Harmaline to THH reduction with zinc and vinegar works! (GC-MS results)

[Elrik]

...Does this mean using ammonia for freebasing solves the potential cadmium contamination issue, as long as enough ammonia is used?

When I was preppin' for a separation of a THH zinc carbonate mixture I did some on-the-fly solubility tests using zinc sulfate as my zinc source to see how to most reliably prevent zinc precipitation.
From memory, the more relevant results went like this:
Zinc sulfate solution slowly based with ammonia formed precipitate, which then dissolved with an obvious excess of ammonia.
Zinc sulfate solution containing 1% ammonium chloride behaved almost the same, but the precipitate redissolved a bit faster.
Zinc sulfate solution containing 5% ammonium chloride produced no precipitate on basing.
Ammonium sulfate was similarly effective at 5%

A fist full of ammonium salts should similarly prevent precipitation of cadmium.
A limitation is I did not do a test series using sodium carbonate as the basing agent, as it wasnt relevant to what I was doing at the time.

Ammonium chloride is cheap in feed stores, it prevents kidney stones in your pet goat.
Ammonium sulfate of very questionable purity is a common fertilizer chemical.

 

[Loveall]

Ammonium sulfate of very questionable purity is a common fertilizer chemical.

I think hese guys have a good spec when it comes to toxic metals in ammonium sulfate. I think they are the exception though.

 

[Jagube]

Ammonium sulfate of very questionable purity is a common fertilizer chemical.

I think hese guys have a good spec when it comes to toxic metals in ammonium sulfate. I think they are the exception though.

This one (for UK / Europe) looks good too? http://vi.vipr.ebaydesc.com/ws/eBay...descgauge=1&cspheader=1&oneClk=1&secureDesc=0

It says "Heavy metals (as Pb): <.0.001%" - does that mean just lead, or each individual heavy metal < 10ppm, or the total of all heavy metals < 10ppm?

Then considering the point of its use is to dissolve heavy metals, it probably doesn't matter so much.

 

[Loveall]

That's not bad either. The spec you posted has <100x times the amount of lead permissable in candy, since we are not planning on eating ammonium sulfate like candy (right?) I think it's fine. The other one has <10x the permissable amount.

 

[Jagube]

I've done my first reduction on what I believe was reasonably isolated harmaline.

The liquid in the reduction vessel lost its green color under UV, but didn't really turn blue. It didn't glow under UV at all (or maybe just not enough to notice much of a glow). Is this something to worry about?

I used a magnetic stirrer for the reduction and basification with ammonia. After the reduction and before basing I added ammonium chloride. The first clouding occurred around pH 6.0. I didn't take notes or add the ammonia slowly enough to notice the other cloudings or depression points. Now the alks need washing and drying and they'll be ready for a bioassay. I'll report back, hopefully in a few days.

Is there a consensus on the best form to store THH long-term? I remember reading it reverts back to harmaline fairly quickly, even in the fridge (or freezer?) and the HCl salt is not much better. Does the same happen in Ayahuasca brews?

 

[Jagube]

The reduction turned 1g of (presumably mostly) harmaline into 660mg of presumably THH.
Since THH has a slightly higher molecular weight (216 vs 214) than harmaline, this means roughly a 35% loss. I wonder what happened? The final pH after basing was around 11, so it shouldn't have been caused by too low a pH.

 

[Elrik]

That drop is about right for going from hydrochloride dihydrate to freebase, but I'll assume you started with freebase.
If you retained the based and filtered liquid you could use vinegar to adjust to pH <7 and do a mini-manske to get the rest out.
Another possibility at those gram weights is that quantity simply getting lost in the filter paper.
Alkaloids tend to be more stable as salts and crystals are easier to filter than fluff so I usually end up with hydrochlorides.

 

[Jagube]

Thanks Elrik. Yes, it was both freebase weights.

I didn't retain the based liquid, will try and remember to do that in the future. Any idea why THH would not precipitate at such a high pH, but precipitate in a subsequent Manske? This goes against my impression that Manske is less reliable than basing. In other threads I've seen suggestions to base the post-Manske supernatant to verify that the Manske was successful or precipitated one alkaloid and not another.

