large scales, I-502 would not allow this procedure unless it was done in a fume hood, which would be a major bottleneck in production.

 

[HG23]

I think the crystallizations are similar to how you might have made rock candy from a saturated sugar solution as a kid. Leaving the hydrocarbon extract runny with the max amount of terpenes/slight residual hydrocarbon allows the THCa molecules to remain mobile in the solution and form crystals. Using the right container shape/size and getting the amount of solvent just right seems to have a big impact. Pangea laid it all out pretty well. Thanks man. I have made some decent little starter seed crystals I will post up when I get back home.

I am guessing they are using column chromatography to separate the THCa from the crude on a larger scale. I have read more than a couple examples of chemists using this technique to separate fractions from plant derived essential oils. The resulting THCa fraction would be in the form of a super saturated solution and would likely crystallize the whole container it was in. Don't you think some of Guild's pictures look like the pieces are shattered from a petry dish or something?

 

[Avinash.miles]

They probably recrystallize it after forming seeds from slow evap, its what I do and it can be done quick and easy.

Most processors could add the slow evap process to their regular extraction/purging process/routine by just adding a step between extracting and purging their product, they'd first form seed crystals on order of 10-30% of your total concentrate solution. The guild guys jumped on it quick they are for sure using the info ive shared, there is no secret and if they are not being open about it to capitalize on being first to market, thats not cool.

Price of crystalline thca should be the same as reg concentrates.

How many guys blast tube all day everyday? Instead of pouring or scraping into vac ovens first pour your solutions into mason jars, fill them at least half full, let them sit in a dark coolish area, my temps have ranged from 5 - 20oC, avoid sudden temp changes, avoid agitation, control evaporation speeds with jar lid and band, you can tighten it and release the preasure at different time intervals, this way allows you some more control vs a loose lid, once your jar head space pressure fills crystallization will slow/stop, until the pressure is released and evaporation can continue. After two to three weeks you will should have decent seed crystal formation, you can remove the crystals and pour the solution onto parchment for regular vac purge processing.

Imagine all the processers out there that could turn 10% of their product into pure thca just by adding a cost free step!

The recrystallization is easy, for simplicity and purity I recommend redissolving into distilled butane because of its low bp it will be basically impossible for there to be any trace residuals, if your seed crystals are nearly pure(no surface area contam, no internal nucleating contam particles).

Ive been able to redissolve purified seed crystals into butane, once the butane off gasses you form an amorphous shatter/glass that is clear and pure as can be. As soon as a nucleating force is exposed to the shatter/glass it literally explodes into pure microscopic crystals, expanding to many times its original covered surface area, instantly. Its really cool. The less pure the slower it happens, but its still quick and cool.

can it really be that easy???
anyone else using this method can elaborate with experiences/pictures?

 

[weedaholic721]

It does appear to be that easy and CBD is being crystallized in a similiar fashion by multiple companies. I'm just surprised that's its not something that's been done before now. All the literature I've read, its never recrystallized, but it is usually the case that they decarb to THC before purification, other then the Rapid Chromatograpy method patents that G.O. Joe has posted.

There are better pics and more info here on my thread in this topic:

https://www.icmag.com/ic/showthread.php?t=304292&page=5

Reading back through that thread, I did see Guilds collobration partner Calilabs did post a picture of their early attempt.

Pangea IMO you have the naming rights to this technique with the practices I've seen adopted by most in this community. It also could be referred to just as its full name Crystallization of THC-a from a Crude Cannabis Extract Solution or something like that.

 

[Pangea]

Your dissolved solution should be a runny/low viscosity, I do not recommend using additional butane or petrol based solvent to achieve this. If your concentrated solution is to high of viscosity add a purified natural sourced terpene to lower it. High terpene varieties produce the proper viscosity naturally, and why I was able to stumble across this.

The evaporation of the solvent(Terpenes Primarily) from the solution creates a super saturated condition, causing crystals to form.

Imagine a glass of water and ice tea sugar powder, if you add to much powder it will not dissolve no matter how much you stir. If you add the perfect amount it will be completely dissolved, BUT if you leave that glass sit on a counter for several days the water will evaporate, eventually there will be so little water remaining that the sugar mixture reaches a super saturation point where it will want to crystallize or precipitate because there is not enough solvent to keep it dissolved.

