Now made a new *Tracking [...] with NMR*. As that whole Harmalas were just for the sake of making THH again, I tried to get towards completely white THH and checked the purity of the respective sample after each step.
Nothing great to show, more just to share data which I have now anyways. Those numbers give the order of processing from what I was left in the first post to some white THH.
1.)
Used sample from batch #4 from first post, which contained 16:100 Harmin:Harmalin - picture.
purity ~ 86 % Harmalin
--> Super annoying that I first thought Harmalin would be the first batch, now that other REAL Harmalin contained a little more of the unwanted Harmala Alkaloid. But well 16 to 100 is still not much.
2.)
Made THH conversion, 3 h of stirring at RT in Zink + Acetic Acid. Crude Product contained 16:100 Harmin:THH - picture.
purity ~ 86 % THH
--> It would be possible to quantify the ratio also with the same signal like first post (#14 at 3,8 ppm), but with THH there is a new signal at 4,0 ppm at that makes stuff less reliable here. Instead the Ratio of aromatic signals was used.
--> Interestingly the Ratio of Harmin : X did not change. As yield is mostly 70 % and 30 % of Alkaloids are always lost, I would have guessed maybe the ratio would have changed as probably 1 alkaloid would undergo stronger whatever process makes it disappear. Instead the same amount Harmin/THH "gets lost" when performing that reduction. Note that sadly it's hard to determine if any Harmin "is hiding" below the THH. As they share mostly the same signals. But combined signals (6,60 ppm / 6,81 ppm / 7,2 ppm) vs. THH-only signals (4,0 ppm) are quite 1:1 so probably only traces of Harmin present, if at all.
3.)
First re-x in boiling Ethanol. Solubility data is now added here. First checked only the composition of the remaining liquid, which should be enriched with Harmin now. So this is what you would THROW AWAY as the liquid decanted from the freezer crystals. Mixture contained 34:100 Harmin:THH - picture.
purity ~ 75 % THH
--> I was hoping for a much more enriched Harmin mix. But sadly solubility of THH at -20 °C Ethanol is still quite high. So while you may purify your precipitates, you will still loose quite a lot of THH within the remaining EtOH at -20 °C.
4.)
Second re-x in boiling Ethanol. Again checked the composition of the remaining liquid. Mixture contained again 16:100 Harmin:THH. So this is what you would THROW AWAY as the liquid decanted from the freezer crystals. Already less staying behind in Ethanol, due to losing most in the first step, but still a lot of THH that would go down the drain when not recovering - picture.
purity ~ 86 % THH
5.)
Second re-x in boiling Ethanol. This time also directly checked the purity of the precipitate. Precipitate was clear white crystals, which contained ~ 2:100 Harmin:THH - now shown directly here:
purity ~ 98 % THH:
--> seems like 2x re-x must be done to get rid of all the Harmin, when starting with 10+ % Harmin like in my case. Probably needed as solubility of both are not too different. Now that stuff is really white, but if you dont salvage the remaining stuff from the Ethanol, seems like not worth the whole process like in my case to just remove *16 Harmin out of 100 THH*. Moreover, THH would be broken up by MAO-A/B anyways? So it would even give a potency/duration boost, if making any interaction at all. So unless you want really white THH I guess there is no real reason to loose that much THH for nothing. Also as I wrote above that Harmala-Separation was quite freestyle and ineffective, so people might end up with only 5:100 Harmin:Harmalin for step 1.) and then final product might be already just yellow-white.
Made this THH again to just eat some more of those ... I made already some trials years ago, but just picked up some interest again. Will report soon.
Pictures attached are some microscope images of that last sample. As usual always 2x pictures per 1x crystal because of both illumination modes.