I don't think that much was lost to the filter as I only filtered it once - to remove the metallic zinc before basing. Come to think of it I should also have filtered the freebase instead of decanting, to minimize the amount of zinc and heavy metal compounds. Instead I just washed it with diluted ammonia 3 times. And this makes me wonder if the unwanted compounds might have precipitated during the washing stage and contaminated my product, as the pH of the diluted ammonia was lower (probably between 8-9) and I didn't put additional ammonium chloride in it.

Another explanation for the loss could be that the freebased THH may have dissolved in the washes.

 

[Brennendes Wasser]

Well I guess this is a noob question, but what is the reason to reduce the Harmalas?

I really dont know anything about THH, but what I read on Wikipedia is that is is not even active anymore as a MAOI. So why do you want ot obtain it?

 

[Jagube]

I did another DHH -> THH conversion, this time 7g.

The collected freebase weighed 5.4g, so a 23% loss. Better than the previous 35% loss, probably due to using a larger amount, resulting in relatively less lost to filtering, sticking to walls etc., but still not great. The final product looks cleaner though, so part of the loss may be impurities.

I tried manske-ing, but nothing crashed out. On heating the re-acidified soup for the Manske, it clouded with fluffy bits, presumably the zinc compounds. I added more vinegar to dissolve them, and it did dissolve them a little bit, but not much. However, adding NaCl made them disappear.
Now I have ~250ml of acidic liquid with 1.6g harmalas (mostly THH?) and 70g of NaCl sitting in the fridge, and nothing seems to be crashing out.

Perhaps I should have decanted and discarded the zinc compounds when they crashed out during the first post-reduction basing. They were so thick they stopped the magnetic stir bar spinning. Upon adding more ammonia, the precipitates dissolved and the bar started spinning again.

 

[blue.magic]

Well I guess this is a noob question, but what is the reason to reduce the Harmalas?

I really dont know anything about THH, but what I read on Wikipedia is that is is not even active anymore as a MAOI. So why do you want ot obtain it?

THH is present in caapi and Ayahuasca brews. It gives the brew its very specific persona.

THH works as MAOI in higher concentrations but it probably works as mood modulator and mild SSRI. Its pharmacology is not completely studied but boy I vaporized some THH freebase on a mushroom trip and yep - it is very well active

We did a group experiment with some people taking just harmine orally, then vaped DMT. Next session was harmine+THH orally, then vaped DMT. The second session took almost 3 hours (!) and people stayed in a deep meditative mood after that.

 

[grollum]

Reading through the whole thread still keeps me unsure about what the best final cleaning step for the THH might be to clean the THH from the unwanted zinc and maybe heavy metal impurities.

Can someone clear this up for me or point me to the regarding post?

 

[Jees]

Reading through the whole thread still keeps me unsure about what the best final cleaning step for the THH might be to clean the THH from the unwanted zinc and maybe heavy metal impurities.

Can someone clear this up for me or point me to the regarding post?

Removing excess zinc is strict mechanically filtering, the extreme fine powder might ask for some extra care, e.g. finer filter than usual. I think a cotton ball in a funnel neck works IIRC.

Removing of the zinc salts: if you make your final base with ammonia you're out of trouble as the zinc salts will re-dissolve just before the THH crashes out.

Heavy metals like they come in the zinc? Buy more pure zinc?

Cleaning the THH, for example: dissolve in vinegar and base with ammonia, filter. Wash a few times with a very light ammonia wash at 3%, filter and dry, traces of ammonia will vapor off.
Or use a sodium carbonate liquid (0.5%) to wash the THH with. These are the methods as presented by Van Der Sypt.

Hope this helps.

 

[grollum]

Removing excess zinc is strict mechanically filtering, the extreme fine powder might ask for some extra care, e.g. finer filter than usual. I think a cotton ball in a funnel neck works IIRC.

Removing of the zinc salts: if you make your final base with ammonia you're out of trouble as the zinc salts will re-dissolve just before the THH crashes out.

Heavy metals like they come in the zinc? Buy more pure zinc?

Cleaning the THH, for example: dissolve in vinegar and base with ammonia, filter. Wash a few times with a very light ammonia wash at 3%, filter and dry, traces of ammonia will vapor off.
Or use a sodium carbonate liquid (0.5%) to wash the THH with. These are the methods as presented by Van Der Sypt.

