Preparation of crystalline THCA

[Pangea]

Hi xizqu, the THCA is being supersaturated, as the terpenes and any other residual solvent evaporate the THCA levels increase to the point of super saturation and crystallization can take place. Crystallization does happen in a vac but will often only result in very tiny crystals, like when BHO "sugars out" and "waxes up". I have only produced decent sized crystals with a terpy extracts, but I believe one could create a mix that would produce seeds with less terpy starting material.

Weedaholic, Ive seen those results as well and they are perplexing. It'll be interesting to see the decarb rates when bound in a crystal lattice, I suspect it will be slowed. Ive boiled some samples for a while with no physical change as well as just having them stored since september.

 

[Tynehead Tom]

man, reading thru this thread makes me wish I took up chemistry LOL
most of this discussion is way hell and gone above my head. that said, I've made crap loads of oil and more recently vac purged to waste butane shatter. I only make small batches for myself

anyhow, I remember years ago we had a oil making set up much like a still, recollecting the alcohol at the end. We used distilled grain alchohol, also made in the still hehehe

anyhow, I remember a particularly large batch that I ran out of time processing and stuck a dozen pint and quart jars in the root room in the basement in the dark to gas off while I went away for a couple weeks.
what I came back to was thickened up oil full of crystallization. weirdest thing I ever saw. now, we are going back to 1991 here so all this weed chemistry was in it's infancy.

were those crystallizations in my oil the THCA crystals you guys are referring to here?
and if I'm understanding, you can remove them and culture them?
what does one do with those crystals? drop em in the vapor pen? or is this crystal being refined for use in medicine, like a "thc" pill
I find this shit fascinating, even if I barely understand it. LOL

 

[thegreenman91]

man, reading thru this thread makes me wish I took up chemistry LOL
most of this discussion is way hell and gone above my head. that said, I've made crap loads of oil and more recently vac purged to waste butane shatter. I only make small batches for myself

anyhow, I remember years ago we had a oil making set up much like a still, recollecting the alcohol at the end. We used distilled grain alchohol, also made in the still hehehe

anyhow, I remember a particularly large batch that I ran out of time processing and stuck a dozen pint and quart jars in the root room in the basement in the dark to gas off while I went away for a couple weeks.
what I came back to was thickened up oil full of crystallization. weirdest thing I ever saw. now, we are going back to 1991 here so all this weed chemistry was in it's infancy.

were those crystallizations in my oil the THCA crystals you guys are referring to here?
and if I'm understanding, you can remove them and culture them?
what does one do with those crystals? drop em in the vapor pen? or is this crystal being refined for use in medicine, like a "thc" pill
I find this shit fascinating, even if I barely understand it. LOL

Makin me think they're just extracting with ethanol and leaving to evap. Or even dissolving bho in ethanol and leaving to evap.... Can it be thaaaat simple??

 

[Tynehead Tom]

hehehe I dunno but I tossed all that oil thinking I fuggered it up somehow with a contaminant. Gotta say, I was really scratching my head. reading this thread today was like deja-vu and I'm getting that sick feeling that there was really nothing wrong with that schwack load of oil as far as safe consumption goes LOL

 

[Twist_918]

THCA Purity

THCA Purity

Posting Just for giggles... a chemist's perspective is that it is better to know than to guess...

There is a procedure that is simple to drop THCA. The two attachments show recent results.

1. A chromatogram of a fairly pure crystalline THCA (I would re-integrate and estimate a reduced purity of 98.2%-ish).
2. The remaining supernatant oil had a THCA depletion of >90%.

Hopefully, this purity infatuation and high potency "Fad" should be short lived as I agree that THC in general alone is boring. Pure THCVA, now that is something to brag about.

Soon the "entourage effect", which creates the more enjoyable effect of cannabis, will be realized (I hope) and people will enjoy blends with much lower potency and much higher-quality effects.

http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3165946/pdf/bph0163-1344.pdf

Twist

 

[Digital Man]

Posting Just for giggles... a chemist's perspective is that it is better to know than to guess...

