Chemistry Discussion

[thecosmicjoke]

Hello,

Over the coming months I plan to do a research paper on optimizing percent yield over an A/B and STB extraction of mimosa hostilis root bark. This is going to be an admittedly amateur paper as my knowledge and equipment are both relatively entry level. However, I find great satisfaction in no longer simply following procedures, but having enough chemistry knowledge to make my own decisions. That being said, it seems that the recommended amount of NaOH to be used for most procedures is just insanely off the mark. A pH of 14 can be attained with 30 grams of NaOH and 750mL distilled water. I have seen recommendations go all the way up to 100 grams, which is expensive, dangerous, and completely unnecessary.

I'm also not even entirely sure how necessary a pH of 14 (often recommended) even is for any STB or A/B extraction. I have heard (and would love if somebody can expand on this) that the amount of freebase to salt ratio of DMT at a pH of 8.68 is 50%. At pH 10.68%, 99% is freebase, which is important of course to be soluble in non-polar solutions. So if this is true, there is not really much benefit to achieving a pH higher than 11-12.

I'm curious if anybody has any insight onto why such a high pH is recommended for STB extracts. It's possible that the root bark is acidic and affects the alkalinity, but surely it is not that much. I only have pH papers so testing this isn't possible due to the color of the solution after the bark is added. The really funny thing is that if a pH of 12 is sufficient, this can be achieved with 0.3 grams of NaOH (for 750mL water).

I'd also appreciate any misunderstandings I have. My math is (0.3g NaOH) x (1mol/40gNaOH) = (0.0075mol NaOH) / (0.750L Solute) = 0.01M, -log(0.01)=2pOH, therefore pH=12.

I did the same for a modified A/B extraction I am running where I first soaked the bark in 750mL of a 0.83M Acetic Acid solution (5% distilled white vinegar). With this I am given DMT-Acetate which is water-soluble, so to the acidic solution I add enough NaOH to not only neutralize but to bring the pH up to 12 again (IF 12 is even sufficient, would love if somebody could comment on that). This should require 25.22g NaOH (1:1 mol ratio for neutralization, 750mL of 0.83M AA is 0.623 mole's Acetic Acid, therefore 0.623 moles of NaOH + 0.3 grams of NaOH (from earlier) is 25.22 grams NaOH).

One last thing, I found a research paper on different organic solvents for DMT extraction, with n-hexane actually found to be the worst performing (Internet method for the extraction of N,N-dimethyltryptamine from Mimosa hostilis roots: Does it really extract dimethyltryptamine?). Would love if somebody also had insight on this. For the longest time I would do simple Naptha pulls until I realized (after far longer than I should have) that my final product was certainly impure and contaminated with plant fats and alkaloids, and quite likely hydrocarbons and alkenes in the Naptha. This prompted me to order n-heptane to do re-x's which generally lead to roughly a 10% "decrease" in product. It's huge to be clearing out 10% of a product to impurities that I have been consistently consuming. Makes me concerned.

Anyways, this was possibly a rant. Would really enjoy some discussion and insights on what I have mentioned, mainly the pH concerns.

Thank you.

 

[drpotato]

root bark is not inert. Its also loaded with all sorts of organic compounds that react with NaOH. you could argue the reason for using a 3x molar excess of NaOH is theres 3x as much organics and salts with ions that will be torn away prefferentially over the DMT.
Not only that but, in order to react with as much DMT as possible, once all it said and done, your pH must still be 12. so your math needs to include the unknown factors here, being just how many mols of ions the bark can provide. Alternatively just monitor pH while adding your given base, this isnt something you can math. react a small sample in a test tube, scale up 80% and then slowly add base until the pH goes where you want.

in STB, no acid is used, and without the benefit of being able to depolymerize the DMT that may exist as a solid-supported goo inside the bark fibers (imagine a sponge that has been caked solid with grease), excess hydroxide is used to degrade the cellulose to some degree. it needs quite a bit of ionic force to reach everything.

the sodium hydroxide also serves the dual-purpose of, i forget the term, ionizing the solution? it causes the miscibility between the aqueous and organic phase to go really low, preventing emulsions, and improving seperation, which allows one to shake the strained solution with ones solvent of choice.

Hexane is chosen specifically BECAUSE it dissolves DMT poorly. you wouldnt be able to precipitate a gram of something out of several hundred ml reliably otherwise. most other solvents behave like they co-solve with the DMT, for example toluene, you can heat up to 200C and it still wont let go of the DMT freebase any quicker, nearly 100C above its boiling point, but if left alone it passively evaporates away at RT.
There is also the fact that hot hexane dissolves a lot of DMT while cold hexane dissolves very little. you can carefully cool the hexane to just above the point dmt precipitates and discard the first lot of goo, then transfer and actually freeze down to -20C. Alternatively you can just evap it away too, hexane is one of the few solvents that DMT will actually precipitate from, since it doesnt disrupt crystal formation, other solvents give you an oil that may not ever crystalize if its not unreasonably pure or devoid of NMT.

Im not totally certain but since hexane is so easily saturated by the DMT, it disuades the dissolution of anything even less soluble than the DMT from entering, which is why subsequent pulls get dirtier, theres more room when theres less DMT. and if you defat, then you cut out a large portion of oils that are hexane soluble.

