[Edit (11 Jan 2013): While I will leave the original post in tact for posterity, I eventually came to the conclusion that calcium bufotenate is a myth. The methods described most likely yield bufotenine as a free base. See post #8 below.]Back when I first started looking into yopo/cebil (Anadenanthera peragrina and Anadenanthera colubrina) snuffs, I remember running into some discussion of "calcium bufotenate", and how better effects can be achieved through the use of slaked lime. Well, at the time I didn't know as much about chemistry, and I dismissed the compound as an internet fiction, since I was unable to find any references to the compound outside of an occasional erowid experience report or message board post. Consequently SWIM substituted baking soda for his snuff, and achieved interesting results... some psychoactivity, but mostly physical discomfort.
Lately I've been seeing people mention this compound, and knowing more about chemistry now than I did before, I decided to give the issue some fresh consideration. And I'm beginning to think that calcium bufotenate might exist. Since SWIM is too busy at the moment to do extractions and analytical work, this is kind of an APB to let extractors know they might be able to have the distinction of being the first to definitively demonstrate the existence of this compound.
First I'll lay out my reasoning in terms of why it's plausible that this compound exists. Then I'll talk about the most convincing piece of corroborating evidence, and how one might go about trying to make this compound, if SWIY is interested. (Sorry if I ramble a bit, I'm done with homework for the night and am taking the opportunity to catch a buzz).
My reasoning:
- The 5-OH group on bufotenine is weakly acidic. Based on the trends for other aromatic alcohols (phenol, naphthol), it's likely that the pKa of this group is somewhere between 9 and 10. It seems utterly inconcievable that it'd be higher than 10.5.
- Calcium hydroxide (slaked lime) is a pretty alkaline material, capable of getting water up to pH 12. Furthermore, as a metal hydroxide, it's capable of participating in
neutralization chemistry (acid + metal hydroxide = metal salt + water).
Obviously the question then is simply whether bufotenine and calcium hydroxide have a sufficient affinity for one another to perform such chemistry. I turned up a reference to calcium phenolate in
Handbook of Inorganic Compounds, which indicates that this sort of salt is plausible. And the
Standard Methods of Chemical Analysis indicates that the phenolate forms by reaction with calcium carbonate, another neutralization reaction ("acid + metal carbonate = metal salt + water + carbon dioxide" ). Since calcium hydroxide is more alkaline than calcium carbonate, this pretty well substantiates the idea that bufotenine might be able to form a calcium salt.
Also, if you look into the ethnographic literature on South American natives, different tribes use/used a variety of bufotenin-containing preparations. In a very large number of these cases, the tribe places a strong emphasis on a preparation ritual where the bufotenin-containing material is mixed with slaked lime. It seems strange for such similar traditions to rise around such diverse materials, among totally unrelated tribes, unless the lime played some role in enhancing the effects. Of course,
Jonathan Ott's bioassays indicate that bufotenine freebase is entirely capable of accounting for the effects of the shamanic snuffs and clysters.
There are various and sundry claims on the internet about different procedures, but many of them are lacking in substance or detail. I was able to find some very good information by a poster on the ayahuasca forums, druiddream, who I've found to be a very reliable poster in the past. Consider the following:
Quote:If you were to do this one day, you could soak the snuff in an appropriate amount of acidified water, filter out the seed material, then basify it with calcium hydroxide until you get a fluffy precipitate at the bottom of your vessel. Then you can either pour this preparation (liquid + precipitate, but with no seed material in it) in a nasal sprayer after pouring out the saline solution that comes in it, or you can simply use a small 1/8tsp measuring spoon and insufflate the liquid, paying special attention to getting some of the fluffy precipitate in your spoon each time.
