THC Acetate

[nabraxas]

SORRY--posted this after reading auxins post---didn't wanna subvert that topic, so made a new post---was gonna put it in chill space, but missed it.

apparently this is what you get if you acetylise THC w/acetyl anhydride---& here's a story 'bout it

"September 1942: The Office of Strategic Services (OSS), wartime precursor to CIA, begins searching for a drug that will force subjects of interrogation, such as captured Nazi U-boat crews, to reveal secrets. As project director Dr. Stanley Lovell will recall, the idea of a "truth drug" is "considered fantastic by the realists, unethical by the moralists, and downright ludicrous by the physicians." But according to OSS records, Lovell goes ahead and tests "mescaline, various barbiturates, scopolamine, benzedrine, cannabis indica (marijuana), etc." The best results are obtained with the marijuana: "A few minutes after administration, the subject gradually becomes relaxed, and experiences a sensation of well-being... thoughts flow with considerable freedom... conversation becomes animated and accelerated. Inhibitions fall away.... [the drug] makes manifest any strong characteristics of the individual.... Whatever the individual is trying to withhold will be forced to the top of his subconscious mind." To "administer" the pot without a subject's knowing it, OSS scientists dissolve marijuana leaves in acetone, then heat the result into a clear, odorless, viscous liquid -- tetrahydrocannabional acetate -- which can be "injected into any type of food, such as mashed potatoes, butter, salad dressing, or in such things as candy."

May 25, 1943: THC acetate is tested on an unknowing subject, Lower East Side mafioso August "Little Augie" Del Gaizo, who has been helping OSS smuggle agents into Nazi-held Sicily. Little Augie is considered an ideal subject because he has secrets he is "most anxious to conceal, the revelation of which might result in his imprisonment"; in fact, he prides himself on having never informed, and has even "been instrumental in killing some persons who have been informants." But after smoking two proffered cigarettes, laced with a total of .14 grams THC, Little Augie becomes "obviously 'high' and extremely garrulous" as he sits in the apartment of OSS officer George White, a former Treasury agent who had arrested him several times in the past. When White turns the subject to law enforcement, Little Augie "with no further encouragement" divulges the identities of city officials on the take; details of the criminal empire run by Meyer Lansky and Bugsy Siegel; "and other information that subject would not give under ordinary circumstances. There is no question but that administration of the drug was responsible for loosening the subject's tongue." Henceforth, OSS refers to the THC acetate simply as "TD," a cryptonym for "Truth Drug."

1944: OSS uses "TD" in secret operations. Lovell reports that "Certain disclosures of the greatest value are in the possession of our military intelligence as a result of this treatment, which it is felt would otherwise not be known. Properly employed... it may be a national asset of incalculable importance." But OSS officials, fearing political backlash if use of the drug is revealed, shut the program down"

[ 18. February 2004, 05:11: Message edited by: nabraxas ]

[theobromos]

Bugsy might have been a cousin of mine but that side of the family ain't blabbin'.

[ 18. February 2004, 05:31: Message edited by: theobromos ]

[John_Barleycorn]

After a bit of a dig around the Hive a while ago, it seems quite controversial whether the acetate is in fact more potent, or possibly that it stores better. Another aspect which has everyone arguing is whether acetic anhydride is in fact necessary to form the ester, or whether glacial acetic will do. The new kid on the block actually seems to involve refluxing THC in toluene and conc. sulphuric acid. It is unclear whether that forms the sulphate ester or soemthing else.

[theobromos]

Refluxing THC with traces of sulphuric acid in toluene will drive the THC to its least vulnerable isomer (if not to something else cannabinoid) and will probably reduce its psychoactivity appreciably. Certainly some things will form an ester with the acid, like yohimbine does, did the bee describe the resulting product at all?

THC will acetylate easily I believe but room temperature and mild detergents are preferable for delicate textiles.

Read this:

http://www.shaman-australis.com/cgi-bin/ub...t=001257#000020

[nabraxas]

theo--sorry, but i'm dim, & you posted the same link in the other topic--what exactly is it you are directing our attention to?

[theobromos]

THC acetate effects, strength and other relevant facts. The "controversy" about strength would be from people who don't understand how to make quality product, grump, grumble. In my first post in the thread.

[nabraxas]

oh, sorry i thought you were obliquely hinting at a way ov making it w/out the acetyl annhydride.

i said i was dim...

[John_Barleycorn]

theobromos:

THC will acetylate easily I believe but room temperature and mild detergents are preferable for delicate textiles.

Read this:

OK, now you're being oblique. Most people seem to think acetylation requires a fairly aggressive reflux, and that previous post of yours where light (UV presumably?) makes a silk purse out of a sow's ear contradicts the conventional wisdom of light degrading THC. So please fill us all in!

My (unconfirmed) scepticism about the acetate derives from the fact that all the oil treatments I have seen seem to do numerous things at once, and no-one seems too interested in controlling for all the individual effects. For example, you boil up some extract in acidified EtOH. It probably has the effect of (a) decarboxylation (ie, THCA -> THC) ( "isomerisation" (ie, CBD -> THC) and possibly © true isomerisation (ie, optical rotation) at the same time as (d) oxidation (ie, THC -> CBN) and possibly (e) polymerisation. So if someone goes to the additional step of (f) acetylation (or some other potency-enhancing step), then most of the time it is hard to tell where the real effect came from.