Ideally you want to use heptane instead, the other primary component of naptha. its even worse (better) than hexane, except its not a potent neurotoxin (look it up, hexane causes brain damage). higher BP means it can evap slower leading to cleaner crystal formation and lower RT solubility means its easy to tune the saturation to exactly where you want, for precipitation.
Also its safer to mix heptane with hot water just in general. it wont flash boil from being shaken for example. hexane is also hard to store as it turns out, it leaks out of containers poisoning the room, heptane you can store closer to people, which was an issue since my options were outdoors in a 50C shed, or cool but, too close/inside the house.



your point about using excesive hydroxide has been noted before. sodium carbonate is, not entirely cheaper at scale, but certainly safer. clean wood ash can be made to work too. the drawback of using a carbonate is just that you get a fizzy mess if you decided you want to acidify the bark slurry.
STB teks exist for prioritizing quality over yield, they already exclude quite a bit of spice, but are quick and easy, especially if using carbonate in a dry tek. its a quick and dirty methodology that yields a higher quality product provided ones source is within certain margins of purity. Its a blunt instrument but thats what you want if you are planning on processing a pound or 2 of bark. its quite difficult to avoid making a huge mess or poisoning yourself with solvent fumes doing a multi stage extraction via A/B to get a pure product with no loss of yield. you might need to rinse various containers out so many times that it becomes worth doing another extraction on that rinse residue alone.

 

[thecosmicjoke]

root bark is not inert. Its also loaded with all sorts of organic compounds that react with NaOH. you could argue the reason for using a 3x molar excess of NaOH is theres 3x as much organics and salts with ions that will be torn away prefferentially over the DMT.
Not only that but, in order to react with as much DMT as possible, once all it said and done, your pH must still be 12. so your math needs to include the unknown factors here, being just how many mols of ions the bark can provide. Alternatively just monitor pH while adding your given base, this isnt something you can math. react a small sample in a test tube, scale up 80% and then slowly add base until the pH goes where you want.

in STB, no acid is used, and without the benefit of being able to depolymerize the DMT that may exist as a solid-supported goo inside the bark fibers (imagine a sponge that has been caked solid with grease), excess hydroxide is used to degrade the cellulose to some degree. it needs quite a bit of ionic force to reach everything.

the sodium hydroxide also serves the dual-purpose of, i forget the term, ionizing the solution? it causes the miscibility between the aqueous and organic phase to go really low, preventing emulsions, and improving seperation, which allows one to shake the strained solution with ones solvent of choice.

Hexane is chosen specifically BECAUSE it dissolves DMT poorly. you wouldnt be able to precipitate a gram of something out of several hundred ml reliably otherwise. most other solvents behave like they co-solve with the DMT, for example toluene, you can heat up to 200C and it still wont let go of the DMT freebase any quicker, nearly 100C above its boiling point, but if left alone it passively evaporates away at RT.
There is also the fact that hot hexane dissolves a lot of DMT while cold hexane dissolves very little. you can carefully cool the hexane to just above the point dmt precipitates and discard the first lot of goo, then transfer and actually freeze down to -20C. Alternatively you can just evap it away too, hexane is one of the few solvents that DMT will actually precipitate from, since it doesnt disrupt crystal formation, other solvents give you an oil that may not ever crystalize if its not unreasonably pure or devoid of NMT.

Im not totally certain but since hexane is so easily saturated by the DMT, it disuades the dissolution of anything even less soluble than the DMT from entering, which is why subsequent pulls get dirtier, theres more room when theres less DMT. and if you defat, then you cut out a large portion of oils that are hexane soluble.

Ideally you want to use heptane instead, the other primary component of naptha. its even worse (better) than hexane, except its not a potent neurotoxin (look it up, hexane causes brain damage). higher BP means it can evap slower leading to cleaner crystal formation and lower RT solubility means its easy to tune the saturation to exactly where you want, for precipitation.
Also its safer to mix heptane with hot water just in general. it wont flash boil from being shaken for example. hexane is also hard to store as it turns out, it leaks out of containers poisoning the room, heptane you can store closer to people, which was an issue since my options were outdoors in a 50C shed, or cool but, too close/inside the house.



your point about using excesive hydroxide has been noted before. sodium carbonate is, not entirely cheaper at scale, but certainly safer. clean wood ash can be made to work too. the drawback of using a carbonate is just that you get a fizzy mess if you decided you want to acidify the bark slurry.
STB teks exist for prioritizing quality over yield, they already exclude quite a bit of spice, but are quick and easy, especially if using carbonate in a dry tek. its a quick and dirty methodology that yields a higher quality product provided ones source is within certain margins of purity. Its a blunt instrument but thats what you want if you are planning on processing a pound or 2 of bark. its quite difficult to avoid making a huge mess or poisoning yourself with solvent fumes doing a multi stage extraction via A/B to get a pure product with no loss of yield. you might need to rinse various containers out so many times that it becomes worth doing another extraction on that rinse residue alone.

Thanks for the response.

I edited my post, I actually ordered n-heptane for the re-x, not hexane, which is good news.

Also, I did run an A/B in the mean time using as little NaOH as possible (30 grams) to reach a pH of 12-13, and it was a mess. Ended up having to add more NaOH (20 grams) and NaCl (50 grams) to break the emulsion. The bark slurry became weirdly mushy and solid, which I have never encountered before. It also turned grey. This further proves your point.

I've become much more concerned with the purity of my DMT lately. I've been vaporizing it for about a year only doing a water wash, no re-x. This never seemed to be an issue until my most recent batch, which was incredibly harsh to smoke and just screamed that something was wrong with it. Even after a second naptha re-x and water wash, I lost 10% of the product but it still burns and I'm unsure why. This is what prompted me to order the 99% Heptane, because I think it has to be some kind of alkene from the naptha that won't evaporate. The naptha was bought from a hardware store, I don't expect it to be very pure. I also wonder if Naptha degrades with time, I really haven't been treating it like a chemical solvent. It's been sitting in an outside closet through fluctuating temperatures, but I'd imagine should still be fine for initial extraction purposes.

Very much looking forward to seeing the effects of the heptane.

 

[doubledog]

Strong hydroxide is used for other reasons, not only for freebasing of alkaloids, but also to decompose plant matter.