Have you tried something like citric acid? Idk any chemist now something about that?
I believe its also in tobacco, or present in the tabbaco plant itself? Or added, or maybe both.
Idk so yeah probably been smoking shit tons of that already by now😂 weirdest shit they put in their tobacco blends.
Yes, citric acid solution. The KOH solution after LLE with the heptane dissolved extract was cloudy white, not quite milky maybe slightly translucent still. Upon addition of low pH solution it reached a point of titration where the whole solution instantly cleared up and a light yellowish brown oil began to be noticeable on the surface of the solution. This led me to take the pH and it was at 6.5.
4.6x100mm, 3.5 µm Eclipse Plus C18 column. Isocratic mobile phase 25:75 (25mM Ammonium Formate + 0.1% Formic Acid: Acetonitrile + 0.1% Formic Acid)
Correct, winterized in EtOH and rotovaped to concentrate.
More important…pH of Mobile phase?
I am going to guess pH 4-5 ?
Actually 3.4-3.6
OK…so no matter what form of salt , COO-X+ or COOH
You extracted at pH 6.5 with LLE…
Running with that mobile phase at 3.5…it will give you a
DAD response of a COOH standard.
But what crystallizes when you evaporate the solvent is sort of a mystery…i.e., the organic extract of the floating material.
It is possible it “oils out” as the COOH and floats….but there should still be a partition of COO-X? in aqueous at that pH=6.5.
You don’t have 1/1000 in the COOH form.
It is complicated…but ok. Evolving theory ….
CBDA is rather soluble in water buffered to pH 6.5…
And more so if hydrotropes are present.
It is interesting to note that sodium salicylate in solution is
A hydrotrope for salicylic acid. This relationship with CBDA and THCA and their salts has not been investigated.
But if we find ourselves thinking about protic solvents where
potassium or sodium salts of cannabinoates are present and at a pH where the r-COOH cannabinoic acids may co-exist…
It is probably best to check for hydrotrope enhancement by dilution with water. A resulting precipitation would be indicative
Of hydrotrope action….if the solutions happen to be rather concentrated. This is just a consideration of the aqueous phase you extracted with alkane….and what you may have left behind.
Of course if you slam it with enough HCl to effect a pH of say 2
All goes away. But just titration with organic acids to pH 6.5
Leaves one in the “never never land” of organic anions.
We should probably warn folks that this is an academic exercise more than a practical application of theory… at least for now.
Most of us who have worked with acid/base chemistry on cannabinoids at a wet bench understand that even the completely ionized variants of cannabinoid acids (e.g. THCcarboxylate anion) are STILL not completely soluble in the alkaline water (e.g. at pH 12-14). That is to say, assuming one has a concentrated solution of THCa in alkane, such as heptane, performing LLE on it with high-pH water to extract the THCa- in anionic form is a tedious and messy process. I would say that THCa- anion behaves more like a hydrotrope itself than a clean solute in water. It tends to drag the alkane solvent with it, into the water, forming emulsion. Ionization of THCa with a relatively small cation (like Na+ or even K+ from their hydroxides) simply isn’t enough to fully overcome the largely hydrophobic surface area of the THCa molecule.
I have some rather vivid empirical evidence for my claim, above: This held true in the case of the genuine ammonium-THCcarboxylate salt I created some years ago, as well. The salt refused to dissolve in water… even boiling water only seemed to melt-soften it a bit (and yes, the ammonium “ligand” increased the melting point AND inhibited decarboxylation of the THCa). It was also rather difficult to get it to dissolve in its parent solvent, hexane, in which it would only dissolve partially with great excess of solvent and energy input. Later, when I added some highly concentrated HCl to this jar of water & ammonium-THCate “floaters” (they had nearly neutral buoyancy in the water), they took a rather long time to notice it! Only after continued vigorous stirring did they begin to swell, agglomerate and gain buoyancy, rising to the water surface as the ammonium (chloride) dissolved and normal THC acid formed. Ultimately, they pooled together into a singular mass which hung from the water’s surface, having significant bulk and incorporated water… somewhat obscenely, I think…
pH 14…you are certainly ionizing fully, both phenolic hydrogens on CBD and CBDA. So both are in solution when you begin to titrate with acid.
Ok…if I’m thinking correctly, at pH 6.5 you have titrated the phenolic hydroxyls.
If you see something “oiling out” at this pH it should be the neutral cannabinoids.
The cannabinoate anion should keep the CBDA in aqueous.
LLE with alkane should solubilize the neutral oil AND partition CBDA between phases.
Now in this case and pH you seem to partition an ion pair?
I have no idea how you got the chromatogram posted…i.e.CBDA>>>CBD.
Ion pair extraction is one possible explanation , I have others undiscussed at present time.
Take the aqueous remaining and add HCl to pH=2 re-extract.
Your procedure is so much like WO2021034718A1 patent…
Thanks for that SAFETY NOTICE, @Ralf !
There is no theory for the cannabinoates/cannabinoics in either protic or non-polar. Butane works, and medusa stones form…
Is about a deep as it gets. Water makes goo.!
The rest is hands on experience…but it is rather amazing what someone with a bit of know how can do with three 50 gallon barrels , a mixer and some water, alcohol and dirt.
You have to wonder about all that stainless. Food prep.
Your presence on, and contributions to this site is all the thanks I need; I just try to soak in everthing you write. I feel like I get smarter every time you, @moronnabis, @anon64373531, @cyclopath, and many others post 
Its so nutritious!!