Hope this helps.

This helps a lot. Thanks! I have <40 μm zinc powder which is 99.995 % clean. I think that should be fine for manual filtering. Was not sure about the info in Van Der Sypt's document since the cleaning was more like a sidenote.

 

[blue.magic]

I filter the liquid through a bed of Celite (a food grade Diatomacous Earth - or DE - works excellent too).

You need a Buchner funnel with a vacuum flask and some vacuum pump (the hand type off ebay works well), then you place a filter in, wet it with water, pump a few times to make the filter stick to the funnel, then mix some DE with water and pour it in, pull some vacuum and the DE will create a cake - a thin cake suffices; then you wash the cake with fresh water, release vacuum, remove the funnel and clean the flask; reattach the funnel, pull vacuum and now pour in the solution; you will get crystal clear filtrate.

You can optionally place second filter on top of the cake to avoid disturbing it when pouring your solution.

Then I crash THH freebase using a strong base, filter out the FB, wash it few times to remove base, cover the FB with small amount of water and finally add concentrated HCl until all the THH dissolves as THH.HCl. This is then dried to yield quite pure tetrahydroharmine hydrochloride.

Of course, you can filter the THH.HCl solution again to get extra purity

 

[Jagube]

Thanks grollum, your post prompted me to order mesh-rated zinc. I think the zinc I've used so far is too coarse and that's why it hasn't worked so well.

The new zinc I ordered is mesh 350+, which I reckon is about 40 microns, so I should still be able to use coffee filters (20 microns).

However, I have a Buchner funnel with a flask, the only gear missing for vacuum filtration is a vacuum pump and DE, so I may go the extra mile and get around to obtaining those and setting it up. Thanks blue.magic. When you say you put a filter in the funnel, is it a special one? Or do you cut out circles from standard coffee filters?

 

[Jagube]

I did a reduction with zinc and vinegar, but also added HCl to bring the pH down as adding more vinegar couldn't bring it down enough without diluting it too much.

Now the zinc has disappeared. If I understand correctly, it has converted to zinc chloride (Zn + HCl -> H2 + ZnCl2), which is highly soluble in water.

Does anyone know if adding ammonia to precipitate the presumed THH will keep the ZnCl2 dissolved? I've read somewhere that ZnCl2 is not soluble in aqueous ammonia.

If zinc chloride precipitates when ammonia is added, how do I safely recover my THH?

 

[Auxin]

Zinc compounds are soluble in excess ammonia, THH is not.
Zinc compounds are also soluble in ammonium chloride and ammonium sulfate, those have been used experimentally to further prevent zinc precipitation when basing with ammonia, but just using excess ammonia is reportedly sufficient.

 

[nan0tEch]

Well I guess this is a noob question, but what is the reason to reduce the Harmalas?

I really dont know anything about THH, but what I read on Wikipedia is that is is not even active anymore as a MAOI. So why do you want ot obtain it?

THH is present in caapi and Ayahuasca brews. It gives the brew its very specific persona.

THH works as MAOI in higher concentrations but it probably works as mood modulator and mild SSRI. Its pharmacology is not completely studied but boy I vaporized some THH freebase on a mushroom trip and yep - it is very well active

We did a group experiment with some people taking just harmine orally, then vaped DMT. Next session was harmine+THH orally, then vaped DMT. The second session took almost 3 hours (!) and people stayed in a deep meditative mood after that.

As blue.magic sees it give you some happy mood change. 25mg of this pure product will uplift your mood to a positive vibe. As i found out. Via dr. google it works on your gaba receptors. With this information i went to my pharmacologist and ask here about the working of this product. She did contacted a neurologist and asked about it he even confirmed my thoughts that it will help uplift your mood and could help with depression. This is my search to help out my wife for here mild depression. So i bought a banisteriopsis caapi 30:1 resin. She says it helps a bit, but my guess is that the harmala and harmaline is overpowering the THH witch is found in the resin to.

 

[nan0tEch]

Is there a written tek to isolate THH. Cause here is given a solution and to different obstacles. I'm really interested in a straight forward solution from seeds to finished product. Maybe a tek to get 0.5g -1g THH or is this to large for a home build amateur lab