Harmine, harmaline and THH from Syrian Rue. Verification and finetuning of the VDS-protocols

[Global_Roaming]

It's been several years since I did a VDS protocol separation, but was it ever established that a zinc reduction of mixed harmalas (from rue) would only convert the harmaline to THH and leave the harmine intact?

If true, I suspect this would be a popular path for most people doing rue extractions.

 

[q21q21]

Ugh, what is this stuff?


I reacted 1g of presumable quite pure harmaline with 355mg magnesium and 56ml vinegar (5%) until all the magnesium was consumed. I started with too little vinegar and used Magnesium granules so it took over 8 hours.

I filtered the liquid through a coffee filter and then added ammonium until the pH was 9.5.

A brown gooey mass formed at the bottom but filtering the liquid resulted in something that looks like harmalas.



I tested the UV color by taking a bit of the tan precipitate and dissolving it in vinegar and it is still VERY GREEN


I'm quite confused with both the brown goo and the lack of blue UV... anyone have any ideas?

 

[q21q21]

Well it seems like the authors of this older thread may not visit the nexus much anymore.

Thankfully I seem to have had some success on my own.



I have no idea the chemistry behind it, it seems that for some reason the magnesium granules taking 8+ hours to react with the vinegar caused some sort of reaction that made ammonia basing precipitate a dark brown goo.

I had the idea to flatten the granules and increase their surface area significantly, making the reaction similar to the magnesium ribbon one that many have done successfully.

I did a dual test on both flattened granules and no harmaline (just vinegar). After a little over 1 hour, the little magnesium flattened disks dissapeared and basing with ammonia caused no precipitation.

I then did a 200mg harmaline test run and after 1.5 hours I got a very similar precipitate as was floating above the brown gunk from my last post, but NO BROWN GUNK! When I tested the UV, it seemed very green.... THEN I RINSED IT, and it was a faint purplish blue!

I tested it sublingually, somewhere around 12-20mg and the effects are very significant. I sometimes have placebo headspace changes for up to 30-40 minutes with inactive things, so I was very careful to be critical if that was happening, but it's been 3 hours and the effects are surely way beyond placebo. I didn't actually try harmaline sublingually before to compare, but precipitating it looks nothing like the sparkly glitter harmaline, it is all fluffy and globby. The effects are quite energizing and while I don't ever get "euphoria" from psychedelics, I do feel a typical serotonin abundance feeling. I hope that it is not just conformation bias, but continues with further tests.

The above picture is from a 1.27g test I did, replicating the apearent success of the 200mg one. I've read with zinc it is typically 75% yield, I got 61% which is okay given the coffee filters likely absorbed a not unsignificant portion of liquid and trap the fine powder within the fibers.

I am very nervous to manske this precious THH, but appearently the freebase is somewhat unstable compared to the THH HCl. So I have the convesion of the other 7ish grams of harmaline and the manske to work on in the near future.

 

[doubledog]

the coffee filters likely absorbed a not unsignificant portion of liquid and trap the fine powder within the fibers.

You can keep all paper filters from your extractions/filtrations and extract harmalas from them later. Last time I've extracted from maybe 10 leftover paper filters and yield was pretty good.

 

[The Sofa Traveler]

You can keep all paper filters from your extractions/filtrations and extract harmalas from them later. Last time I've extracted from maybe 10 leftover paper filters and yield was pretty good.

Oh nice idea, never thought about it. I'm gonna start a harmalas extraction paper filters collection

 

[doubledog]

I was surprised how much harmalas are trapped in my paper filters (I am using quite thick ones).

Extraction is very simple: just wash the filters in acidic water and precipitate harmalas with any base.

Edit: I am using paper filters only for washing alkaloids from alkaline water and drying them directly in it. There is always some harmalas stuck to it.

 

[Transform]

Oh nice idea, never thought about it. I'm gonna start a harmalas extraction paper filters collection

I've got stacks of the things, along with multiple paper towels from mopping up spillages, so some kindof re-extraction is definitely on the cards here too

 

[Transform]

Ugh, what is this stuff?

Maybe the slowness of the reaction led to some polymer formation? Just a guess.

 

[q21q21]

I finally converted the rest of my stock of harmaline (8.16g) to THH and it yielded 6.57g

This is an 80% yield, with transfer losses it seems a tad high and might have a bit of magnesium salt contamination. If oral tests result in nausea or other symptoms then I'll try out a Manske on it.


While I thought of writing up what I did, I just followed this video 90% and the visual nature of it really helped me.