There is a procedure that is simple to drop THCA. The two attachments show recent results.

1. A chromatogram of a fairly pure crystalline THCA (I would re-integrate and estimate a reduced purity of 98.2%-ish).
2. The remaining supernatant oil had a THCA depletion of >90%.

Hopefully, this purity infatuation and high potency "Fad" should be short lived as I agree that THC in general alone is boring. Pure THCVA, now that is something to brag about.

Soon the "entourage effect", which creates the more enjoyable effect of cannabis, will be realized (I hope) and people will enjoy blends with much lower potency and much higher-quality effects.

http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3165946/pdf/bph0163-1344.pdf

Twist

Hear Hear .......... I agree 100%. Way too many "Fads" going on in this business. I used to strive and stress over potency levels until I began to focus on the "entourage effect". Haven't cared about potency since really. In this scenario my oil is stonier then ever at much lower potency levels.

 

[thegreenman91]

Hopefully, this purity infatuation and high potency "Fad" should be short lived as I agree that THC in general alone is boring. Pure THCVA, now that is something to brag about.

Soon the "entourage effect", which creates the more enjoyable effect of cannabis, will be realized (I hope) and people will enjoy blends with much lower potency and much higher-quality effects.

Could not have said it better!

 

[x3n0ne2012]

Is there a dilution rate you are using w the hexane???

 

[ThunderFnk420]

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!

are you just taking unpurged bho and then putting it into vial and letting it set or mixing the bho with ?? is that damn simple

 

[weedaholic721]

^^Yes, basically. It can also be achieved with other solvents.

 

[ThunderFnk420]

Every time I start reading here ,I learn or affirm something .Thankyou for sharing the knowlege..U all rock!!!!!!!!!!!!!!!!!!!!!!!!!!!!

 

[DrNibs]

Like I said the fact that mine did not test at 99+% is incidental to the concerns, as A)the process to produce my tested crystals is half of the process, they are seed crystals, recrystallization will form 99+%, and Id wager many seeds will if cleaned properly as well. @pangea did I miss what the other half of it is? How do you clean them properly?
Thank you for all your info

 

[Pangea]

Ive found that cleaning them is a bit tricky, I usually just manually rub them clean with a ipa or etoh /h20 mixture of various strengths, or soak and agitate to dissolve only the "mother liquor" while being careful not to melt the crystals!

I follow up with a vacuum purge to get any residuals as well.

Still havent got the camera or a new analysis, soon hopefully!

 

[DrNibs]

Have an off topic question for you, if you don't mind me asking Pangea I have a bunch of nucleated sugared and straight crumble that occurred from me not running right, my goal was shatter, I used to be able to take that messed up stuff load it into a 2lb bhogart CLS (solvent was unchilled N-tane, 600 not 600a) material tube with a couple coffee filters at the end and just re-blast it and would not have too much loss and have pretty much a great pour and vac to shatter, now im using a PX1 with pretty much Propane chilled to -40C and trying to re run it, the results are terrible, I only get about 10% in the collection and its runny, looks great, but no stability and 90% of the material in the tube is now white almost like what I would find in a dewax layer. would switching my gass back to butane and not chilling it so much be a solution here? sry I know this is way off topic, but just thought I would try and pick ur brain a bit, been kinda tuff using almost all propane, but the material required it cuz of the color that was coming out from a mix or just N-tane. wish I still had that bhogart laying around to use for re running mess ups.
hey for the BHO ur letting evap for the crystals, is that iso or reg butane? Great info here, love what you have shared

 

[Eldrazi]

dear DrNibs
heavy to pure propane as a solvent is effective at grabbing the goods out of old material that otherwise would come out dark and sappy if a more polar solvent such as butane was used. so basically what your doing is getting the best out of what you have with a sacrifice to yield because its grabbing far less lipids, chlorophyl,ect...if you have good material than heavier to pure butane will get you more yield and hopefully a viable color and stability.