[theobromos]

Conventional and wisdom seldom go together.

UV light is quite specific for turning CBD to THC, presumably a specific wavelength within the sunbed spectrum. White light is a different creature entirely.

a) would be unlikely in alcohol. Better in solid state.

is a cyclisation with dehydration, of course.

c) Surely a positional rather than optical isomerisation? The double bond position changes.

d) better called a dehydrogenation?

Why in alcohol? Butane is a better solvent except for its ecological effects. Ethyl acetate would be good for acetylating.

[John_Barleycorn]

theobromos:

UV light is quite specific for turning CBD to THC, presumably a specific wavelength within the sunbed spectrum. White light is a different creature entirely.

That absolutely rocks. No more refluxing and worrying about attendant oxidation. Any idea whether the co-solvent or the CBD concentration matters? I guess I am starting to think here about the possibility of irradiating home-brew, as opposed to an oil - only for research purposes or where legal, of course . Another way-cool idea is simply to pick up a UV lamp and lose all that sneaking around the solarium stuff!

 

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a) would be unlikely in alcohol. Better in solid state.

Steeping herb in home-brew seems to work, but it may not be a particularly fast process. Either that, or the original herb has spontaneously decarboxylated, which I understand is also possible.

 

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c) Surely a positional rather than optical isomerisation? The double bond position changes.

D'oh! I simply assumed there was a chiral centre somewhere without checking.

 

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d) better called a dehydrogenation?

True. No-one ever seems to talk about the alcohol group being oxidised, but it could be an intermediate step. That could also suggest that ester formation improves stability, provided the ester doesn't subsequently start hydrolysing. Maybe desaturation expresses a bit better what is going on when THC converts to CBN. You haven't got any secret tips for hydrogenating CBN up your sleeve by any chance? It would be way cool to be able to avoid messing around with catalytic hydrogenation, although saturating all of the rings would be an interesting possibility. The only quick 'n' dirty possibility I can come up with off the top of my head is treatment with an anti-oxidant like metabisulphite.

 

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Why in alcohol? Butane is a better solvent except for its ecological effects.

No hard reason. It's cheap, available, non-toxic, and the fact that it is both protic and polar could have advantages in some situations (eg, if using an anti-oxidant, or maybe if using hydroxide to separate cannabinoids). Plus, it results in a more solid end product than hydrocarbons yield - oils are a pain to handle IMHO.

 

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Ethyl acetate would be good for acetylating.

And presumably would do as a cannabinoid solvent as well? Is a reflux required? Is a water-scavenging technique required as per usual with ester formation? Another left-field idea that absolutely rocks, thanks.

[John_Barleycorn]

Hey Theo

Would you have any pointers to that ethyl acetate method? I think a few people could be interested.

[theobromos]

I meant it would be a good solvent for acetylating, the conditions for it to acetylate would be a little brutal for delicate cannabinoids.

[Tryptameanie]

I've read somewhere that o-toluenesulphonic acid is much more efficient(less side reactions to weak or inactive products) than conc. sulfuric for the decarboxylation/isomerisation step.

This could be produced by reacting toluene and conc. sulfuric(or preferably, oleum), throwing away the aqueous layer and drying the organic layer with NaSO4.

This layer would then contain the sulphonic acid in toluene and could be reacted with a butane-extracted oil.

Unreacted acid could then be removed with aqueous NaOH, and the toluene evaporated to give your product.

Unfortunately, glacial acetic will not work for acetylation. I would not reccomend purchasing acetic anhydride either, as it is also used to convert morphine to heroin and the cops may take an interest in your order.

[theobromos]

Still a bunch of pointless chemicals and effort for no reason. If you haven't decarboxylated before the extraction it is too late.

Your method for making toluenesulphonic acid is not specific to the ortho variety, you will certainly get meta and para as well.

Evaporation of toluene from a resin of low-boiling point could be a little difficult at home. Toluene is not generally recommended for herb extractions.

My advice for cyclisation of CBD:

Heat your herb gently to decarboxylate. This might be better after the extraction and before a second extraction so that as little of the product has been exposed to heat as possible.

Extract a clean oil, by butane or whatever.

Use UV light from a tanning tube to irradiate the oil in a relatively thin layer.

KISS applies in chemistry too.

[ 18. March 2004, 21:27: Message edited by: theobromos ]

[Tryptameanie]

"If you haven't decarboxylated before the extraction it is too late."

Why is that?

"Your method for making toluenesulphonic acid is not specific to the ortho variety, you will certainly get meta and para as well."

True, although you'd get very little meta product, as the methyl group is o/p directing. I don't imagine this would be a problem though, I only mentioned the ortho variety because I think this was what was used in the synthesis I read.

"Still a bunch of pointless chemicals and effort for no reason."

Shit, I only skimmed the thread and failed to notice your simpler method (heat/UV). Right you are! Do you know what wavelength is ideal? Or even if near or far UV would be better?

JB, I don't share your scepticism as to the merits of acetylation. I'm sure I've seen reputable data showing o-acetyl to be considerably stronger than plain THC (6x rings a bell).

Also, does anyone know whether the dry mouth/red eyes are centrally mediated or are a result of action at peripheral receptors? If the latter is true, then they would most probably be greatly reduced with the acetyl derivative, assuming it's increased potency is a consequence of it's greater lipophilicity.

[theobromos]

Red eyes are probably due to CBD.