The only thing is that I believe he used 7% vinegar, so it is 340mg magnesium 56ml vinegar for 1g harmaline for my 5% vinegar (rather than 40ml vinegar for 7%)

I'm glad to be done my harmala extraction possibly for a lifetime. It was interesting but challenging. My wife did NOT like the smell of ammonia and vinegar and the mess I left in our garden area for weeks though.

 

[Orion]

Nice one q21q21. I was planning on doing this exact same thing so I'm glad to see a trusted Nexian having good results.

You say it's enough for a lifetime, but I hear THH will eventually turn back into harmaline, and the best you can do is slow down the process. I thought converting to HCL might solve it but the bonding site is in the wrong place IIRC.

 

[modern]

You can do Manske to precipitate THH from my attempt it worked

 

[Transform]

attempt

Have you described this in any detail anywhere?

 

[q21q21]

Nice one q21q21. I was planning on doing this exact same thing so I'm glad to see a trusted Nexian having good results.

You say it's enough for a lifetime, but I hear THH will eventually turn back into harmaline, and the best you can do is slow down the process. I thought converting to HCL might solve it but the bonding site is in the wrong place IIRC.

That;s what I thought too, but it turns out to be a random issue An1cca's experiment.
In the thread "THH > DHH... does it convert back?" Jees has 2 years old freebase THH verified to be still THH by microscopy and taste

Also, in post 441 of this thread An1cca confirms the validity of Jees' experiment

"OK, padawan, it's a good thing I was wrong there . Jees' experiment convincingly showed the THH to be stable."


Maybe I'm trusting these posts too much, if anyone has some insights into the stability of THH I'm not aware of, let me know!

 

[modern]

Have you described this in any detail anywhere?

I checked and didn't post here but I shared it on FB during my experiments and attempt at converting using magnesium strips. I didn't have ammonia so attempted mansake... MAYBE incorrect since it was earlier in my experiments but easy to test. I don't have any harmalas at the moment though.

 

[Orion]

Here's my recent test. It may have yielded THH, it might not have. Some signs say it's THH, others not.

So... 2g of harmaline was dissolved into 80ml of 5% dist. vinegar with 680mg of chopped magnesium ribbon. This took about half an hour or so to dissolve with stirring. Raised the pH to 9.5 with ammonia and filtered off what should be THH. Globs of something, possibly a magnesium product, appeared and remained when adding each drop.

Raised the pH of the filtered solution to 10 and nothing more settled out.

The product once dried had an appearance like pale cracked earth and lacked the sparkle of harmaline.

The dried product was dissolved in a minimum of vinegar, topped up to a total of 150ml with distilled water and heated in a pan to dissolve sediment. A small portion did not dissolve. It looked like small pale flakes of material, perhaps less than 5% of the total product. This was filtered out.

A manske was performed by saturating the heated solution with salt and pouring into a jar when a slight temperature drop caused clouding. The clouding appeared like DMT precipitating from saturated naphtha. Perhaps I've never done a manske this clean before and this is why? Or it's a THH thing?

The jar was heated in a double boiler until the solution cleared, was covered with foil and left to sit in the pan of hot water overnight to slowly cool.
In the morning there wasn't much precipitate, just a dark residue. Added more salt and microwaved until dissolved and left to slowly cool in a pan of hot water.
Along with brown blobs and crud at the bottom there was a layer of colorless white needle-like crystals. I poured away the solution through a filter and dissolved all of the solids in 150ml of heated distilled water.

The solution was based with ammonia and precipitation began already at pH 7. It did not stop clouding with each drop until 9.5. <Remember this part.

Collected precipitate in filter and dried. Dissolved it some in vinegar and distilled water and it fluoresces under UV the same color as the other harmalas I have. Dissolved it all and based it out again but collected everything that crashed out below pH 8.7 separately.

There was no precipitation between pH 8.7 to 9.5 when the solution became hazy, then gradually precipitate as it increased up to 9.8 when no more clouding from each drop of ammonia occurred. < Isn't that weird? Now it crashed out above 9.5

Poured off the solution through a filter leaving the product in the jar and added 300ml of distilled water and some ammonia to keep the pH above 10. Did this twice to wash away any colored solution which may contain non-THH harmalas.

Collected and dried precipitate. Dissolved a small amount and it and checked with UV. Same colour as other harmalas.. Non-THH? Contaminants which crashed out even at pH levels this high? Seems like that shouldn't be the case.

Dissolved it all in 80ml of vinegar with 680mg of magnesium ribbon. This time I will leave it overnight to reduce instead of basing as soon as the magnesium had dissolved. There should be far less of this product, probably barely a sample at this point, but the purity should be higher.

 

[Transform]

Here's my recent test. It may have yielded THH, it might not have. Some signs say it's THH, others not.