And some more detail on a method used to alleviate sciatic nerve pain:
Quote:What she found so exceptionally effective was a 2g cold-water phosphoric-acid infusion of the seeds just as outlined in the recent LSA thread, leaving a practically CLEAR liquid with minimal nasty seed oils. She then boiled this down from 8oz. to 2oz. and basified with edible lyme to ph10. Then, before working with this liquid, she drank *without any revulsion* 2g of a similarly prepared cold-water infusion of Syrian Rue, but with no basification and sweetened to taste. (The cold infusion came out very light yellow without the characteristic foul, nauseating smell or taste of hot water Syrian rue extractions, she said). She then took a 1/8tsp. measuring spoon and began insufflating the equivalent of 1 tsp. of the LIQUID form of the basified yopo infusion over a 5 minute period. The small amount of liquid was easily snuffed up and there was no spillage or leakage. If liquid came down the nasal passage into the mouth, she just held the liquid sublingually and spat it out as need be (she said that surprisingly it didn't taste nasty like the hot water infusion of yopo does).
First off: Yes, it was ingested potentiated by an MAOI, so the effects she recieved may be different than those that are typically encountered. This is irrelavent; I'm not concerned with the specific effects right now (and the effects described did not include nausea, which would be expected from a typical rue+yopo mix).
Here's what interests me: A precipitate froms at pH 9-10. This would not be remarkable in itself, since this was made with a crude extract, that precipitate could be the result of any phytochemical soluble in acidic water. What interests me is the emphasis on making sure to get some of the precipitate in every sniff, implying that the precipitate is psychoactive. Bear in mind this is something that swidruiddream has done repeatedly, as she apparently finds it to be an effective remedy for sciatic nerve pain, not just a one-time report.
So when an acidic extract of yopo is treated with calcium hydroxide, a precipitate forms, and this precipitate appears to be centrally active. This is very interesting, because it's not possible that this precipitate is bufotenin freebase. Bufotenin freebase is sufficiently polar to be somewhat soluble in water; if it weren't, Jonathan Ott would have seem a precipitate in the ammonia step of his extraction, and been saved the trouble of recrystallization.
A couple of other things. I asked druiddream if this experimentor had tried collecting the precipitate, and using that material dry, without the liquid. Apparently she had not, as the liquid adminitration was found to be plenty effective. I should mention that it's entirely possible calcium bufotenin is unstable in the presence of air at atmospheric conditions; calcium phenoxide was found to be unstable under these conditions. So if SWIy decides to try this method, they ought to confirm psychoactivity of the precipitate before collecting it out of the water and drying it.
But of course shamanic snuffs were traditionally left to dry for a substantial period of time. There are three possibilities to my mind in this issue:
-The first is that they weren't preparing calcium bufotenate, just bufotenin freebase. Ott's published bioassays confirm that bufotenin freebase is capable of producing substantial visionary effects. (This is the currently accepted hypothesis)
-The second is that they were preparing calcium bufotenate, but it's unstable to environmental conditions and decomposed into bufotenin freebase and calcium (oxide? hydroxide? carbonate?). Again, the bufotenin freebase can entirely account for the shamanic effects of the snuff.
-The third possibility is that they were preparing calcium bufotenate, and that the material was at least semi-stable in their preparation. This is concievable; consider: when they left the snuff to dry, it's been reported that the excess calcium hydroxide (which is pretty alkaline for the nasal cavity) reacts with atmospheric carbon dioxide to make calcium carbonate (chalk). This material is less uncomfortable on the nasal passages than lime, but it's still alkaline. It's possible that being mixed thoroughly with an alkaline material prevents atmospheric moisture from dissociating the salt so easily.
If SWIM is interested in extracting this compound, an accurate melting point apparatus would be the simplest piece of equipment that I can see as capable of characterizing it definitively... If SWIY has isolated calcium bufotenate, SWIY could treat it with HCl and seperate the calcium from the bufotenine salt. Then treat the salt with aqueous ammonia (a la Ott's isolation) and isolate the freebase. The melting point of this material should correspond to one fo the three known melting points of bufotenine freebase, and differ from the melting point of the suspected calcium bufotenate.