The butane is incidental, its a means to dissolve and carry cannabinoids and terpenes in a purified concentrated manner. You could literally dissolve rosin into a solution of limonene and let it evaporate and it will form the same large crystals. I would like to use distilled or purified Limonene, as in LHO but the method to remove mystery contams from it is not public knowledge as far as I know.

I have old purged razor thin slabs that have sit for to long form single large crystals on them(1-5mg) from 2mm slabs. You can pluck them out and wash them.

Pull out your microscopes and look at your wax`s shatters and what not, take a look at father earths classic microscope photos of crystals forming in his shatter.

Solvent choice is important and many dangers are associated with each and much be done in safe and controlled manners.

-

As for the safety and purity and utility of the crystals themselves. I`m not so sure I completely understand the criticisms of Chimera's, as its seemed not at all with the production/mfg safety, but with the results themselves.

This is not pharmaceutical formulating or compounding. This is a method of purification, which will allow for proper and more more precise formulating, compounding and experimenting.

The fact that my crystals have not yet tested for 99+% is also incidental. The nature of crystallization and recrystallization will result in extremely pure compounds and that is the point.
Before this method was utilized the only people selling or forming 99+% pure THCA was analysis standard companies, and they charge $100,000 per gram, now its $100/gram in California.

THCA is safe, THC is safe. People eat and smoke impure THC products all the time. Its one thing to suggest people take caution and warn against selling an untested or un-analysed product(which no one selling large thca crystals is(myself or guild/calilabs(they test)), as all products should be analysed and labeled properly if sold commercially.

Its an entirely different matter to suggest that because the level of purification of THCA is now at such a high level that it should be kept out of the "basement" and only be researched in a scientifically regulated and bureaucratic controlled environment. Pehaps I am not understanding Chimera's statements, perhaps Chimera doesnt fully understand the science and nature of crystallization itself?

Its sometimes difficult to fully explain ones position through web chat, so I hope Chimera can take a moment and write out specifically what are his concerns and views, because after giving it some thought and a sleep, from what Ive heard you are way off base. The line you've drawn is wrong, and I hope to hear your justification of why and where you've drawn it.

(wrote most of this last night, for those completely lost its regarding hash church)

@avinash, It really is this simple. I could take pics of my jar's but its just a pic of a jar there is nothing else to it, viscosity is key and could maybe be captured on video for comparison.
@HG23, glad to hear youve had success, youve described it correct! Im doubting they use such secondary methods, once youve got a decent amount of seed crystals its very easy and can be done much quicker to recrystallize in decent size or shaped crytals, but once you redissolve them they will want to form microscopic crystalline precipitate vs larger, so slow evap imo must be done to achieve such a result. There really are two prime routes to crystallization, evaporation and cooling, which effect the solubility of the solution. Learning how manipulating those factors influences the formation of crystals is the name of the game.

@liveresin, time will tell, but this can be scaled up so simply, a small fume hood could handle the vapors of a vessel sized to produce kilo's of crystals per batch, no problem. The off gassing is low and controlled, its such a small and simple issue to cover.

@weedaholic, ive seen some cbd crystallization posts, def cool stuff, and very relevant, like Ive mentioned, its all been under our eyes the entire time, it was inevitable someone figured it out or stumbled across it in such a manner as I did.

Slow evaporative crystallization, is what I call it, its the most accurate imo.

PS:

Its just the beginning, it may be possible to form larger seeds in a shorter amount of time, the limits are completely unknown at this point.

 

[Billy Liar]

Crystal forming is a fun sport lol...

My experience comes from D M T extractions. Cooling the D M T saturated heptane/hexane very very slowly is the key to large crystals. And iirc the crystals always test as pure and other precipitates are, well, other precipitates.. I last did a day in a cool pantry, followed by a day in a cool fridge, then a day in a colder fridge, then onto a day or more in a freezer, got white crystal sat on top of yellow powder. Picked off the crystals and discarded the rest..

Just a brain fart lol..

Peace
BL

 

[HG23]

Here is a shot of my little seeds. I haven't rinsed off the mother liquor so they look kind of dirty. I produced these in a 250ml mason jar filled about half way. I let it sit for 4 weeks.

 

[River_Ramblin]

@pangea, azeotropic distillation is how its done. Just add water. You just have to find the right ratio to get an extract you can smoke. If your going to make clear its not as big of a deal

 

[Pangea]

@RiverRamblin, Re: Limonene distilling and extracting?

 

[River_Ramblin]

yes. they will from two fractions in the boiling flask before you start spinning it and, you will end up with two clean fractions in your receiving flask.