So... 2g of harmaline was dissolved into 80ml of 5% dist. vinegar with 680mg of chopped magnesium ribbon. This took about half an hour or so to dissolve with stirring. Raised the pH to 9.5 with ammonia and filtered off what should be THH. Globs of something, possibly a magnesium product, appeared and remained when adding each drop.

Raised the pH of the filtered solution to 10 and nothing more settled out.

The product once dried had an appearance like pale cracked earth and lacked the sparkle of harmaline.

The dried product was dissolved in a minimum of vinegar, topped up to a total of 150ml with distilled water and heated in a pan to dissolve sediment. A small portion did not dissolve. It looked like small pale flakes of material, perhaps less than 5% of the total product. This was filtered out.

A manske was performed by saturating the heated solution with salt and pouring into a jar when a slight temperature drop caused clouding. The clouding appeared like DMT precipitating from saturated naphtha. Perhaps I've never done a manske this clean before and this is why? Or it's a THH thing?

The jar was heated in a double boiler until the solution cleared, was covered with foil and left to sit in the pan of hot water overnight to slowly cool.
In the morning there wasn't much precipitate, just a dark residue. Added more salt and microwaved until dissolved and left to slowly cool in a pan of hot water.
Along with brown blobs and crud at the bottom there was a layer of colorless white needle-like crystals. I poured away the solution through a filter and dissolved all of the solids in 150ml of heated distilled water.

The solution was based with ammonia and precipitation began already at pH 7. It did not stop clouding with each drop until 9.5. <Remember this part.

Collected precipitate in filter and dried. Dissolved it some in vinegar and distilled water and it fluoresces under UV the same color as the other harmalas I have. Dissolved it all and based it out again but collected everything that crashed out below pH 8.7 separately.

There was no precipitation between pH 8.7 to 9.5 when the solution became hazy, then gradually precipitate as it increased up to 9.8 when no more clouding from each drop of ammonia occurred. < Isn't that weird? Now it crashed out above 9.5

Poured off the solution through a filter leaving the product in the jar and added 300ml of distilled water and some ammonia to keep the pH above 10. Did this twice to wash away any colored solution which may contain non-THH harmalas.

Collected and dried precipitate. Dissolved a small amount and it and checked with UV. Same colour as other harmalas.. Non-THH? Contaminants which crashed out even at pH levels this high? Seems like that shouldn't be the case.

Dissolved it all in 80ml of vinegar with 680mg of magnesium ribbon. This time I will leave it overnight to reduce instead of basing as soon as the magnesium had dissolved. There should be far less of this product, probably barely a sample at this point, but the purity should be higher.

The trouble here is that magnesium hydroxide or its carbonate will be as insoluble as freebase harmalas, and will also dissolve in the same acids as harmalas. I'm not sure what other folks did when using magnesium ribbon, but I took advantage of the fact that magnesium ammonium phosphate (MAP) is highly insoluble. By using phosphoric acid along with the magnesium ribbon, it was then possible to precipitate the MAP by careful addition of ammonia. The MAP crashes out as a dense, pure white powder at a pH sufficiently distinct from either harmine or harmaline that these compounds are very easy to tell apart from the MAP. I (or maybe @downwardsfromzero) documented the pH measurements somewhere around here a couple of years or so ago.

In your case, another Manske should clear up the magnesium [salt] contamination, as would picking up the harmalas with something like EA or butyl acetate. [I'd need to look up the solubility of magnesium hydroxide in things like methanol or other alcohols, although I can't imagine it would be particularly high - then again, neither is it for harmalas. Just considering other solvent options here, aka thinking aloud ]

Whichever way you choose, it will have to exploit some kind of solubility difference in order to clear up the residual magnesium.

 

[doubledog]

It's also my experience that conversion with magnesium ribbon produces some weird behaviour during precipitation.

 

[Transform]

It's also my experience that conversion with magnesium ribbon produces some weird behaviour during precipitation.

Like I've said, the MAP approach takes care of that, if you can get hold of phosphoric acid and ammonia.

 

[doubledog]

Yes, I remember that you described the procedure (and also have both ingredients), so would probably try it next time.

 

[Transform]

[I'd need to look up the solubility of magnesium hydroxide in things like methanol or other alcohols, although I can't imagine it would be particularly high - then again, neither is it for harmalas. Just considering other solvent options here, aka thinking aloud ]

check this thread with very impressive harmala crystals.
not sure about the solubility of freebase harmalas in ethanol but it's not terribly high from my experience. here's a thread with crystallization from ethanol.

some useful discussion to be found from following those links