Of course, more sophisticated analytical equipment would make the job easier... but it occurs to me that SWIY could even make a fair confirmation without access to melting point apparatus, simply by bioassays. Isolate bufotenin freebase, become familiar with the effects. Generate (suspected) calcium bufotenate, and sample the effects. Then generate the freebase from the (suspected) calcium bufotenate as above, and bioassay to confirm its identity. Obviously this method puts the experimentor at a bit more risk.
I think that's about it, in terms of what I've thought through so far anyway... so I guess I'll just tack Jonathan Ott's preparation and some links.
Quote:ISOLATION AND PURIFICATION OF BUFOTENINE FREE-BASE
Coarse-ground powder of 125g of seeds of A. colubrina var. Cebil was stirred twice for eight hours in 500 ml of 96% ethanol 1% tartaric acid, the combined filtrates concentrated to 150 ml and diluted with 200 ml water in a separatory-funnel, causing precipitation of considerable fat. The pH was adjusted to 3-4 with concentrated hydrochloric acid, and the solution defatted by shaking six times with chloroform, which was set aside. The defatted extract was basified to pH 8-9 with ammonium hydroxide, then again extracted eight times with 200 ml chloroform; the combined chloroform extracts were concentrated to a foamy, yellowish oil that dissolved completely in 50 ml hot ethyl acetate, then concentrated to 15 ml and refrigerated overnight. In the morning there were a brace of minuscule rosettes of dark-brownish crystals growing at the base of the flask, which was alternated between periods under refrigeration and standing unstoppered at room temperature during 48 hours, leading to the formation of large masses (some greater than 1cm) of dark-brownish, prismatic crystals. The mother-liquor was decanted and the crystalline mass rinsed with cold ethyl acetate dried over magnesium sulfate, then dried under reduced pressure to yield 4.1 g of large, free-flowing, sparkling brownish crystals. These were twice recrystallized from dry ethyl acetate, yielding 3.87 g of off-white bufotenine free-base crystals (3. 10%), m.p. 125-126° C. Despite loss of chromophores on recrystallizations, the melting point remained 124-126°. Six reports of isolated bufotenine free-base, from Amanita citrina (Schaef.) Gray (Agaricaceae) (Wieland & Motzel 1953) and Anadenanthera species (Rendón 1984; lacobucci & Rdveda 1964; Pachter, Zacharias & Ribeiro 1959; Alvares Pereira 1957; Stromberg 1954-yields reported were from 0.94-7.4% for A. peregrina to 0.5-2.1 % for A. colubrina), disclosed two crystalline isoforms from ethyl acetate, one melting from [123-]124-126[-129]° C, the other 146-147[-150]° C. Two reports of synthetic material disclosed a third isoform, with melting points of 138-140° C (Stoll et al. 1955); and again 146-147° C (Speeter & Anthony 1954). In all cases involving the lower-melting-point isoforms, repeated purification did not alter the melting point, although Iacobucci and Rdveda (1964), upon seeding a recrystallization-solution of their lower melting point isoform (123-124° C) with crystals having m.p. 146-147° C, got only crystals of the latter type, which operation was not reversible. By manipulating conditions of recrystallization from ethyl acetate, I was able to generate crystals melting at 145-147° C, and confirmed Iacobucci and RtIveda's observation. DMT free-base from hexane likewise exists as at least three isoforms, melting points from 44-74° C having been reported, and Fish, Johnson and Horning (1956) replicated the irreversible transformation of a lower-melting-point isoform (47-49° C) into a higher-melting-point isoform (71-73° C). Identity and purity of isolated bufotenine were verified by mass-spectral analysis and thin-layer chromatographic comparison with an authentic sample in several solvent systems.
Links - By no means exhaustive, just the first handful I saw
Anadenthera colubrina / peregrina ,bufotenine , 5-OH-DMTYopo and CebilYopo/Vilca as Medicinal HerbsYopo experiencesIsopropyl DMT extractionSharing Information about Yopo(A.Peregrina)Vaporized Extract of Anadenanthera colubrinaYopo - Anadenanthera colubrina BasicsEntropymancer attached the following image(s):
Calcium bufotenate.jpg
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