 

[Old Gold]

Have an off topic question for you, if you don't mind me asking Pangea I have a bunch of nucleated sugared and straight crumble that occurred from me not running right, my goal was shatter, I used to be able to take that messed up stuff load it into a 2lb bhogart CLS (solvent was unchilled N-tane, 600 not 600a) material tube with a couple coffee filters at the end and just re-blast it and would not have too much loss and have pretty much a great pour and vac to shatter, now im using a PX1 with pretty much Propane chilled to -40C and trying to re run it, the results are terrible, I only get about 10% in the collection and its runny, looks great, but no stability and 90% of the material in the tube is now white almost like what I would find in a dewax layer. would switching my gass back to butane and not chilling it so much be a solution here? sry I know this is way off topic, but just thought I would try and pick ur brain a bit, been kinda tuff using almost all propane, but the material required it cuz of the color that was coming out from a mix or just N-tane. wish I still had that bhogart laying around to use for re running mess ups.
hey for the BHO ur letting evap for the crystals, is that iso or reg butane? Great info here, love what you have shared

All three hydrocarbons you mentioned should extract the material you want. You could very likely be leaving plant waxes behind. Maybe try [re]extracting the oil with WARM solvent. Isolate your material column and then chill it to -40, and let waxes precipitate out and drop in solution. See if this changes yields or what is left behind.

 

[DrNibs]

Thank You

Thank You

Ya I did have some older material which is why I switched, and OLD thank you that re-affirms why that bhogart did a good job at re-runs, ill do what you recommend , Thanks guys

 

[SkyHighLer]

of course theyre recrystallizing and of course they wont say anything. its Guild.

I've been avoiding this discussion since the product wasn't being personally put before me, things change... pics from the 3rd Annual Chalice California 'hash oil' festival yesterday.

I bought half a gram of the 'pure' THC-A crystals, and was given a half of the 95%. No taste or flavor with the first, and just a slight awareness of something flowery with the yellowish, sandy less pure stuff. No stand out effect after a couple of hits of each.

Sorry some of the pics are sideways, I didn't upload them that way... and yes they 'add terpenes' if you so desire to your pure THC-A crystals with that that there glass pipet thingee. They were even blowing out terpene holy water out their tent's mister system... gettin' them terpenes from somewhere/how..... ;-)

....fixed sideways pics today, 7/27/'16 - don't miss today's post with more!

 

[jazz messenger]

maybe one could recrystallize both cbd and thc and make a mixture of the two and make an inhalable product with a spray dryer

"Spray freeze drying to produce a stable Delta(9)-tetrahydrocannabinol containing inulin-based solid dispersion powder suitable for inhalation."
http://www.ncbi.nlm.nih.gov/pubmed/16084699

here is some information i found through google that seems to be about purifying cbd from "red oil".

https://www.google.com/patents/US2304669

["(Formula I) CHa With the exception of the position of the double bond in the left hand cycle in the above formula the structure of cannabidiol is well established. Investigations show this left hand cycle to be a tetrahydro benzene ring.

Cannabidiol is a crystalline compound, M. P. 66-67 (con), and forms long white rods when crystallized from petroleum ether (B. P. 30-60). It has an [a] D-125, and. is physiologically inactive so far as marihuana activity is concerned.

It has now been found that cannabidiol isomerizes upon treatment, for example, with a variety of reagents such as hydrochloric acid and ethanol, hydrogen chloride in ether, pyridine hydrochloride, sulfamic acid, zinc chloride, ethanolic phosphoric acid, etc. and is converted to tetrahydro cannabinol which has marihuana activity. The isomerizing processes and resulting physiologically active tetrahydro cannabinols form the subject matter of my co-pending application Serial No. 440,971.

The principal object of the present invention is to provide an improved process for isolating cannabidiol from red oil obtained from hemp.

Other objects of the present invention will be apparent as the description proceeds.

The isolation of cannabidiol from red oil obtained from hemp is described in detail in J. A. C. S. 62, 196 (1940). This process which includes the treatment of purified red oil with 3,5-dinitrobenzoyl chloride and the formation of cannabidiol bis-3,5-dinitrobenzoate has been found of particular value for the isolation of the desired product. Ammonolysis of the benzoate, i. e. diester, yields cannabidiol in pure form.

The process as set forth in the J. A. C. S. 62,

, two cc. portions of petroleum ether.

196, 198, 199 (1940) serves to illustrate the present invention.

cannabidiol bis-3,5-dinitrobenzoate.-A solution of about 50 grams of purified red oil, B. P. 175-195 C. (2 mm.), in 200 cc. of dry pyridine was poured rapidly with shaking and cooling on grams of 3,5-dinitrobenzoyl chloride. The mixture was heated on a steam cone for two hours with occasional shaking and was then poured into ice and hydrochloric acid (200 cc. of concentrated hydrchloric acid, 500 cc. of ice). It was filtered or decanted and the insoluble material was washed several times with dilute hydrochloric acid. The residue was dissolved in 600 cc. of benzene and filtered. The insoluble material consisted mainly of 3,5-dinitrobenzoic acid.

The benzene solution was washed with dilute hydrochloric acid, then with aqueous sodium bicarbonate and finally with water. The benzene was evaporated and the residue was dissolved in 500 cc. of dry ether. This solution was treated with norit (20 grams), filtered, and then concentrated to 300 cc. On cooling in an ice-salt mixture with constant stirring, crystallization set in. After one hour, the product was filtered and washed with cold dry ether. Upon purification of the desired product by recrystallization from 800 cc. of a mixture of methanol and methyl acetate (2:1), it was obtained as white rods M. P. l06-l07 C. (corr.)

Cannabidiol.A solution of 50 grams of cannabidiol bis-3,5-dinitrobenzoate in cc. of toluene was placed in the glass liner of a high pressure bomb. The mixture was cooled by dryice and about 100 cc. of liquid ammonia passed into it. The liner was then placed in the bomb and the cover quickly fastened. The bomb was allowed to stand for five hours at room temperature. At the end of that time the excess ammonia was allowed to escape and the product, which had set to a solid mass, was digested with 400 cc, of petroleum ether (B. P. 60-110 C.) The solid 3,5- dinitrobenzamide was filtered and washed with Filtrate and washings were combined and extracted six times with cc. portions of boiling water to remove the last traces of 3,5-dinitrobenzamide. The petroleum ether was then evaporated and the residue distilled, B. P. 187-190 C. (2 mm.) (bath temperature 220 C.). The resulting product, i. e. cannabidiol, was obtained as a pale yellow resin.

It will be obvious to those skilled in the art that the present invention is not limited to the details of the process outlined above. The scope of the 3. A process for isolating substantially pure cannabidiol from red oil obtained from hemp which comprises (a) treating hemp red oil with 3,5-dinitrobenzoy1 chloride, (12) separating the cannabidiol bis-3,5-dinitr0benzoate formed in (a) from the red oil mixture, and (c) subjecting the benzoate ester of (b) to ammonolysis."]

I belive that peer-reviewed research by scientists of impeccable and relevant credentials is necessary to create a manufacturing process that is optimized for human health. I also think that distributing recrystallized thc-a as a medicine is an indolent and legally dangerous attempt at legitimizing the distribution. I.e. for US buisness, consideration of FD&C Act, sec. 201(g)(1), and GMP. An adult should have the right to purchase any form of non-living matter, however selling an item under false pretenses is fraud.

 

[turtl3]

@pangea i have some questions is there anyway i could send you a private message to ensure I'm doing this correctly?